CN101462887B - Dry type magnesium-calcium gravity flow fire-resistant material and preparation thereof - Google Patents
Dry type magnesium-calcium gravity flow fire-resistant material and preparation thereof Download PDFInfo
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- CN101462887B CN101462887B CN2009100604585A CN200910060458A CN101462887B CN 101462887 B CN101462887 B CN 101462887B CN 2009100604585 A CN2009100604585 A CN 2009100604585A CN 200910060458 A CN200910060458 A CN 200910060458A CN 101462887 B CN101462887 B CN 101462887B
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Abstract
The invention relates to a dry magnesia-calcia free-flowing refractory material and a preparation method thereof. The adopted technical proposal is as follows: the refractory material is prepared by stirring and mixing 20-50wt% of electrocast magnesia-calcia clinker or sintered magnesia-calcia clinker, 10-40wt% of electrocast magnesia or sintered magnesia, 0.5-20wt% of forsterite, 10-30wt% of sodium silicate hydrate particles, 1-8wt% of fine silicon dioxide powder, 0.5-5% of fine limestone powder and 1-5% of polyphosphate sodium particles. The dry magnesia-calcia free-flowing refractory material prepared by the method has good fluidity and fire resistance, convenient site operation and use and no environmental pollution and can be used for quickly patching a liner material of a smelting furnace.
Description
Technical field
The invention belongs to technical field of refractory materials.Relate in particular to a kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof.
Background technology
Environment protection is the key subjects that present refractory materials production and application face, and the repair material of metallurgical furnace liner is used organic bond more at present, is prone to generate harmful flue dust during sintering; Cause atmospheric severe contamination; The harm workmen's is healthy, and on the other hand, the on-the-spot repair maintenance that uses will add entry or other liquid wedding agent usually with refractory materials; Construction link is comparatively complicated, and labor strength is big.Our the present research work of doing is through improving wedding agent, adding suitable admixture and solve this realistic problem.The material of being developed is the dry type refractory materials, need not to add entry or other liquid wedding agent during use.
At present, the quickening of converter smelting rhythm makes the long shortcoming of traditional carbon containing mending material sintering time fully come out, some the time this shortcoming become the restricted link of converter high yield.The most of steel mills of China still adopt relatively backward method and raw material to repair boiler face and furnace lining, and the filling time is long, and effect is not good enough.Minority steel mill is also arranged, adopt useless brick to subsidize, and spread and expect in vain that with Jiao it is big to repair consumption like this, the repairing time is also long.In order to satisfy the needs of the high rhythm of converter smelting, urgently to carry out the research and development of hot quick mending material.On the other hand, be the External refining vessel of core with the steel teeming ladle, its molten steel impact zone needs on-line maintenance to prolong the work-ing life of steel teeming ladle often; Moreover, thereby the mouth of a river wherein often exists big slit need stop the turnover rhythm that jar repairing has influenced steel teeming ladle with steel teeming ladle bottom refractory materials after replacing.
Summary of the invention
The present invention is intended to overcome above-mentioned technological deficiency, and purpose provides a kind of have good flowing property, fire performance and sintering character, easy-to-use and dry type magnesium-calcium gravity flow fire-resistant material that can not pollute environment and preparation method thereof.
Be to realize above-mentioned purpose, the technical scheme that the present invention adopted is: the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 20～50wt% or sintering calcium magnesia sand, 10～40wt% or magnesite clinker, the forsterite of 0.5～20wt%, fine silica 10～30wt%, 1～8wt%, 0.5～5% limestone fines and 1～5% sodium polyphosphate particle are made after mixing.Wherein:
Electric smelting calcium magnesia sand or sintering calcium magnesia sand are the mixture of its particle and fine powder, and the grain composition of electric smelting calcium magnesia sand or sintering calcium magnesia sand is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
Electrosmelted magnesite clinker or magnesite clinker are the mixture of its particle and fine powder, and the grain composition of electrosmelted magnesite clinker or magnesite clinker is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
The hydrated sodium silicate particle is more than one particulate mixtures in a hydrated sodium silicate, two hydrated sodium silicates, three hydrated sodium silicates, four hydrated sodium silicates, five hydrated sodium silicates, six hydrated sodium silicates, seven hydrated sodium silicates, eight hydrated sodium silicates, nine hydrated sodium silicates, and the hydrated sodium silicate grain diameter is 0.5～6mm.
Forsterite is the mixture of its particle and fine powder, particle and fine powder grain composition be: 10～60wt% is that particle diameter is that particle, the 40～90wt% of 1～5mm is that particle diameter is the fine powder of 2～100um.
The particle diameter of fine silica is 0.001～100um; The particle diameter of limestone fines is 2～100um.
The sodium polyphosphate particle is that biphosphate is received, phosphoric acid one hydrogen is received, more than one particulate mixtures of sodium phosphate, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, and the sodium polyphosphate particle grain size is for being 0.1～1mm.
Owing to adopt technique scheme; The present invention introduces hydrated sodium silicate as staple; Wherein the introducing amount of hydrated sodium silicate is more than 10%, and at high temperature hydrated sodium silicate discharges combination water wherein, has improved the flowing property of material greatly and has sprawled effect; Repair efficiency to the metallurgical furnace liner is better, therefore has good flowing property, fire performance and sintering character.Simultaneously, sintering time required for the present invention is very short, under normal circumstances only needs 10～15 minutes, is significantly less than 30～60 minutes of the conventional repair material, thereby has characteristics easy to use.
Because hydrated sodium silicate is solid at normal temperature, thereby prepared material be the dry type state at normal temperatures, is convenient to transportation and use.And in traditional refractory materials; Often water glass is regarded as reducing the material of refractory materials fire performance and lacks usefulness as far as possible; The present invention is then through choosing other suitable raw material, at high temperature form high-temperature flame-proof with the introducing that reduces hydrated sodium silicate to the material at high temperature Effect on Performance.This is that the exploration of having a mind to has been made in the use of giving full play to hydrated sodium silicate.
The prepared product of the present invention can be used as the material of quick repairing metallurgical furnace and container inside lining; On the one hand environment is not polluted because material in the sintering process of being heated, discharge have only water vapor (hydrated sodium silicate decompose due to), can satisfy environmental protection requirement; And often having added organism, traditional patching material makees wedding agent; Like pitch, resin etc., they can discharge toxic gas in receiving thermal process, human and environment is worked the mischief; On the other hand, need not to add water or other liquid wedding agent during use, greatly reduce working strength of workers.This material can also be as the fast repairing material of other metal melt smelting furnace.
Embodiment
Below in conjunction with embodiment the present invention being done further description, is not the restriction to protection domain of the present invention:
This embodiment is electric smelting calcium magnesia sand or sintering calcium magnesia sand, electrosmelted magnesite clinker or magnesite clinker, forsterite, hydrated sodium silicate particle, fine silica, limestone fines and sodium polyphosphate particle to be made after mixing in each embodiment through different quality percentage compositions.Above-mentioned compound will relate in following examples, no longer be repeated in this description for making each embodiment, and the physical index unification of above-mentioned compound is described below:
Electric smelting calcium magnesia sand or sintering calcium magnesia sand are the mixture of its particle and fine powder, and the grain composition of electric smelting calcium magnesia sand or sintering calcium magnesia sand is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
Electrosmelted magnesite clinker or magnesite clinker are the mixture of its particle and fine powder, and the grain composition of electrosmelted magnesite clinker or magnesite clinker is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
The hydrated sodium silicate particle is more than one particulate mixtures in a hydrated sodium silicate, two hydrated sodium silicates, three hydrated sodium silicates, four hydrated sodium silicates, five hydrated sodium silicates, six hydrated sodium silicates, seven hydrated sodium silicates, eight hydrated sodium silicates, nine hydrated sodium silicates, and the hydrated sodium silicate grain diameter is 0.5～6mm.
Forsterite is the mixture of its particle and fine powder, particle and fine powder grain composition be: 10～60wt% is that particle diameter is that particle, the 40～90wt% of 1～5mm is that particle diameter is the fine powder of 2～100um.
The particle diameter of fine silica is 0.001～100um; The particle diameter of limestone fines is 2～100um.
The sodium polyphosphate particle is that biphosphate is received, phosphoric acid one hydrogen is received, more than one particulate mixtures of sodium phosphate, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, and the sodium polyphosphate particle grain size is for being 0.1～1mm.
Embodiment 1
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the hydrated sodium silicate particle of the forsterite of the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 20～30wt%, 30～40wt%, 15～20wt%, 10～15wt%, 1～2wt%, 4～5% limestone fines, 1～2% biphosphate are received particle after mixing, make.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 33.4% 1300 ℃ of processing, and volume density is 2.01g/cm
3
Embodiment 2
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the two hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 30～35wt%, 20～30wt%, 10～15wt%, 15～20wt%, 2～4wt%, 3～4% limestone fines and 2～3% tripoly phosphate sodium STPP particle are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 29.4% 1300 ℃ of processing, and volume density is 2.22g/cm
3
Embodiment 3
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the three hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 35～40wt%, 15～20wt%, 5～10wt%, 20～25wt%, 4～6wt%, 2～3% limestone fines and 3～4% Sodium hexametaphosphate 99 particle are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 28.4% 1300 ℃ of processing, and volume density is 2.28g/cm
3
Embodiment 4
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: phosphoric acid one hydrogen of the fine silica of the four hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 40～50wt%, 10～15wt%, 0.5～5wt%, 25～30wt%, 6～8wt%, 0.5～2% limestone fines and 4～5% is received particle after mixing, make.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 36.5% 1300 ℃ of processing, and volume density is 2.04g/cm
3
Embodiment 5
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the phosphoric acid of the fine silica of the five hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the sintering calcium magnesia sand of 20～30wt%, 30～40wt%, 15～20wt%, 10～15wt%, 1～2wt%, 4～5% limestone fines and 1～2% is received particle after mixing, make.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 32.4% 1300 ℃ of processing, and volume density is 2.12g/cm
3
Embodiment 6
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the six hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the sintering calcium magnesia sand of 30～35wt%, 20～30wt%, 10～15wt%, 15～20wt%, 2～4wt%, 3～4% limestone fines and 2～3% sodium phosphate and Sodium hexametaphosphate 99 particulate mixture are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 30.4% 1300 ℃ of processing, and volume density is 2.18g/cm
3
Embodiment 7
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the seven hydrated sodium silicate particles of the forsterite of the electrosmelted magnesite clinker of the sintering calcium magnesia sand of 35～40wt%, 15～20wt%, 5～10wt%, 20～25wt%, 4～6wt%, 2～3% limestone fines and 3～4% sodium phosphate and tripoly phosphate sodium STPP particulate mixture are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 31.4% 1300 ℃ of processing, and volume density is 2.11g/cm
3
Embodiment 8
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the hydrated sodium silicate particle of the forsterite of the electrosmelted magnesite clinker of the sintering calcium magnesia sand of 40～50wt%, 10～15wt%, 0.5～5wt%, 25～30wt%, 6～8wt%, 0.5～2% limestone fines and 4～5% tripoly phosphate sodium STPP particle are made after mixing.
Hydrated sodium silicate particle in the present embodiment is the particulate mixture of eight hydrated sodium silicates, six hydrated sodium silicates, five hydrated sodium silicates, two hydrated sodium silicates and three hydrated sodium silicates.Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 34.4% 1300 ℃ of processing, and volume density is 2.07g/cm
3
Embodiment 9
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the nine hydrated sodium silicate particles of the forsterite of the magnesite clinker of the electric smelting calcium magnesia sand of 20～30wt%, 30～40wt%, 15～20wt%, 10～15wt%, 1～2wt%, 4～5% limestone fines and 1～2% Sodium hexametaphosphate 99 particle are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 45.4% 1300 ℃ of processing, and volume density is 1.81g/cm
3
Embodiment 10
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the particulate mixture that the Sodium hexametaphosphate 99 and the biphosphate of the fine silica of the composite grain of five hydrated sodium silicates of the forsterite of the magnesite clinker of the electric smelting calcium magnesia sand of 30～35wt%, 20～30wt%, 10～15wt%, 15～20wt% and six hydrated sodium silicates, 2～4wt%, 3～4% limestone fines and 2～3% are received makes after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 44.8% 1300 ℃ of processing, and volume density is 1.97g/cm
3
Embodiment 11
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the biphosphate of the fine silica of the particulate mixture of six hydrated sodium silicates of the forsterite of the magnesite clinker of the electric smelting calcium magnesia sand of 35～40wt%, 15～20wt%, 5～10wt%, 20～25wt% and nine hydrated sodium silicates, 4～6wt%, 2～3% limestone fines and 3～4% is received and phosphoric acid one hydrogen is received particulate mixture and after mixing, made.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 38.4% 1300 ℃ of processing, and volume density is 1.99g/cm
3
Embodiment 12
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the hydrated sodium silicate particle of the forsterite of the magnesite clinker of the electric smelting calcium magnesia sand of 40～50wt%, 10～15wt%, 0.5～5wt%, 25～30wt%, 6～8wt%, 0.5～2% limestone fines and 4～5% tripoly phosphate sodium STPP particle are made after mixing.
Hydrated sodium silicate particle in the present embodiment is the particulate mixture of three hydrated sodium silicates, seven hydrated sodium silicates, five hydrated sodium silicates and nine hydrated sodium silicates.Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 36.4% 1300 ℃ of processing, and volume density is 2.11g/cm
3
Embodiment 13
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the tripoly phosphate sodium STPP of the fine silica of the particulate mixture of two hydrated sodium silicates of the forsterite of the magnesite clinker of the sintering calcium magnesia sand of 20～30wt%, 30～40wt%, 15～20wt%, 10～15wt% and four hydrated sodium silicates, 1～2wt%, 4～5% limestone fines and 1～2% and phosphoric acid are received particulate mixture after mixing, make.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 48.4% 1300 ℃ of processing, and volume density is 1.75g/cm
3
Embodiment 14
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: phosphoric acid one hydrogen of the fine silica of the particulate mixture of the hydrated sodium silicate of the forsterite of the magnesite clinker of the sintering calcium magnesia sand of 30～35wt%, 20～30wt%, 10～15wt%, 15～20wt% and seven hydrated sodium silicates, 2～4wt%, 3～4% limestone fines and 2～3% is received and the particulate mixture of sodium phosphate makes after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 46.7% 1300 ℃ of processing, and volume density is 1.81g/cm
3
Embodiment 15
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the tripoly phosphate sodium STPP of the fine silica of the particulate mixture of three hydrated sodium silicates of the forsterite of the magnesite clinker of the sintering calcium magnesia sand of 35～40wt%, 15～20wt%, 5～10wt%, 20～25wt% and eight hydrated sodium silicates, 4～6wt%, 2～3% limestone fines and 3～4% and the particulate mixture of Sodium hexametaphosphate 99 are made after mixing.
Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 47.9% 1300 ℃ of processing, and volume density is 1.82g/cm
3
Embodiment 16
A kind of dry type magnesium-calcium gravity flow fire-resistant material and preparation method thereof, its technical scheme is: the fine silica of the hydrated sodium silicate particle of the forsterite of the magnesite clinker of the sintering calcium magnesia sand of 40～50wt%, 10～15wt%, 0.5～5wt%, 25～30wt%, 6～8wt%, 0.5～2% limestone fines and 4～5% Sodium hexametaphosphate 99 particle are made after mixing.
The hydrated sodium silicate particle is a hydrated sodium silicate, six hydrated sodium silicates, nine hydrated sodium silicates and four hydrated sodium silicate particulate mixtures.Material is without moulding, and after 10 minutes, the void content of the material that obtains behind the naturally cooling is 45.8% 1300 ℃ of processing, and volume density is 1.88g/cm
3
Present embodiment 1～16 at high temperature hydrated sodium silicate discharges combination water wherein, has improved the flowing property of material and has sprawled effect, so have good flowing property, fire performance and sintering character.Sintering time of the present invention is short, under normal circumstances only needs 10～15 minutes, is significantly less than 30～60 minutes of the conventional repair material, thereby has characteristics easy to use.Prepared product discharges in the sintering process of being heated has only water vapor, satisfies environmental requirement, need not to add water or other liquid wedding agent during use, greatly reduces working strength of workers.This material is the dry type state at normal temperatures, is convenient to transportation and use, can be used as the material of quick repairing metallurgical furnace and container inside lining, can also be as the fast repairing material of other metal melt smelting furnace.
Claims (8)
1. the preparation method of a dry type magnesium-calcium gravity flow fire-resistant material is characterized in that the fine silica of the hydrated sodium silicate particle of the forsterite of the electrosmelted magnesite clinker of the electric smelting calcium magnesia sand of 20～50wt% or sintering calcium magnesia sand, 10～40wt% or magnesite clinker, 0.5～20wt%, 10～30wt%, 1～8wt%, 0.5～5% limestone fines and 1～5% sodium polyphosphate particle are made after mixing;
Described sodium polyphosphate particle is more than one particulate mixtures of SODIUM PHOSPHATE, MONOBASIC, disodium-hydrogen, sodium phosphate, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, and the sodium polyphosphate particle grain size is for being 0.1～1mm.
2. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1; Its characteristic is the mixture of its particle and fine powder at described electric smelting calcium magnesia sand or sintering calcium magnesia sand; The grain composition of electric smelting calcium magnesia sand or sintering calcium magnesia sand is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
3. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1; Its characteristic is the mixture of its particle and fine powder at described electrosmelted magnesite clinker or magnesite clinker; The grain composition of electrosmelted magnesite clinker or magnesite clinker is: 80～100wt% is that particle diameter is the particle of 0.5～12mm, and 0～20wt% is that particle diameter is the fine powder of 3～95um.
4. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1; Its characteristic is more than one particulate mixtures in a hydrated sodium silicate, two hydrated sodium silicates, three hydrated sodium silicates, four hydrated sodium silicates, five hydrated sodium silicates, six hydrated sodium silicates, seven hydrated sodium silicates, eight hydrated sodium silicates, nine hydrated sodium silicates at described hydrated sodium silicate particle, and the hydrated sodium silicate grain diameter is 0.5～6mm.
5. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1; Its characteristic is the mixture of its particle and fine powder at described forsterite, particle and fine powder grain composition be: 10～60wt% is that particle diameter is that particle, the 40～90wt% of 1～5mm is that particle diameter is the fine powder of 2～100um.
6. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1, its characteristic is 0.001～100um at the particle diameter of described fine silica.
7. the preparation method of dry type magnesium-calcium gravity flow fire-resistant material according to claim 1, the particle diameter that it is characterized in that described limestone fines is 2～100um.
8. according to each is described with the prepared dry type magnesium-calcium gravity flow fire-resistant material of the preparation method of dry type magnesium-calcium gravity flow fire-resistant material in the claim 1～7.
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| CN113277836B (en) * | 2021-05-31 | 2022-02-18 | 武汉钢铁有限公司 | Gunning mix for RH dip pipe and preparation method thereof |
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| US6284688B1 (en) * | 1992-12-22 | 2001-09-04 | Foseco International Limited | Refractory compositions |
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| US6284688B1 (en) * | 1992-12-22 | 2001-09-04 | Foseco International Limited | Refractory compositions |
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