CN103601521A - Low-porosity periclase-magnesium aluminate spinel-zirconia sintered composite refractory material and production process thereof - Google Patents
Low-porosity periclase-magnesium aluminate spinel-zirconia sintered composite refractory material and production process thereof Download PDFInfo
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- CN103601521A CN103601521A CN201310587230.8A CN201310587230A CN103601521A CN 103601521 A CN103601521 A CN 103601521A CN 201310587230 A CN201310587230 A CN 201310587230A CN 103601521 A CN103601521 A CN 103601521A
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- magnesia
- magnesium aluminate
- aluminate spinel
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Abstract
The invention provides a low-porosity periclase-magnesium aluminate spinel-zirconia sintered composite refractory material, which is prepared from the following materials: 35-48% of 5-1mm magnesia, 15-30% of 1-0.088mm magnesia or synthetic magnesium aluminate spinel, 10-30% of less than 0.088mm synthetic magnesium aluminate spinel, 0-12% of less than 0.020mm synthetic magnesium aluminate spinel, 0-10% of G alumina micro powder, 0-4% of magnesium oxide micro-powder, 1-10% of zirconium oxide micro-powder, 0.05-0.2% of external third generation water reducing agent and 3-7% of external sulfite lye. During production, the magnesia is taken as an aggregate, and the composite magnesium aluminate spinel-zirconium oxide is taken as a base material; in the base material, the synthetic magnesium aluminate spinel is taken as coarse particles, while in-situ spinel-zirconium oxide is taken as fine particles; a brick-making material is dispersed in an efficient dispersant and then formed into compact green bricks under high pressure; then the compact green bricks are sintered at high temperature to form the refractory material with a compact structure; according to the proportions of the raw materials, all the raw materials are weighed, blended, mixed, molded and dried, and then sintered in the temperature range from 1650 to 1800 DEG C for 5-10 hours, and finally, the refractory materials is obtained. The refractory material has extremely low apparent porosity, and excellent high-temperature resistance, thermal shock resistance and erosion resistance; therefore, the refractory material is applicable for the grid of the heat accumulating chamber of a glass kiln as an erosion-resistant refractory material.
Description
Technical field
The present invention is the sintered combined refractory materials of a kind of periclasite-magnesia alumina spinel-zirconia of low pore, is suitable for corroding medium position in regenerator chamber of glass kiln, is applicable to doing the contour anti-corrosion refractory materials of regenerator chamber of glass kiln checker.
Background technology
At present, regenerator chamber of glass kiln mainly use MgO content is 97% magnesia brick, MgO content is 95% magnesia brick and directly in conjunction with magnesia chrome brick as checker.Due under high temperature, alkalescence and oxidizing atmosphere, containing chromium refractory materials, can produce poisonous sexavalent chrome, magnesia chrome brick will be eliminated gradually.Because glass furnace is used the alternative fuel such as refinery coke in a large number, a large amount of SO that contain in gas in kiln
2deng acidic substance, Eroded is to alkaline magnesian, the life-span of magnesia brick is reduced to 1-3 from 5-8.
Magnesium-aluminium spinel (MA) be high, the anti-weakly alkaline of a kind of fusing point to the strong material of neutral substance erosional competency, its chemical constitution is Al
2o
3=71.8%, MgO=28.2%.As too high in alumina content, will form rich magnalium aluminate (magnesium-aluminium spinel-corundum heterogeneous structure); As too high in content of magnesia, will form rich magnesium aluminate spinel (magnesium-aluminium spinel-periclasite heterogeneous structure).
In Iron And Steel Industry, usually use rich aluminium magnesium-aluminum spinel raw material.Because mainly rely on MA to absorb FeO in slag containing the refractory materials of magnesium-aluminium spinel
x, CaO to be to reduce the erosional competency of slag, and aluminium riched spinel has FeO in stronger absorption slag
x, CaO, form FeOAl
2o
3and CaO6Al
2o
3ability.Test shows, adds after rich aluminium magnesium-aluminum spinel raw material in refractory castable, and this spinel absorbs Fe in slag
2o
3, CaO ability be stoichiometry magnesium-aluminium spinel 3-5 doubly.
At present, China's glass furnace adopts refinery coke as fuel in a large number, though can significantly reduce fuel cost, the life-span of regenerator refractory materials significantly shortens.So, in the urgent need to the regenerator chamber of glass kiln refractory materials of Development of New Generation.Magnesium-aluminium spinel is a kind of candidate material of using for regenerator chamber of glass kiln.But, use in some cases the magnesium-aluminium spinel life-span not good, one of reason is just in magnesium-aluminium spinel, to contain in dimension stone of magnesia alumina spinel corundum.If the soda ash in cell furnace volatilizees in a large number, make to fly the R of material
2o/SO
3mol ratio>=1, remaining Na
2o, by the corundum phase in erosion of refractory, forms Na
2o11Al
2o
3, the expansion of reaction association will make refractory materials damage sooner.So, the crucial content that will control exactly objectionable impurities corundum phase in dimension stone of magnesia alumina spinel.
Formerly therefore two be: the fusing point of magnesium-aluminium spinel is up to 2135 ℃, and pure dimension stone of magnesia alumina spinel need to be at 1800 ℃ of left and right sintering, material difficulty burns till, yielding, and this makes neat appearance and the refractory materials of internal structure densification with regard to being difficult to.
Formerly therefore three be: the price of magnesium-aluminium spinel is very high.As regenerator, all use spinel refractory materials, will significantly improve refractory materials buying expenses ，Shi glass producer and be difficult to accept.
Summary of the invention
Order of the present invention is the sintered combined refractory materials of a kind of periclasite-magnesia alumina spinel-zirconia of research, and this refractory materials relies on magnesia as aggregate, usings composite magnesium aluminate spinel-zirconium white as matrix.In matrix, using synthetic MgAl spinal as fine particle, with In-suit spinel-zirconium white effect ultrafine particle.Brickmaking material, after dispersant with high efficiency disperses, then forms fine and close adobe through high pressure, then forms compact structure through high temperature sintering.By proposing following technique measures, manufacture regenerator chamber of glass kiln fireproof magnesia alumina spinel material: one, is used magnesia as aggregate, to reduce the price of material.Its two, the rich magnesium aluminate spinel or the pure magnesium-aluminium spinel that use composition to approach recently stoichiometry magnesium-aluminium spinel are made raw material, to avoid bringing into the most harmful corundum phase.Its three, during brickmaking, add a small amount of α-Al
2o
3with MgO micro mist, in making it to burn till and in refractory materials matrix, remain MgO reaction, form original position magnesium-aluminium spinel, to improve dense packing degree, strengthen sintering and also further reduce the content of periclasite.Finally, during brickmaking, add a small amount of zirconium white micro mist, to reduce sintering temperature, improve resistance to fouling and thermal shock resistance.Also have, use high efficiency water reducing agent, effectively to disperse micro mist, form finer and close structure.Owing to having formed the tissue of the magnesia alumina spinel-zirconia matrix encirclement periclasite aggregate of high resistance to corrosion, material has significantly reduced manufacturing cost, the erosion of acidic substance is had again to certain resistibility simultaneously, is suitable for the medium position of erosion in regenerator chamber of glass kiln.This refractory materials has very low apparent porosity and good high temperature resistant, anti-erosion, thermal shock resistance, is applicable to doing the contour anti-corrosion refractory materials of regenerator chamber of glass kiln checker.
According to above-mentioned design, following concrete measure is proposed:
The weight percent compatibility of material:
Wherein said magnesia is that commercially available refractory raw material of the same name can be sintering or electrosmelted magnesite clinker, described synthetic MgAl spinal is that aluminium sesquioxide content is the magnesium-aluminum spinel raw material of 64-73%, if the trade mark in GB/T26564-2011 is the product of SMA66 or FMA66, described α-aluminum oxide micro mist is commercially available product of the same name, its particle diameter <10 μ m, described fine magnesium oxide micro-powder is the ultrafine powder that commercially available magnesia makes, its particle diameter <10 μ m, described zirconium white micro mist is the ZrO that commercially available zirconium white or desilicated zirconia process
2>=90% raw material, its particle diameter <10 μ m, described third generation water reducer is commercially available product of the same name, take poly carboxylic acid as main building concrete industry water reducer, the liquid of the proportion 1.1-1.2 that the byproduct wooden calcium sulfonate that described spent pulping liquor is paper industry prepares.
Technical process:
Rely on magnesia as aggregate, using composite magnesium aluminate spinel-zirconium white as matrix, in matrix, using synthetic MgAl spinal as coarse particle, with In-suit spinel-zirconium white effect fine particle, brickmaking material is after dispersant with high efficiency disperses, through high pressure, form fine and close adobe again, then form compact structure refractory materials through high temperature sintering, according to proportioning raw materials, by various raw materials through weighing, coordinate, mix, die mould, dry after, through 1650-1800 ℃ * 5-10 hour, after burning till, make described refractory materials.
Embodiment
Embodiment 1:
Adopt magnesite clinker and the alumina content 66% of MgO content 97%, the synthetic MgAl spinal of content of magnesia 34% is as major ingredient, proportioning is: 5-1mm magnesite clinker 45%, 1-0.088mm magnesite clinker 22%, <0.088mm magnesium-aluminium spinel 20%, fine magnesium oxide micro-powder 3%, α-aluminum oxide micro mist 4%, zirconium white micro mist 6%, additional commercially available polycarboxylate water-reducer 0.05%, additional spent pulping liquor 5%, take after each raw material, through coordinating, mixing, moulding, dry, through 1700 ℃ * 6 hours, burn till again, the ultimate compression strength that makes refractory materials is 58.2MPa, volume density 3.18g/cm
3, apparent porosity 14.2%, refractoriness under load T
0.6=1680 ℃, 1100 ℃ of water-cooled>=8 time of thermal shock resistance, made there is well high temperature resistant, anti-thermal shock, the refractory materials of low pore physics and desirable chemical mineral composition.
Embodiment 2:
Adopt electrosmelted magnesite clinker and the alumina content 66% of MgO content 97%, the synthetic MgAl spinal of content of magnesia 34% is as major ingredient, proportioning is: 5-1mm electrosmelted magnesite clinker 40%, 1-0.088mm synthetic MgAl spinal 25%, <0.088mm synthetic MgAl spinal 23%, <0.020mm synthetic MgAl spinal 12%, zirconium white micro mist 0%, additional commercially available polycarboxylate water-reducer 0.05%, additional spent pulping liquor 5%, take after each raw material, through coordinating, mixing, moulding, dry, through 1760 ℃ * 8 hours, burn till again, the ultimate compression strength that makes refractory materials is 69.3MPa, volume density 3.25g/cm
3, apparent porosity 12.8%, refractoriness under load T
0.6>1700 ℃, 1100 ℃ of water-cooled=2 time of thermal shock resistance, made the refractory materials with better physicochemical property and desirable chemical mineral composition.
Claims (2)
1. the sintered combined refractory materials of low pore periclasite-magnesia alumina spinel-zirconia, is characterized in that: the weight percent proportioning of described refractory materials is:
Wherein said magnesia is that commercially available refractory raw material of the same name comprises magnesite clinker and electrosmelted magnesite clinker, described synthetic MgAl spinal is that aluminium sesquioxide content is the magnesium-aluminum spinel raw material of 64-73%, described α-aluminum oxide micro mist is commercially available product of the same name, its particle diameter <10 μ m, described α fine magnesium oxide micro-powder is the ultrafine powder that commercially available magnesia makes, its particle diameter <10 μ m, described zirconium white micro mist is the ZrO that commercially available zirconium white or desilicated zirconia process
2>=88% raw material, its particle diameter <10 μ m, described third generation water reducer is commercially available product of the same name, take poly carboxylic acid as main building concrete industry water reducer, the liquid of the proportion 1.1-1.2 that the byproduct wooden calcium sulfonate that described spent pulping liquor is paper industry prepares.
2. a production technique of manufacturing refractory materials described in claim 1, it is characterized in that: rely on magnesia as aggregate, using composite magnesium aluminate spinel-zirconium white as matrix, in matrix, using synthetic MgAl spinal as coarse particle, with In-suit spinel-zirconium white effect fine particle, brickmaking material is after dispersant with high efficiency disperses, through high pressure, form fine and close adobe, through high temperature sintering, form again the refractory materials of compact structure, according to proportioning raw materials, by various raw material weighing, coordinate, mix, die mould, after dry, through 1650-1800 ℃ * 5-10 hour, after burning till, make described refractory materials.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177103A (en) * | 2014-08-28 | 2014-12-03 | 青岛永通电梯工程有限公司 | Magnesium aluminate spinel refractory material |
| CN106478116A (en) * | 2016-09-29 | 2017-03-08 | 上海大学 | A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material |
| CN107311669A (en) * | 2017-06-13 | 2017-11-03 | 武汉科技大学 | A kind of periclase spinel refractory bricks and preparation method thereof |
| CN107686339A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of high magnesia refractories for tundish |
| CN107935609A (en) * | 2017-12-02 | 2018-04-20 | 芜湖乾凯材料科技有限公司 | High chemical stability cement kiln clinkering zone refractory brick and preparation method thereof |
| CN108503342A (en) * | 2018-04-25 | 2018-09-07 | 华北理工大学 | A kind of Carbon-free refractories and its preparation method and application |
| CN113443898A (en) * | 2021-06-17 | 2021-09-28 | 鞍山市奥鞍耐火材料有限责任公司 | Low-thermal-conductivity spinel refractory homogeneous brick and preparation method and application thereof |
| CN114671673A (en) * | 2022-03-31 | 2022-06-28 | 安徽瑞泰新材料科技有限公司 | Corrosion-resistant light-weight refractory material and preparation method thereof |
| CN116283317A (en) * | 2023-03-08 | 2023-06-23 | 湖南金铠新材料科技股份有限公司 | Sagger for sintering sodium ion battery anode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219535A (en) * | 2011-04-22 | 2011-10-19 | 瑞泰科技股份有限公司 | Recombined magnesia-alumina spinel brick with properties of nodulation and blockage prevention and high corrosion resistance, and production technology thereof |
-
2013
- 2013-11-15 CN CN201310587230.8A patent/CN103601521B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219535A (en) * | 2011-04-22 | 2011-10-19 | 瑞泰科技股份有限公司 | Recombined magnesia-alumina spinel brick with properties of nodulation and blockage prevention and high corrosion resistance, and production technology thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177103A (en) * | 2014-08-28 | 2014-12-03 | 青岛永通电梯工程有限公司 | Magnesium aluminate spinel refractory material |
| CN106478116A (en) * | 2016-09-29 | 2017-03-08 | 上海大学 | A kind of thermal shock resistance ZrO of magnesium aluminate spinel doping2The preparation method of MgO refractory material |
| CN107311669A (en) * | 2017-06-13 | 2017-11-03 | 武汉科技大学 | A kind of periclase spinel refractory bricks and preparation method thereof |
| CN107311669B (en) * | 2017-06-13 | 2020-01-24 | 武汉科技大学 | Periclase-spinel refractory brick and preparation method thereof |
| CN107686339A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of high magnesia refractories for tundish |
| CN107935609A (en) * | 2017-12-02 | 2018-04-20 | 芜湖乾凯材料科技有限公司 | High chemical stability cement kiln clinkering zone refractory brick and preparation method thereof |
| CN108503342A (en) * | 2018-04-25 | 2018-09-07 | 华北理工大学 | A kind of Carbon-free refractories and its preparation method and application |
| CN108503342B (en) * | 2018-04-25 | 2020-07-07 | 华北理工大学 | Carbon-free refractory material and preparation method and application thereof |
| CN113443898A (en) * | 2021-06-17 | 2021-09-28 | 鞍山市奥鞍耐火材料有限责任公司 | Low-thermal-conductivity spinel refractory homogeneous brick and preparation method and application thereof |
| CN114671673A (en) * | 2022-03-31 | 2022-06-28 | 安徽瑞泰新材料科技有限公司 | Corrosion-resistant light-weight refractory material and preparation method thereof |
| CN116283317A (en) * | 2023-03-08 | 2023-06-23 | 湖南金铠新材料科技股份有限公司 | Sagger for sintering sodium ion battery anode material and preparation method thereof |
| CN116283317B (en) * | 2023-03-08 | 2023-10-24 | 湖南金铠新材料科技股份有限公司 | Sagger for sintering sodium ion battery anode material and preparation method thereof |
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