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WO2016013384A1 - Alumine-zircone-silice réfractaire coulé par fusion, four de fusion du verre, et procédé de production de plaque de verre - Google Patents

Alumine-zircone-silice réfractaire coulé par fusion, four de fusion du verre, et procédé de production de plaque de verre Download PDF

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Publication number
WO2016013384A1
WO2016013384A1 PCT/JP2015/069252 JP2015069252W WO2016013384A1 WO 2016013384 A1 WO2016013384 A1 WO 2016013384A1 JP 2015069252 W JP2015069252 W JP 2015069252W WO 2016013384 A1 WO2016013384 A1 WO 2016013384A1
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Prior art keywords
zirconia
glass
alumina
refractory
sio
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PCT/JP2015/069252
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English (en)
Japanese (ja)
Inventor
小川　修平
戸村　信雄
泰夫 篠崎
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C04B35/657—Processes involving a melting step for manufacturing refractories
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs

Definitions

  • the present invention relates to an alumina / zirconia / silica fused cast refractory, a glass melting furnace, and a method for producing a glass plate, and particularly as a stone of badelite crystal in contact with molten glass in a temperature range of 1450 ° C. or lower.
  • the present invention relates to an alumina / zirconia / siliceous fusion cast refractory with suppressed outflow, a glass melting furnace, and a method for producing a glass plate.
  • the molten cast refractory is usually obtained by pouring hot water in which a refractory raw material having a predetermined composition is completely melted in an electric furnace into a mold having a predetermined shape, and cooling and re-solidifying to normal temperature.
  • the molten cast refractory obtained in this way is widely known as a highly erodible refractory that is completely different from the structure and manufacturing method of the fired and unfired bonded refractory.
  • the molten cast refractory obtained by the present invention is generally produced by casting a refractory raw material melted in an electric furnace into a desired shape, it will be described as a molten cast refractory hereinafter.
  • the molten cast refractory in the present specification includes those that are solidified in the furnace after melting, and the molten cast refractory obtained by pulverizing the molten refractory is useful as an aggregate of the bonded refractory. .
  • alumina or zirconia molten cast refractories used in conventional glass melting furnaces there are mainly fused cast refractories of high alumina, alumina / zirconia / silica, and high zirconia.
  • high-alumina melt-cast refractories have high erosion resistance against glass, do not cause defects such as bubbles and cords in glass, are stable against alkali vapor, and deform under load. There is nothing to do. However, since the content of alumina, which is lower in erosion resistance than zirconia, is larger, the erosion resistance is lower than in other molten cast refractories.
  • the alumina / zirconia / silica fused cast refractory contains a relatively large amount of zirconia as disclosed in, for example, Patent Document 1, and has a high erosion resistance against molten glass.
  • Patent Document 1 a high zirconia molten cast refractory containing 90% or more of ZrO 2 has also been proposed as described in Patent Document 2, and a molten cast refractory containing a large amount of zirconia is molten glass or scattered raw refractory. It has very high erosion resistance with respect to the batch, and is sufficiently satisfactory in terms of erosion resistance when used in a portion in direct contact with molten glass.
  • refractories containing a relatively large amount of zirconia are preferably used for glass melting kilns because they are particularly excellent in erosion resistance.
  • Typical refractory is a high zirconia fused cast refractories containing alumina-zirconia-silica fusion cast refractories containing ZrO 2 33% to 41% and ZrO 2 80% to 95%.
  • high zirconia fused cast refractories with high zirconia content and high erosion resistance have high erosion resistance to glass and low probability of causing glass defects. It came to be used for.
  • high zirconia melt cast refractories have a very high ZrO 2 content, so such refractories are expensive and costly during production.
  • alumina, zirconia, and siliceous molten cast refractories have been used most widely over decades because they have good erosion resistance and low manufacturing costs, and are mainly in contact with molten glass. It is also used for the zones to be used and for the superstructure of the glass melting furnace.
  • This alumina / zirconia / silica fused cast refractory generally consists of about 80-85% crystals and 15-20% matrix glass phase filling the crystal gaps.
  • the crystal phase is composed of corundum crystals, which are trigonal crystals of alumina, and badelite crystals, which are monoclinic crystals of zirconia.
  • the composition thereof is, for example, 45.8% to 52% of alumina / zirconia / silica fused cast refractories such as ZB1681, ZB1691, ZB1711 (above, trade name, manufactured by AGC Ceramics Co., Ltd.) currently available on the market.
  • Al 2 O 3 33% to 41% ZrO 2 , 12% to 13.5% SiO 2 , and 1% to 1.9% Na 2 O.
  • the matrix glass is an amorphous glass phase having no specific crystal structure mainly composed of silica.
  • zirconia has a transformation transition due to monoclinic and tetragonal phase transitions at around 1150 ° C. when the temperature is raised and around 1000 ° C. when the temperature is lowered, and exhibits rapid contraction and expansion.
  • the matrix glass phase acts as a cushion between crystals, and absorbs stress due to transformation expansion due to the transition from tetragonal to monoclinic zirconia in the production of fused refractories of alumina, zirconia, and siliceous. Therefore, it plays an important role for producing an ingot without cracks.
  • Alumina / zirconia / silica fused cast refractories that suppress the occurrence of stone defects include alumina / zirconia / Al 2 O 3 / SiO 2 ratio of 1 or less in Patent Document 3 containing 62% or more of ZrO 2.
  • Siliceous fused cast refractories have been proposed. In the said refractory material, it is possible to suppress the cracking of the refractory material that occurs during production, and to reduce the wear rate and the amount of stone generated on the glass.
  • Patent Document 3 the alumina / zirconia / silica fused cast refractory of Patent Document 3 is expensive because of its high ZrO 2 content, and it is difficult to use it widely as a general-purpose glass melting refractory.
  • JP 62-065981 A Japanese Patent Laid-Open No. 3-028175 Japanese Patent Laid-Open No. 48-032408 Japanese Patent Laid-Open No. 10-072264
  • the present invention solves the problems of the prior art described above, suppresses the generation of stone in the glass, and also has high erosion resistance against the glass, and is suitable as a refractory for a glass manufacturing apparatus.
  • An object of the present invention is to provide an alumina / zirconia / silica fused cast refractory and a glass melting furnace using the same.
  • the inventors of the present invention are alumina / zirconia / siliceous fusion cast refractories containing Al 2 O 3 , ZrO 2 , SiO 2 and Na 2 O as essential components, and the content of the above essential components It was found that the above-mentioned problems could be solved by blending so as to be a predetermined amount, and the present invention was completed.
  • [2] The alumina / zirconia / silica fusion cast refractory according to [1], wherein Al 2 O 3 / SiO 2 ⁇ 25.0.
  • [3] The alumina / zirconia / silica fusion cast refractory according to [1] or [2], further comprising 0.8 to 5.0% of Y 2 O 3 .
  • [4] The alumina / zirconia / silica fused cast refractory according to any one of [1] to [3], further comprising 0.1 to 3.0% in total amount of K 2 O and Li 2 O.
  • [5] The alumina / zirconia / silica fusion cast refractory according to any one of [1] to [4], further containing CaO in an amount of 0.1% to 2.0%.
  • [6] The alumina / zirconia / siliceous fusion cast refractory according to any one of [1] to [5], wherein ZrO 2 / (Al 2 O 3 + ZrO 2 ) ⁇ 0.39.
  • [7] The alumina / zirconia / siliceous molten cast refractory according to any one of [1] to [6], wherein 0.33 ⁇ ZrO 2 / (Al 2 O 3 + ZrO 2 ).
  • [8] The alumina / zirconia / silica fused cast refractory according to any one of [1] to [7], which has an open porosity of 1.0% or less.
  • a glass melting furnace comprising the alumina / zirconia / silica electrocast refractory according to any one of [1] to [8].
  • a method for producing a glass plate comprising: heating a glass raw material in the glass melting furnace according to [9] or [10] to obtain molten glass, and forming the molten glass into a plate shape.
  • the generation of stones in the glass at the time of melting the glass is suppressed, the glass has high erosion resistance and low open porosity.
  • An alumina / zirconia / silica fusion cast refractory suitable as a refractory for a production apparatus can be provided.
  • the glass melting furnace of the present invention since the generation of stones in the molten glass is suppressed and the glass has high erosion resistance, the glass can be stably melted, and the quality is improved. Good glass products can be manufactured with good yield.
  • the generation of stones in the molten glass is suppressed, the glass can be stably melted, and high-quality glass can be produced with a high yield.
  • the alumina / zirconia / silica fusion cast refractory according to one embodiment of the present invention contains Al 2 O 3 , ZrO 2 , SiO 2 and Na 2 O as essential components, and the content of these essential components Is characterized in that it is blended so as to have a predetermined amount.
  • the molten cast refractory may be referred to as a refractory or an ingot.
  • a nepheline layer is formed on the back side of the remaining beddelite layer.
  • a nepheline layer may be formed on the surface side of the remaining badelite layer.
  • Non-Patent Document 1 does not specify whether it is crystalline or glassy, but it is described that a nepheline layer is formed on the surface of the alumina / zirconia / silica fused cast refractory after use.
  • a nepheline crystal is a tridymite-based silica derivative compound having a stoichiometric composition of NaAlSiO 4 , and is known to undergo a crystal transition to a cristobalite-based carnegiaite crystal in a high-temperature field exceeding 1254 ° C. Further, as described in Non-Patent Document 2, nepheline crystals maintain their crystal structures in a wide range of compositions, and the crystal transition temperature and melting point to carnegite crystals change. The crystal transition temperature and melting point are greatly affected by the composition.
  • nepheline layer means a nepheline crystal represented by a stoichiometric composition of NaAlSiO 4 , a carnegiaite crystal that is a high-temperature form of nepheline, and a composition range in which the crystal structure is maintained. It includes all crystals and glass containing these crystals by melting (hereinafter also referred to as nepheline glass).
  • the carnegite crystal is a crystal that is generated when the nepheline crystal undergoes a crystal transition in a high temperature field.
  • the melting point of nepheline crystal or carnegite crystal varies greatly with the composition as described above. For example, as the content of SiO 2 increases, the melting point of nepheline crystal or carnegite crystal decreases.
  • the nepheline crystal composition of Na 2 Al 2 Si 3 O 10 starts to partially melt at around 1120 ° C. and around 1330 ° C. Then it melts completely. Further, the melting point is further lowered by including impurities such as CaO, K 2 O, Fe 2 O 3 in this crystal composition.
  • nepheline-like glass means a glass rich in Na 2 O and Al 2 O 3 , and is not limited to a glass represented by the composition of NaAlSiO 4 , for example, K 2 O, CaO, MgO, etc.
  • the impurities may be included.
  • This nepheline glass is known to have a very high viscosity as compared with ordinary soda lime glass.
  • the above-mentioned nepheline layer is composed of Na 2 O contained in the soda lime glass and Al 2 O 3 eluted from the refractory in the vicinity of the surface of the refractory.
  • the present inventors have studied to use this nepheline layer positively to suppress stones.
  • the nepheline layer is actively generated to the vicinity of the surface layer of the refractory during use of the refractory, and the condition where the residual beddelite is protected by the nepheline layer and the stone is prevented from falling off is completed. did.
  • nepheline crystals or carnegite crystals can be generated near the surface of the refractory during use of the refractory, the outflow of badelite as a stone is physically suppressed.
  • the melting point of the nepheline crystal or the carnegite crystal varies greatly with the composition, so depending on the composition formed near the surface of the refractory and the operating temperature of the refractory, it is not always possible to use the It may not exist, and may exist as a molten highly viscous nepheline glass. However, even when a highly viscous nepheline-like glass is produced, the viscosity of the glass is very high, so that the stone can be prevented from falling.
  • the alumina / zirconia / silica fusion cast refractory according to an embodiment of the present invention is a vitreous layer of a nepheline layer made of glass or a highly viscous glass, and actively uses the refractory in the vicinity of the surface layer of the refractory. And the remaining beddelite layer is protected by this nepheline layer, so that the stone can be prevented from falling off.
  • Al 2 O 3 is an essential component in one embodiment of the present invention.
  • Alumina constitutes a corundum crystal, and this corundum crystal has high erosion resistance and does not exhibit abnormal expansion and contraction due to temperature change.
  • alumina is a component that has the effect of forming a nepheline layer near the surface of the refractory when the refractory comes into contact with the molten glass, and this nepheline layer is a protective layer that suppresses the loss of stones. Therefore, it is possible to suppress the generation amount of stone.
  • the Al 2 O 3 content is 30% ⁇ Al 2 O 3 ⁇ 75%.
  • the content of Al 2 O 3 is 75% or less, the content of ZrO 2 becomes relatively low without being too low, and the erosion resistance is good. Moreover, it is difficult to produce mullite and it is easy to obtain an ingot without cracks.
  • the content of Al 2 O 3 is 30% or more, the content of ZrO 2 is relatively high without becoming too high, and in this case as well, it becomes easy to obtain an ingot without cracks.
  • the content of Al 2 O 3 is preferably 40% or more and 72% or less, more preferably 50% or more and 70% or less, and further preferably 55% or more and 65% or less. Unless otherwise indicated, all percentages in the present specification are mass percentages based on oxides.
  • ZrO 2 is a component that constitutes a badelite crystal and enhances the erosion resistance of the refractory to the molten glass, and is an essential component in one embodiment of the present invention.
  • the ZrO 2 content is 22% ⁇ ZrO 2 ⁇ 50%.
  • ZrO 2 is preferably contained in a larger amount from the viewpoint of improving the erosion resistance. When the content is 22% or more, the erosion resistance is improved.
  • the content of ZrO 2 is 50% or less, in the range of the amount of matrix glass described later, expansion and contraction due to the phase transition of zirconia are alleviated, and an ingot without cracks is obtained.
  • the ZrO 2 content is preferably 26 to 45%, more preferably 28% to 41%, and even more preferably 30% to 37%.
  • eutectic zirconia is a small zirconia crystal that precipitates at the eutectic point at the end of cooling during the production of alumina, zirconia, and siliceous refractories by the melting method.
  • primary zirconia is a large zirconia crystal that precipitates in the early stage of cooling. The distinction between the two can be easily distinguished by the size of the crystal by observing with a microscope. Moreover, when observed with a microscope, eutectic zirconia crystals are observed as a collection of fine crystals in corundum grains, and adjacent crystals are oriented in the same direction, but primary zirconia crystals are present.
  • the crystal grain size of the eutectic zirconia crystal is about 1/5 or less of the maximum crystal grain size of the zirconia crystal.
  • SiO 2 is a main component that forms the skeleton of the matrix glass, and is an essential component in one embodiment of the present invention.
  • the content is 2.0% ⁇ SiO 2 ⁇ 10.0%. If it exceeds 2.0%, the absolute amount of the matrix glass increases, and an ingot without cracks is easily obtained, and the obtained ingot exhibits a good structure.
  • the content is 10.0% or less, the content of Al 2 O 3 and ZrO 2 which are relatively crystalline components is increased, erosion resistance is improved, and the thickness of the remaining bedrite layer is reduced, resulting in the formation of stone. The amount decreases.
  • Content of SiO 2 is preferably 3.5% ⁇ SiO 2 ⁇ 8.5% , 4.5% ⁇ SiO 2 ⁇ 7.5% , more preferably, 5.0% ⁇ SiO 2 ⁇ 7.0 % Is more preferable.
  • Na 2 O has the effect of controlling the viscosity of the matrix glass and the melting point of nepheline formed when using the refractory in the production of alumina / zirconia / silica fused cast refractories. In one embodiment of the invention, it is an essential component.
  • the content of Na 2 O is 0.5% ⁇ Na 2 O ⁇ 2.5%.
  • a nepheline layer can be formed near the surface of the refractory when the refractory comes into contact with the molten glass. Since this nepheline layer acts as a protective layer that suppresses the falling off of the stone, it is possible to suppress the amount of generated stone.
  • nepheline crystals do not begin to partially form in the matrix glass during the production of the refractory.
  • This nepheline crystal causes microcracks due to the stress generated from the difference in expansion coefficient between zirconia and alumina, and its presence increases the open porosity of the refractory. If the open porosity of the refractory increases, the use of the refractory increases the bubble defects due to the gas contained in the refractory being released into the glass. End up. Therefore, it is preferable that the open porosity of the refractory is small. As described above, since the Na 2 O content in the present invention is less than 2.5%, the generation of microcracks can be suppressed, and the open porosity of the refractory can be kept small.
  • the content of the Na 2 O is preferably 0.7% ⁇ Na 2 O ⁇ 2.2 %, more preferably 0.9% ⁇ Na 2 O ⁇ 1.8 %, 1.1% ⁇ Na 2 O ⁇ 1.6% is more preferable.
  • Y 2 O 3 is not an essential component, but Y 2 O 3 has the effect of stabilizing part or all of ZrO 2 into cubic crystals. Therefore, when using a refractory, zirconia is generated when the temperature is increased. The shrinkage and expansion due to the phase transition can be alleviated. For this reason, at the time of refractory use, it becomes possible to suppress the opening of the joint between refractories, and it becomes possible to improve erosion resistance and to suppress the amount of stone formation.
  • the content of Y 2 O 3 is preferably 0.8 to 5.0%.
  • Y 2 O 3 content is, relaxation effect of expansion and contraction due to a phase transition of Y 2 O 3 ⁇ 0.8% in the zirconia is increased, the content of Y 2 O 3 ⁇ 5% in Y 2 O 3 Therefore, it is inexpensive and easy to use widely as a general-purpose glass melting refractory.
  • the content of Y 2 O 3 is preferably 1.0 to 4.0%, more preferably 1.3 to 3.0%, further preferably 1.5 to 2.7%, and 1.7 to 2%. .4% is particularly preferred.
  • Y 2 O 3 may be used in combination with a component containing at least one member of the group consisting of CeO 2 , MgO, Sc 2 O 3 and V 2 O 5 , or may be replaced by a combination of these components alone or in combination. May be.
  • K 2 O and Li 2 O are not essential components, but are components that have an effect of adjusting the viscosity of the matrix glass and the high-temperature viscosity of the nepheline layer. These K 2 O and Li 2 O are preferably contained in a total content of 0.1% to 3.0%. K 2 O and Li 2 O in the total amount the production of low-viscosity matrix glass and 3.0% or less can be suppressed.
  • CaO is not an essential component, but is a component that exhibits an effect of adjusting the viscosity of the matrix glass and the high temperature viscosity of the nepheline layer.
  • This CaO is preferably contained in the range of 0.1% to 2.0%. When CaO is within this range, the production of low-viscosity matrix glass is suppressed. Further, the zirconia crystals are not dissolved, and the erosion resistance of the product is improved.
  • the total amount of essential components of Al 2 O 3 + ZrO 2 + SiO 2 + Na 2 O contained in the refractory is 85% or more. To do. This is because if the refractory contains too many other components, the content of Al 2 O 3 and ZrO 2 decreases, the erosion resistance to the glass decreases, and the amount of stone generated increases. It is because it will do.
  • the total amount of Al 2 O 3 + ZrO 2 + SiO 2 + Na 2 O is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and 99% The above is particularly preferable.
  • the content of Al 2 O 3 , ZrO 2 , SiO 2 , and Na 2 O in the refractory is set within a predetermined range, and further, the relationship between the amounts of these components is set as a predetermined relationship.
  • an alumina / zirconia / silica fused cast refractory material that suppresses the generation of stones and has high erosion resistance to glass can be obtained.
  • Na 2 O is an essential component, the content of Al 2 O 3 and Na 2 O with respect to SiO 2, respectively Al 2 O 3 / SiO 2 ⁇ 6.6,0.08 ⁇
  • the reason for limiting to the range of Na 2 O / SiO 2 ⁇ 0.25 will be described in more detail.
  • the nepheline crystal is a compound having a stoichiometric composition of NaAlSiO 4 .
  • nepheline crystals and carnegite crystals are actively formed near the surface of the refractory, and in order to produce highly viscous nepheline-like glass in which these crystals melt, It is necessary to positively supply Al 2 O 3 not contained in the refractory from the inside. That is, as the Al 2 O 3 content in the refractory is increased, a nepheline layer is more likely to be generated near the surface layer of the refractory.
  • a nepheline layer can be generated near the surface of the refractory and the amount of generated stones can be suppressed depends on the amount of zirconia contained in the refractory, the ZrO 2 / (ZrO 2 + Al 2 O 3 ) ratio, and Na 2 O / SiO. Also affected by 2 ratios. However, the inclusion of Al 2 O 3 in the range of Al 2 O 3 / SiO 2 ⁇ 6.6 is particularly significant, and under such conditions, a protective layer made of a nepheline layer is placed near the refractory surface layer. It can be formed effectively, and the generation amount of stone can be suppressed.
  • the content of Al 2 O 3 with respect to SiO 2 in the alumina-zirconia-silica fusion cast refractories is Al 2 O 3 / SiO 2 ⁇ 6.6.
  • the content ratio is preferably Al 2 O 3 / SiO 2 ⁇ 7.5, more preferably Al 2 O 3 / SiO 2 ⁇ 8.5, further preferably Al 2 O 3 / SiO 2 ⁇ 9.5, Al 2 O 3 / SiO 2 ⁇ 10.0 is particularly preferred.
  • the nepheline crystal has a melting point of 1526 ° C. ⁇ 2 ° C. in the case of the stoichiometric composition as described above, but the composition of nepheline generated in the vicinity of the surface of the refractory by contact with glass is the stoichiometric composition. a low compositional a content of Na 2 O than, the melting point is greatly reduced in such nepheline crystals.
  • a conventional alumina / zirconia / silica fusion cast refractory it starts to partially melt at approximately 1100 ° C. to 1400 ° C., depending on the use environment.
  • the melting point of nepheline is low, the heat resistance of the refractory is lowered, and the protective effect of the nepheline layer is reduced.
  • nepheline layer having a high Na 2 O content in the vicinity of the refractory surface layer, it becomes possible to suppress the generation amount of stones to a higher temperature range.
  • the nepheline layer is generated by supplying Na 2 O from molten soda lime glass, but the Na 2 O content in the refractory is increased as in the present invention, and Na 2 O is also added from the refractory side. Is supplied, the melting point of the nepheline layer formed near the surface of the refractory is improved (increased).
  • the melting point of the nepheline layer is affected by the amount of zirconia, the ZrO 2 / (ZrO 2 + Al 2 O 3 ) ratio, the Al 2 O 3 / SiO 2 ratio, and the like.
  • the inclusion of Na 2 O in the range of Na 2 O / SiO 2 ⁇ 0.08 has a particularly large influence, and if such conditions are used, a protective layer made of a nepheline layer can be used as a refractory to a higher temperature range. It can be formed near the surface layer.
  • the content ratio of Na 2 O with respect to SiO 2 in the alumina / zirconia / silica fusion cast refractory is 0.08 ⁇ Na 2 O / SiO 2 ⁇ 0.25.
  • the content ratio is preferably 0.10 ⁇ Na 2 O / SiO 2 ⁇ 0.23, more preferably 0.12 ⁇ Na 2 O / SiO 2 ⁇ 0.21, and 0.15 ⁇ Na 2 O / SiO 2. ⁇ 0.19 is more preferred. With such a blending amount, it is possible to obtain an alumina / zirconia / silica fused cast refractory that suppresses the generation of stones in the glass, has a low open porosity, and has high erosion resistance against the glass. It is done.
  • the content ratio of Al 2 O 3 with respect to SiO 2 in the alumina / zirconia / silica fusion cast refractory according to one embodiment of the present invention is preferably Al 2 O 3 / SiO 2 ⁇ 25. This content is more preferably Al 2 O 3 / SiO 2 ⁇ 20, more preferably Al 2 O 3 / SiO 2 ⁇ 15, and particularly preferably Al 2 O 3 / SiO 2 ⁇ 12.
  • the alumina / zirconia / siliceous fusion cast refractory according to an embodiment of the present invention may include hafnium oxide HfO 2 naturally present in a zirconia source.
  • the content of the refractory of the present invention is 5% or less, and generally 2% or less.
  • ZrO 2 means zirconia and trace amounts of hafnium oxide contained therein.
  • the other components are not particularly limited as long as they do not impair the characteristics of the alumina / zirconia / silica fusion cast refractory according to one embodiment of the present invention, and the alumina / zirconia / silica fusion
  • the well-known component used for a cast refractory is mentioned.
  • examples of other components include oxides such as SnO 2 , ZnO, CuO, MnO 2 , Cr 2 O 3 , P 2 O 5 , Sb 2 O 5 , As 2 O 5 , and Yb 2 O 3 .
  • the total amount is preferably 10% or less, more preferably 3% or less, and further preferably 1% or less.
  • the amount of stone generated is affected by the Al 2 O 3 / SiO 2 ratio, Na 2 O / SiO 2 ratio, ZrO 2 content, etc.
  • zirconia and The ratio of zirconia to alumina is preferably ZrO 2 / (Al 2 O 3 + ZrO 2 ) ⁇ 0.39. This is because primary crystal zirconia is not continuous with crystal particles, and primary crystal zirconia is more likely to fall out as stone than eutectic zirconia. This is because the amount of primary zirconia produced can be reduced. Further, it is preferable that 0.33 ⁇ ZrO 2 / (Al 2 O 3 + ZrO 2).
  • Alumina-zirconia-silica melt cast refractory according to an embodiment of the present invention is a component present in the starting material used or produced during the manufacture of the product, i.e. halogens such as fluorine, chlorine, Magnesium, boron, titanium, and iron may be contained as impurities, but these impurities are preferable because they reduce the erosion resistance.
  • halogens such as fluorine, chlorine, Magnesium, boron, titanium, and iron may be contained as impurities, but these impurities are preferable because they reduce the erosion resistance.
  • the term “impurity” means an unavoidable composition that is inevitably incorporated in the starting material or due to the reaction of these compositions.
  • iron or titanium oxides are harmful and their content must be limited to the traces incorporated into the starting material as impurities.
  • the mass of Fe 2 O 3 + TiO 2 is preferably 1% or less, and more preferably less than 0.5%.
  • the mass of P 2 O 5 + B 2 O 3 is preferably less than 0.15%, more preferably less than 0.10%.
  • the alumina / zirconia / silica fusion cast refractory is configured to contain such a predetermined amount of components, for example, when immersed in soda lime glass at 1300 ° C.
  • the protective layer of the nepheline layer can be formed in the vicinity of the surface layer of the refractory, and the amount of stone generated can be suppressed.
  • the amount of stone generated is determined by directly observing the amount of stone falling from the surface of the refractory by observing the cross section of the refractory with an optical microscope (Nikon Corporation, ECLIPSE LV100) after performing an erosion test. Can be evaluated.
  • the amount of generated stone is evaluated by a sample in which a predetermined shear rate is given after immersion in glass at 1300 ° C. for 20 days (480 hours). This result is compared with the result of the same test in the alumina / zirconia / silica fusion cast refractory (AGC Ceramics Co., Ltd., trade name: ZB-1691) that is widely used in glass manufacturing equipment. % Or less refractory is preferred.
  • the generation amount of stone is more preferably 80% or less, further preferably 70% or less, and particularly preferably 60% or less.
  • the shape, size, and mass of the alumina / zirconia / silica fusion cast refractory according to an embodiment of the present invention are not limited.
  • it may be in the form of a slab having a thickness of 100 mm or less.
  • the block or slab forms part of a glass melting furnace or constitutes a wall or hearth.
  • the block or the slab is disposed in a region in contact with the molten glass or in a region in contact with the gas released from the molten glass because the effect of suppressing the generation of stone as described above can be exhibited.
  • the alumina / zirconia / silica fusion cast refractory according to an embodiment of the present invention is, for example, alumina / zirconia widely used in a glass manufacturing apparatus when the amount of generated stone is tested as described above. ⁇ Compared to siliceous molten cast refractory (manufactured by AGC Ceramics, trade name: ZB-1691), the amount of generated stone is 90% or less, and the erosion rate for glass is 115% or less (the relative erosion amount is 115). (Synonymous with the following).
  • the erosion resistance is determined by, for example, immersing the glass at 1300 ° C.
  • erosion resistance is preferably a refractory having a relative erosion amount with ZB-1691 of 115 or less, more preferably 105 or less, and even more preferably 95 or less.
  • the protective layer made of a nepheline layer is difficult to form near the surface of the refractory in an environment where the convection speed of the glass is very high. Therefore, depending on the environment of use, it is difficult to generate a protective layer consisting of a nepheline layer near the refractory surface layer in the flux line where strong convection called Marangonin convection occurs, which improves erosion resistance. The contribution is limited. Therefore, the erosion resistance of the flux line is basically strongly influenced by the zirconia content.
  • the use of the alumina / zirconia / silica fusion cast refractory of the present invention makes it possible to sufficiently generate a protective layer composed of a nepheline layer up to the vicinity of the refractory surface layer. Therefore, the amount of generated stones can be effectively reduced.
  • the alumina / zirconia / silica fusion cast refractory according to an embodiment of the present invention preferably has an open porosity of 1.0% or less.
  • the open porosity is measured according to JIS R1634 (1998).
  • the open porosity is more preferably 0.8% or less, further preferably 0.6% or less, and particularly preferably 0.4% or less.
  • the alumina / zirconia / silica fusion cast refractory according to an embodiment of the present invention is obtained by mixing homogeneously powder raw materials so as to have the above-mentioned blending ratio, melting the mixture in an arc electric furnace, and converting the molten raw material into graphite. It is manufactured by pouring into a mold and cooling.
  • This refractory is expensive because it takes a large amount of energy when melted, but the structure of the ZrO 2 crystal is dense and the size of the crystal is large. Therefore, the refractory has better corrosion resistance stability than the sintered refractory.
  • the heating at the time of melting is performed by bringing a graphite electrode and raw material powder into contact with each other and energizing the electrode.
  • the thus obtained alumina / zirconia / silica fusion cast refractory according to one embodiment of the present invention exhibits excellent erosion resistance against molten glass, and is used when producing glass products such as plate glass. It is suitable for furnace materials for glass melting kilns.
  • a glass melting furnace comprises the above-described alumina / zirconia / silica melting cast refractory according to an embodiment of the present invention. If it is a glass melting furnace equipped with the above-described alumina / zirconia / siliceous molten cast refractory according to one embodiment of the present invention, the generation of stones in the molten glass is suppressed, and the glass has a high erosion resistance. Therefore, the glass can be stably melted, and a glass product with good quality can be manufactured with a high yield.
  • the above-described alumina / zirconia / siliceous fusion cast refractory according to one embodiment of the present invention is preferably used in a place where it comes into contact with glass.
  • a glass melting kiln according to an embodiment of the present invention is the above-described alumina / zirconia / silica molten cast refractory according to an embodiment of the present invention. You may arrange
  • a gas containing Na or K is generated from molten glass or glass melting.
  • the refractory is a glass melting kiln made of quartz brick, the refractory is lowered in melting point and easily deformed by these gases.
  • it is a glass melting kiln using an alumina / zirconia / siliceous fusion cast refractory according to an embodiment of the present invention, it contains high heat-resistant ZrO 2 and has an Al 2 O 3 / SiO 2 ratio of Since it is difficult to be deformed due to a small number of matrix glass portions that are high and easily melted, even if it is disposed in a region that is in contact with gas released by melting glass, it can have high heat resistance.
  • the manufacturing method of the glass plate which concerns on one Embodiment of this invention heats a glass raw material in the glass melting furnace which concerns on one Embodiment of this invention mentioned above, obtains molten glass, and shape
  • the raw material prepared so as to have the composition of the obtained glass plate is charged into the glass melting furnace according to the embodiment of the present invention, preferably Heat to about 1400-1650 ° C. to obtain molten glass.
  • Etc. may be used SO 3 and SnO 2 as a fining agent to the raw material.
  • Bubbles can be removed from the glass by using a fining agent. Further, a defoaming method using reduced pressure may be applied.
  • the molten glass is formed into a plate shape by a fusion method, a float method, a press molding method, or the like.
  • molten glass is flowed over molten metal and formed into a plate shape.
  • the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not construed as being limited to these descriptions.
  • the refractory of the present invention is not limited to a specific shape or dimension, and is not limited to application to a glass melting furnace.
  • Example 1 to Example 37 ZrO 2 raw materials such as desiliconized zirconia and zircon sand, Al 2 O 3 raw materials such as Bayer alumina, SiO 2 raw materials such as silica sand, Na 2 O, Y 2 O 3 , Li 2 O, K 2 O, CaO, MgO, A batch mixture in which raw materials such as Cr 2 O 3 , P 2 O 5 , and B 2 O 5 were adjusted to a predetermined amount was charged into a 500 KVA single-phase arc electric furnace and completely melted at a melting temperature of around 1900 ° C. did.
  • the hot water obtained by melting was poured into a mold made of sand surrounded by a heat insulating material made of siliceous hollow spheres or Bayer alumina around an inner volume of 130 mm x 160 mm x 350 mm, and cast to room temperature. Chilled.
  • melting is a so-called long arc method in which the electrode is lifted from the molten metal surface. For example, oxygen is blown in the middle of melting to keep the melt in an oxidized state as much as possible. I got a thing.
  • Tables 1 to 5 show the chemical analysis values (unit: mass%) and various properties of the obtained molten cast refractories.
  • Examples 1 to 22 are examples, and examples 23 to 37 are comparative examples.
  • Examples 23 and 24 are alumina / zirconia / silica fused cast refractories (trade names; ZB1691 and ZB1711) manufactured by AGC Ceramics, which are widely used in glass manufacturing apparatuses.
  • ZrO 2 , SiO 2 , and Al 2 O 3 are quantitative analysis values determined by a wavelength dispersive X-ray fluorescence analyzer (manufactured by Rigaku Corporation, apparatus name: ZSX Primus II).
  • the other components are quantitative analysis values determined by a high-frequency inductively coupled plasma emission spectrometer (manufactured by Seiko Instruments Inc., apparatus name: SPS 1100).
  • SPS 1100 high-frequency inductively coupled plasma emission spectrometer
  • the quantification of each component is not limited to this analysis method, and can be carried out by other quantitative analysis methods.
  • the obtained molten cast refractories all had (A) corundum crystal, (B) badelite crystal, and (C) matrix glass and / or nepheline crystal as a basic structure.
  • the type and presence of the crystal is determined by cutting the molten cast refractory after manufacture and cutting the cut surface with SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray Detector, manufactured by Hitachi High-Technologies Corporation, product name: S-3000H ), And the crystal structure was analyzed by XRD (X-ray Diffraction, manufactured by Rigaku Corporation, trade name: RINT-TTRIII).
  • the presence or absence of cracks on the appearance of the manufactured molten cast refractory was evaluated as follows. First, visually inspect the presence or absence of cracks. For refractories with cracks, grind the surface of the refractory to a depth of 10 mm on each surface, cut the resulting refractory from the center, and observe the cut surface. The crack length was evaluated. When the crack length in the refractory after grinding becomes 10 mm or less, the crack at the time of manufacture is “small”, and when the crack length exceeds 10 mm and is 50 mm or less, the crack at the time of manufacture is “medium”. When the crack length exceeded 50 mm, the crack at the time of manufacture was classified as “large”.
  • the open porosity of the manufactured molten cast refractory was evaluated by the Archimedes method according to JIS R1634 (1998).
  • the sample for measurement used what cut out the test piece of 15 mm x 25 mm x 50 mm (length x width x length) from the dense location where a crack is not visually confirmed. Since open pores are one of the causes of bubbles generated during the use of refractory, it is preferable that the open pore ratio is small.
  • the stone formation characteristics of the manufactured molten cast refractories were evaluated as follows.
  • a test piece of 15 mm ⁇ 25 mm ⁇ 50 mm (length ⁇ width ⁇ length) was cut out from the refractory and immersed in soda lime glass (Asahi Glass Co., Ltd., trade name: Clear FL) at 1300 ° C. for 480 hours in an air atmosphere. Thereafter, the test piece was drawn upward at a shear rate of 0.8 / s, held for 5 minutes, and then cooled at a rate of 300 ° C./Hr. After cooling, the test piece covered with glass was cut in half from the center, the cross-section was observed with an optical microscope, and the number of stones that fell from the refractory surface layer to the glass side was counted.
  • the erosion resistance was evaluated as follows. A 15 mm x 25 mm x 50 mm (length x width x length) test piece is cut from the refractory and immersed in soda lime glass (manufactured by Asahi Glass Co., Ltd., trade name: Clear-FL) at 1300 ° C in air for 480 hours. Thereafter, the amount of erosion was measured to examine the erosion resistance.
  • soda lime glass manufactured by Asahi Glass Co., Ltd., trade name: Clear-FL
  • Stone formation amount and erosion resistance are known alumina / zirconia / silica fusion cast refractories widely used in glass manufacturing equipment in the temperature range of 1300 ° C. (trade name: ZB-1691, manufactured by AGC Ceramics)
  • ZB-1691 manufactured by AGC Ceramics
  • the amount of stone formation of this ZB-1691 (Example 23) or the maximum erosion depth of the eroded portion after the erosion test was taken as 100, and the relative amount of stone formation and erosion were shown.
  • the amount of stone generated is small, but if the amount of relative generation with ZB-1691 is 90 or less, the stone generation characteristics are sufficiently improved than before, which is satisfactory.
  • the amount of erosion is small, but in recent years, for example, by placing another alumina, zirconia, siliceous fused cast refractory outside the alumina, zirconia, siliceous fused cast refractory used in the kiln, Since it is possible to extend the life of the melting furnace, the erosion resistance is not necessarily high. Therefore, practically, the erosion resistance is satisfactory when the relative erosion amount with ZB-1691 is 115 or less.
  • Examples 23 and 24 are alumina / zirconia / siliceous fused cast refractories having a known composition, and are refractories having a small composition of Al 2 O 3 / SiO 2 and Na 2 O / SiO 2 . Although the erosion resistance to the glass is almost the same as that of Examples 1 to 22, the amount of stones generated is large due to the lack of the formation component of the nepheline layer.
  • Example 25 is an alumina / zirconia / silica fused cast refractory with a larger Na 2 O / SiO 2 composition, and the erosion resistance to glass is almost the same as in Examples 1 to 22, but Na 2 O / SiO Since 2 is large and a nepheline layer is produced during production, the open porosity is large.
  • Example 26 is alumina-zirconia-silica fusion cast refractory composition with a reduced content of ZrO 2, very corrosion resistance against glass to ZrO 2 content is small as compared with Examples 1 to 22 Low.
  • Example 27 is alumina-zirconia-silica fusion cast refractory compositions that many ZrO 2 content is high in corrosion resistance to glass, is very large cracks during production for ZrO 2 content is high .
  • Example 28 is an alumina / zirconia / siliceous fusion cast refractory with a reduced SiO 2 content. Although the amount of generated stone is small, cracks during production are very large because the SiO 2 content is small.
  • Example 29 is an alumina / zirconia / silica fusion cast refractory having a composition with an increased SiO 2 content. Since the SiO 2 content is large, the erosion resistance is low and the amount of generated stones is large.
  • Examples 30 and 36 are alumina / zirconia / siliceous fused cast refractories having a composition with a reduced Na 2 O content, and a large amount of stones are generated and cracks during production are very large.
  • Example 31 is an alumina / zirconia / silica fusion cast refractory having a composition with an increased Na 2 O content. Although the amount of generated stone is small, the open porosity is large due to the large content of Na 2 O. .
  • Example 32 is an alumina / zirconia / siliceous fusion cast refractory having a composition with a high Al 2 O 3 content. Although the amount of generated stone is small, cracks during production are very large.
  • Example 33 is an alumina / zirconia / siliceous fused cast refractory with a composition having a low Al 2 O 3 content, which has high erosion resistance, but has a large amount of stones generated and very large cracks during production. .
  • Example 34 is an alumina / zirconia / silica fused cast refractory having a composition with an increased content of Li 2 O, CaO, and K 2 O, respectively. Large amount. Further, Na 2 O / SiO 2 is large and the open porosity is relatively large.
  • Examples 35 and 36 are alumina / zirconia / silica fusion cast refractories having a composition with an essential component content of less than 85%, because the contents of Al 2 O 3 and ZrO 2 in the refractories are small. , Low erosion resistance to glass and a large amount of stones.
  • Example 37 is an alumina / zirconia / siliceous fused cast refractory having a composition with reduced ZrO 2 content and Na 2 O content. Since the content of ZrO 2 in the refractory is low, corrosion resistance to glass It has low properties, has a large amount of stones, and has very large cracks during production.
  • Examples 1 to 22 which are examples of the present invention, are alumina / zirconia / silica fusion cast refractories containing a predetermined amount of components. Compared with Examples 23 to 37, the amount of generated stones and corrosion resistance And the manufacturing characteristics are good results. More specifically, compared to conventional alumina / zirconia / silica fused cast refractories, the amount of stone formation is small and the erosion resistance is practically satisfactory, and there are no cracks during production or cracks. Even if it exists, it is medium or less, and the open porosity is 1% or less.
  • Example 2 Example 5, Example 6, Example 8, Example 10, Example 11, and Examples 13 to 21 were prepared by using alumina, zirconia, and a composition having relatively large compositions of Al 2 O 3 / SiO 2 and Na 2 O / SiO 2.
  • Silica fusion cast refractory with low stone production. In addition, it has good erosion resistance and has no more cracks during production.
  • Example 5, Example 6, Example 10, and Example 13 since ZrO 2 / (Al 2 O 3 + ZrO 2 ) is in a more preferable range, the amount of generated stone is particularly small.
  • Example 1 Example 4, Example 7, Example 9, Example 12 and Example 22 are alumina / zirconia / siliceous fusion cast refractories having a relatively small composition of Al 2 O 3 / SiO 2 within the scope of the present invention.
  • the effect of suppressing the occurrence of stone is maintained, the erosion resistance is good, and there are few manufacturing cracks.
  • Example 3 is an alumina / zirconia / silica fusion cast refractory having a composition in which Na 2 O / SiO 2 is reduced within the scope of the present invention.
  • the effect of suppressing the generation of stone is maintained, and the erosion resistance is maintained. It is good, has few manufacturing cracks, and has a low open porosity.
  • the generation of stones in the molten glass is suppressed. Moreover, since it has high erosion resistance with respect to glass, glass can be stably melted, and a glass plate with good quality can be manufactured with high yield.
  • the alumina / zirconia / siliceous fusion cast refractory of the present invention suppresses the occurrence of stones in the glass, and also has high erosion resistance against the glass, it can be easily manufactured with high productivity.

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Abstract

La présente invention concerne une alumine-zircone-silice réfractaire coulé par fusion qui supprime l'apparition de pierres en verre et a une résistance à la corrosion élevée contre le verre. Cette alumine-zircone-silice réfractaire coulé par fusion comprend Al2O3, ZrO2, SiO2, et Na2O en tant que constituants essentiels et est caractérisé par le fait qu'il contient, en % en masse en termes d'oxydes, 30% ≤ Al2O3 ≤ 75%, 22% ≤ ZrO2 ≤ 50%, 2,0% < SiO2 ≤ 10,0%, 0,5% ≤ Na2O < 2,5%, dans lequel Al2O3/SiO2 ≥ 6,6, 0,08 ≤ Na2O/SiO2 < 0,25, et la teneur de ces constituants principaux est égal ou supérieur à 85%.
PCT/JP2015/069252 2014-07-24 2015-07-03 Alumine-zircone-silice réfractaire coulé par fusion, four de fusion du verre, et procédé de production de plaque de verre Ceased WO2016013384A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019115466A1 (fr) 2017-12-11 2019-06-20 Saint-Gobain Centre De Recherches Et D'etudes Europeen Procédé d'identification de la classe de réfractaires électrofondus azs générant des « pierres » dans un produit verrier
CN111278789A (zh) * 2017-11-07 2020-06-12 旭硝子陶瓷株式会社 氧化铝/氧化锆/二氧化硅质熔融铸造耐火物和玻璃熔融窑
CN112225543A (zh) * 2020-10-12 2021-01-15 郑州方铭高温陶瓷新材料有限公司 一种应用于玻璃窑炉蓄热室的熔铸成型筒型陶瓷砖及其制备方法
CN115368118A (zh) * 2022-09-21 2022-11-22 淄博艾杰旭刚玉材料有限公司 超低气泡析出率azs电熔砖及其制备方法
WO2023182007A1 (fr) * 2022-03-25 2023-09-28 サンゴバン・ティーエム株式会社 Matériau réfractaire coulé électrofondu à haute teneur en zircone

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JPH1072264A (ja) * 1996-08-30 1998-03-17 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物の製造方法
JPH10101439A (ja) * 1996-10-01 1998-04-21 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物
JPH11343174A (ja) * 1998-02-26 1999-12-14 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物およびそれを使用したガラス溶融窯

Patent Citations (3)

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JPH1072264A (ja) * 1996-08-30 1998-03-17 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物の製造方法
JPH10101439A (ja) * 1996-10-01 1998-04-21 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物
JPH11343174A (ja) * 1998-02-26 1999-12-14 Asahi Glass Co Ltd アルミナ・ジルコニア・シリカ質溶融耐火物およびそれを使用したガラス溶融窯

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111278789A (zh) * 2017-11-07 2020-06-12 旭硝子陶瓷株式会社 氧化铝/氧化锆/二氧化硅质熔融铸造耐火物和玻璃熔融窑
CN111278789B (zh) * 2017-11-07 2022-12-27 旭硝子陶瓷株式会社 氧化铝/氧化锆/二氧化硅质熔融铸造耐火物和玻璃熔融窑
WO2019115466A1 (fr) 2017-12-11 2019-06-20 Saint-Gobain Centre De Recherches Et D'etudes Europeen Procédé d'identification de la classe de réfractaires électrofondus azs générant des « pierres » dans un produit verrier
CN112225543A (zh) * 2020-10-12 2021-01-15 郑州方铭高温陶瓷新材料有限公司 一种应用于玻璃窑炉蓄热室的熔铸成型筒型陶瓷砖及其制备方法
WO2023182007A1 (fr) * 2022-03-25 2023-09-28 サンゴバン・ティーエム株式会社 Matériau réfractaire coulé électrofondu à haute teneur en zircone
CN115368118A (zh) * 2022-09-21 2022-11-22 淄博艾杰旭刚玉材料有限公司 超低气泡析出率azs电熔砖及其制备方法
CN115368118B (zh) * 2022-09-21 2023-05-16 淄博艾杰旭刚玉材料有限公司 超低气泡析出率azs电熔砖及其制备方法

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