WO2025154809A1 - Matériau réfractaire électroformé, procédé de production de matériau réfractaire électroformé, et four de fusion du verre - Google Patents

Matériau réfractaire électroformé, procédé de production de matériau réfractaire électroformé, et four de fusion du verre

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Publication number
WO2025154809A1
WO2025154809A1 PCT/JP2025/001432 JP2025001432W WO2025154809A1 WO 2025154809 A1 WO2025154809 A1 WO 2025154809A1 JP 2025001432 W JP2025001432 W JP 2025001432W WO 2025154809 A1 WO2025154809 A1 WO 2025154809A1
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WO
WIPO (PCT)
Prior art keywords
mass
refractory material
less
total
refractory
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/001432
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English (en)
Japanese (ja)
Inventor
壮真 野村
ジャワード サーワー
健児 俣野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Ceramics Co Ltd
Original Assignee
AGC Ceramics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AGC Ceramics Co Ltd filed Critical AGC Ceramics Co Ltd
Publication of WO2025154809A1 publication Critical patent/WO2025154809A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/484—Refractories by fusion casting
    • 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

Definitions

  • This disclosure relates to electrocast refractories, a method for manufacturing electrocast refractories, and a glass melting furnace.
  • High-zirconia electrocast refractories containing a large amount of ZrO2 as a chemical component are known.
  • High-zirconia electrocast refractories have high corrosion resistance and low contamination against molten glass, and are therefore often used in parts that come into contact with molten glass in glass melting furnaces.
  • Such high-zirconia electrocast refractories contain a large amount of zirconia crystal grains and a small amount of matrix glass between the grains.
  • Patent Documents 1 to 9 propose high-zirconia refractories containing various components in specific proportions in addition to ZrO2 .
  • ZrO2 undergoes transformation expansion due to phase transition between monoclinic and tetragonal crystals at around 1150°C during heating and at around 850°C during cooling, resulting in a large volume change with heating and cooling.
  • the matrix glass filling the gaps in ZrO2 plays a role in mitigating the stress caused by the volume change of ZrO2 .
  • the volume change during heating and cooling is large, it can cause cracks in the refractory, so it is desirable to reduce the expansion coefficient after the temperature cycle, i.e., the residual volume expansion coefficient.
  • the matrix glass in the refractory may seep into the molten glass at the contact points between the refractory and the molten glass (also known as "glass seepage"). Glass seepage can cause defects in the resulting glass product.
  • Means for solving the above problems include the following aspects. ⁇ 1> Chemical composition, on an oxide basis, with the total of oxides being 100% by mass, ZrO2 is 85.0% by mass or more, SiO2 : 8.0 to 12.0% by mass, Al 2 O 3 is 0.10 mass% or more and less than 0.80 mass%; P2O5 : 0.01 to 1.0 mass%; Na 2 O and/or K 2 O in a total amount of 0.10 to 0.20 mass %, B2O3 : 0.05 to 2.0 mass% Including, An electrocast refractory material having a total content of Fe2O3 and TiO2 of less than 0.55% by mass.
  • the refractory may or may not independently contain components other than the above-mentioned components (i.e., ZrO2, SiO2, Al2O3, P2O5 , Na2O , K2O , B2O3 , Fe2O3 , TiO2 ).
  • components derived from the raw materials other than the above-mentioned components include CaO, MgO, SrO, BaO, CuO, Y2O3 , ZnO, etc.
  • the total amount of components other than the above-mentioned components is preferably 0.7 mass% or less, more preferably 0.5 mass% or less , even more preferably 0.4 mass% or less, particularly preferably 0.2 mass% or less, extremely preferably 0.1 mass% or less, even more preferably less than 0.1 mass%, and even more preferably 0.05 mass% or less.
  • CuO may be contained as an impurity in refractory raw materials.
  • the amount of CuO is preferably small.
  • the amount of CuO is preferably 0.1 mass% or less, more preferably 0.05 mass% or less, and further preferably 0.01 mass% or less.
  • MgO and CaO may also be contained as impurities in the refractory raw materials. From the viewpoint of suppressing the decrease in the electrical resistance efficiency, it is preferable that the amount of MgO and CaO is small, and each independently is preferably 0.1 mass% or less, and more preferably 0.05 mass% or less.
  • Y 2 O 3 may be contained as an impurity in the refractory raw material.
  • the amount of Y 2 O 3 is preferably small, preferably 0.3 mass% or less, and more preferably 0.2 mass% or less.
  • high electrical resistivity , low residual volume expansion coefficient, and suppression of glass exudation can be achieved without intentionally adding components such as V2O5 , CrO3 , Nb2O5 , MoO3 , Ta2O5 , WO3 , and SnO2 described in Patent Documents 7 and 8.
  • the total mass of V2O5 , CrO3 , Nb2O5 , MoO3 , Ta2O5 , WO3 , and SnO2 on an oxide basis may be less than 0.01 mass% and may be 0.005 mass% or less, with the total of the oxides being 100 mass%.
  • the refractory preferably has a chemical composition based on oxides, the total of the oxides being 100 mass%.
  • Al 2 O 3 0.10 to 0.70 mass %
  • P2O5 0.01 to 0.5 mass%
  • the refractory has a chemical composition based on oxides, the total of oxides being 100 mass%.
  • Al 2 O 3 0.10 to 0.60 mass %, P2O5 : 0.01 to 0.3 mass%; Contains 0.50% to 1.3% by mass of B 2 O 3 .
  • the refractory preferably has a chemical composition based on oxides, the total of the oxides being 100 mass%.
  • ZrO2 is 85.0% by mass or more, SiO2 : 8.0 to 12.0% by mass, Al 2 O 3 0.10 to 0.65 mass% P2O5 : 0.01 to 0.15 mass% B2O3 : 0.50 to 1.0 mass% Including, The total amount of Fe2O3 and TiO2 is 0.30 mass% or less.
  • the refractory can be produced by heating and melting refractory raw materials and cooling them in a mold.
  • the method for producing a refractory material comprises, relative to the total mass of oxides, ZrO2 is 85.0% by mass or more, SiO2 : 8.0 to 12.0% by mass, Al 2 O 3 is 0.10 mass% or more and less than 0.80 mass%; P2O5 : 0.01 to 1.0 mass%; Na 2 O and/or K 2 O in a total amount of 0.10 mass % to 0.20 mass %, 0.05% to 2.0% by mass of B 2 O 3 Including, The method includes heating and melting a refractory raw material having a total content of Fe2O3 and TiO2 of less than 0.55 mass%, and then cooling the refractory raw material in a mold. The details of each component contained in the refractory raw material are as described above.
  • the refractory is manufactured, for example, by mixing the powder raw materials in the above-mentioned blending ratio, melting them in an electric arc furnace, forcing the molten raw materials into a graphite mold, and cooling them.
  • the refractory manufactured by melt casting in this way tends to have excellent corrosion resistance because the ZrO2 crystal structure is dense and the crystal size is large. Heating during melting is performed, for example, by contacting the raw material powder with a graphite electrode and passing electricity through the electrode.
  • the electrical resistivity of the refractory material at 1600° C. is preferably 300 ⁇ cm or more, more preferably 350 ⁇ cm or more, even more preferably 400 ⁇ cm or more, and particularly preferably 450 ⁇ cm or more.
  • the upper limit of the electrical resistivity is not particularly limited, and may be, for example, 1000 ⁇ cm.
  • the electrical resistivity is measured using an AC voltage of 120 Hz with a three-terminal electrode configuration equipped with a guard electrode.
  • the residual volume expansion coefficient determined as follows is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 4% or less.
  • a thermal cycle test is carried out on the refractory material, in which the temperature is increased from 800° C. to 1250° C. at 450° C./h and then decreased from 1250° C. to 800° C. at 450° C./h, and this cycle is repeated 40 times.
  • the heating from room temperature (about 25° C.) to 800° C. and the cooling from 800° C. to room temperature (about 25° C.) are carried out at a rate of about 160° C./h.
  • the bulk density of the refractory material is preferably 4.7 g/cm 3 or more, more preferably 4.8 g/cm 3 or more, and even more preferably 4.9 g/cm 3 or more.
  • the bulk density is measured by the Archimedes method.
  • the porosity of the refractory is preferably 1.5% or less.
  • a porosity of 0.1 to 1% is more preferable. Porosity is measured by the Archimedes method.
  • the glass melting furnace contains the refractory material of the present disclosure described above.
  • the refractory material of the present disclosure in the area that comes into contact with the molten glass of the glass melting furnace, for example, the electrode installation area and its surroundings.
  • desiliconized zirconia, alumina, zircon sand, silica, sodium carbonate, potassium carbonate, boron phosphate, and boron oxide were mixed to obtain a refractory raw material.
  • the refractory raw material was melted by electric heating using a so-called arc method in which a graphite electrode was raised from the surface of the molten metal.
  • the molten refractory raw material was poured into a graphite mold that had been previously embedded in Bayer alumina or silica sand, which was a cooling material, and cast, and was allowed to cool to a temperature near room temperature (about 25°C).
  • the mold was prepared so that a rectangular refractory of 130 mm x 160 mm x 300 mm was obtained in Examples 1 to 7 and 10 to 15, and 125 mm x 575 mm x 950 mm was obtained in Examples 8 and 9.
  • the ingot and the graphite mold were removed from the cooling material, and the graphite mold and the ingot were separated to obtain a refractory.
  • Glass Exudation A cylindrical sample having a diameter of 30 mm and a height of 30 mm was cut out using a diamond core drill, and then fired in an electric furnace at 1500° C. for 16 hours and then allowed to cool naturally within the furnace. The sample was visually observed for the presence or absence of glass exudation before and after firing.
  • composition of the components is expressed as the percentage (mass%) of each component when the total of the oxides is 100 mass% on an oxide basis as a chemical composition. "-" in the composition of the components indicates that the corresponding component was not detected, and "-" in the evaluation indicates that the corresponding evaluation was not performed or could not be measured.
  • Na2O + K2O represents the total percentage (mass%) of Na2O and K2O
  • Fe2O3 + TiO2 represents the total percentage (mass%) of Fe2O3 and TiO2
  • ( Na2O + K2O )/ SiO2 represents the value obtained by dividing the total mass of Na2O and K2O by the mass of SiO2
  • ( B2O3 +P2O5 ) / Al2O3 represents the value obtained by dividing the total mass of B2O3 and P2O5 by the mass of Al2O3 .
  • Numbers in parentheses in the table are values with one decimal place added.
  • the total mass of V2O5 , CrO3 , Nb2O5 , MoO3 , Ta2O5 , WO3 , and SnO2 on an oxide basis was less than 0.01 mass%, with the total of the oxides being 100 mass%.
  • the refractory material of Example 1 in which the total ratio of Na 2 O and K 2 O was low, had a high residual volume expansion coefficient.
  • the refractory material of Example 2 in which the total ratio of Na 2 O and K 2 O was low, had a high residual volume expansion coefficient and glass exudation was observed after firing.
  • the refractory material of Example 3 which has a low total ratio of Na 2 O and K 2 O, glass exudation was observed after firing.
  • glass exudation was observed after firing.
  • Example 10 the proportion of P 2 O 5 was low, and the total proportion of Na 2 O and K 2 O was high, and a high coefficient of permanent volume expansion and a low electrical resistivity were observed.
  • Example 11 the proportion of B 2 O 3 was high, the coefficient of permanent volume expansion was high, and glass exudation was observed.
  • Example 12 the total proportion of Na 2 O and K 2 O was high and the electrical resistivity was low.
  • Example 15 the proportion of SiO2 was low, and the total proportion of Na2O and K2O was low, so the volume expansion was large and the residual volume expansion rate could not be measured. Glass exudation was also observed. Furthermore, the electrical resistivity was high.
  • the present disclosure includes the following aspects. ⁇ 1> Chemical composition, on an oxide basis, with the total of oxides being 100% by mass, ZrO2 is 85.0% by mass or more, SiO2 : 8.0 to 12.0% by mass, Al 2 O 3 is 0.10 mass% or more and less than 0.80 mass%; P2O5 : 0.01 to 1.0 mass%; Na 2 O and/or K 2 O in a total amount of 0.10 to 1.0 mass %, B2O3 : 0.05 to 3.0 mass% Including, An electrocast refractory material having a total content of Fe2O3 and TiO2 of less than 0.55% by mass.
  • Residual volume expansion rate (%) ⁇ (volume after thermal cycle test/volume before thermal cycle test) ⁇ 1 ⁇ 100 ⁇ 10>
  • a glass melting furnace comprising the electrocast refractory material according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> Relative to the total mass of oxides, ZrO2 is 85.0% by mass or more, SiO2 : 8.0 to 12.0% by mass, Al 2 O 3 is 0.10 mass% or more and less than 0.80 mass%; P2O5 : 0.01 to 1.0 mass%; Na 2 O and/or K 2 O in a total amount of 0.10 mass % to 1.0 mass %, 0.05% by mass to 3.0% by mass of B 2 O 3
  • a method for producing an electrocast refractory comprising heating and melting a refractory raw material having a total content of Fe2O3 and TiO2 of less than 0.55 mass%, and then cooling the refractory raw material in a mold.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

L'invention concerne un matériau réfractaire électroformé ayant une composition chimique comprenant, en termes d'oxydes, pas moins de 85,0 % en masse de ZrO2, 8,0 à 12,0 % en masse de SiO2, pas moins de 0,10 % en masse mais moins de 0,80 % en masse d'Al2O3, 0,01 à 1,0 % en masse de P2O5, 0,10 à 0,20 % en masse du total de Na2O et/ou K2O, et 0,05 à 2,0 % en masse de B2O3, où le total d'oxydes est de 100 % en masse, et la quantité totale de Fe2O3 et de TiO2 est de moins de 0,55 % en masse. L'invention concerne également un procédé de production du matériau réfractaire électroformé et un four de fusion du verre qui utilise le matériau réfractaire électroformé.
PCT/JP2025/001432 2024-01-18 2025-01-17 Matériau réfractaire électroformé, procédé de production de matériau réfractaire électroformé, et four de fusion du verre Pending WO2025154809A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024006270 2024-01-18
JP2024-006270 2024-01-18

Publications (1)

Publication Number Publication Date
WO2025154809A1 true WO2025154809A1 (fr) 2025-07-24

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PCT/JP2025/001432 Pending WO2025154809A1 (fr) 2024-01-18 2025-01-17 Matériau réfractaire électroformé, procédé de production de matériau réfractaire électroformé, et four de fusion du verre

Country Status (1)

Country Link
WO (1) WO2025154809A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287059A (ja) * 1993-02-03 1994-10-11 Asahi Glass Co Ltd 高ジルコニア質溶融鋳造耐火物
JPH08277162A (ja) * 1995-04-06 1996-10-22 Toshiba Monofrax Co Ltd 高ジルコニア溶融耐火物
JPH092870A (ja) * 1995-06-20 1997-01-07 Toshiba Monofrax Co Ltd 高ジルコニア電鋳煉瓦
JP2009155150A (ja) * 2007-12-26 2009-07-16 Saint-Gobain Tm Kk 高電気抵抗高ジルコニア鋳造耐火物
WO2010116960A1 (fr) * 2009-04-06 2010-10-14 旭硝子株式会社 Matériau réfractaire à forte base de zircone et four de fusion
WO2012046785A1 (fr) * 2010-10-06 2012-04-12 旭硝子株式会社 Produit réfractaire à teneur élevée de zircone
WO2015025901A1 (fr) * 2013-08-21 2015-02-26 Saint-Gobain Tm K.K. Produit réfractaire électrofondu à haute teneur en zircone
WO2016125317A1 (fr) * 2015-02-02 2016-08-11 Saint-Gobain Tm K.K. Matériau réfractaire coulé, électrofondu, à haute teneur en zircone
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287059A (ja) * 1993-02-03 1994-10-11 Asahi Glass Co Ltd 高ジルコニア質溶融鋳造耐火物
JPH08277162A (ja) * 1995-04-06 1996-10-22 Toshiba Monofrax Co Ltd 高ジルコニア溶融耐火物
JPH092870A (ja) * 1995-06-20 1997-01-07 Toshiba Monofrax Co Ltd 高ジルコニア電鋳煉瓦
JP2009155150A (ja) * 2007-12-26 2009-07-16 Saint-Gobain Tm Kk 高電気抵抗高ジルコニア鋳造耐火物
WO2010116960A1 (fr) * 2009-04-06 2010-10-14 旭硝子株式会社 Matériau réfractaire à forte base de zircone et four de fusion
WO2012046785A1 (fr) * 2010-10-06 2012-04-12 旭硝子株式会社 Produit réfractaire à teneur élevée de zircone
WO2015025901A1 (fr) * 2013-08-21 2015-02-26 Saint-Gobain Tm K.K. Produit réfractaire électrofondu à haute teneur en zircone
WO2016125317A1 (fr) * 2015-02-02 2016-08-11 Saint-Gobain Tm K.K. Matériau réfractaire coulé, électrofondu, à haute teneur en zircone
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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