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WO2012157432A1 - Procédé de production de verre fondu, four de fusion pour verre, procédé de production d'un article en verre et dispositif afférent - Google Patents

Procédé de production de verre fondu, four de fusion pour verre, procédé de production d'un article en verre et dispositif afférent Download PDF

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Publication number
WO2012157432A1
WO2012157432A1 PCT/JP2012/061269 JP2012061269W WO2012157432A1 WO 2012157432 A1 WO2012157432 A1 WO 2012157432A1 JP 2012061269 W JP2012061269 W JP 2012061269W WO 2012157432 A1 WO2012157432 A1 WO 2012157432A1
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WO
WIPO (PCT)
Prior art keywords
glass
molten glass
raw material
gas phase
heated gas
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.)
Ceased
Application number
PCT/JP2012/061269
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English (en)
Japanese (ja)
Inventor
達也 山下
千禾夫 田中
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 Inc
Original Assignee
Asahi Glass 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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to KR1020137027054A priority Critical patent/KR101965003B1/ko
Priority to CN201280022826.7A priority patent/CN103534214B/zh
Priority to JP2013515065A priority patent/JP5971241B2/ja
Publication of WO2012157432A1 publication Critical patent/WO2012157432A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting furnaces
    • C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
    • C03B3/026—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet by charging the ingredients into a flame, through a burner or equivalent heating means used to heat the melting furnace
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting furnaces
    • C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
    • 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
    • C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
    • C03B5/025—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by arc discharge or plasma heating
    • 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
    • C03B5/12—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in shaft furnaces
    • 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
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/183—Stirring devices; Homogenisation using thermal means, e.g. for creating convection currents
    • 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
    • C03B5/235—Heating the glass
    • C03B5/2353—Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping

Definitions

  • the present invention relates to a molten glass manufacturing method, a glass melting furnace, a glass article manufacturing method, and a glass article manufacturing apparatus.
  • a Siemens type that melts glass raw materials in a glass melting furnace (hereinafter also referred to simply as a melting furnace). It is produced based on a melting furnace (Siemensementype furnace).
  • a melting furnace Siemens-type melting furnace
  • a mixture of powdered glass raw materials is charged on the surface of the glass melt previously melted in the melting furnace, and the mixture becomes a lump (hereinafter also referred to as a batch). It is heated by a burner or the like to cause melting to proceed from the surface to gradually form a glass melt.
  • FIG. 5 is a schematic cross-sectional view showing the melting furnace described in Patent Document 1.
  • Melting furnace 100 of Patent Document 1 as the heating means for forming a high-temperature gas-phase atmosphere K 100, and includes a plurality of arc electrode 102 and the oxygen combustion nozzle 103.
  • a high-temperature gas phase atmosphere K 100 of about 1600 ° C. or higher is formed in the furnace body 101 by a thermal plasma arc formed by the plurality of arc electrodes 102 and / or an oxyfuel flame (frame) F 100 by the oxyfuel nozzle 103.
  • the air melting method has an advantage that a glass melt can be produced in a short time by heating and melting at a high temperature by passing the glass raw material particles through a high temperature gas phase atmosphere.
  • the present inventors have studied, and aiming for rapid melting in a short time, if the glass raw material particles are heated at an excessively high temperature, the fining agent contained in the glass raw material particles disappears due to excessive heat. It turned out that there was a case.
  • the glass melt storing the liquid glass particles in the state where the fining agent has disappeared does not exhibit the effect of defoaming by the fining agent in the glass melt, and when a lot of bubbles are mixed, It takes time to perform the defoaming process.
  • the temperature of the gas phase atmosphere is lowered too much to prevent the fining agent from disappearing, the liquid glass particles are not sufficiently melted due to insufficient heating, and the clarification in the glass melt is not promoted. It may be in the state.
  • an object of the present invention is to provide a molten glass manufacturing method and a glass melting furnace capable of manufacturing a molten glass having a high bubble quality with few bubbles. Moreover, this invention aims at provision of the manufacturing method of the glass article using the manufacturing method of the above-mentioned molten glass. Furthermore, this invention aims at provision of the manufacturing apparatus of the glass article provided with the above-mentioned glass melting furnace.
  • the present inventors diligently studied on a method capable of heating glass raw material particles with an appropriate temperature history in order to produce a high-foam quality molten glass with few bubbles, and reached the present invention.
  • the present invention forms two or more heated gas phase atmospheres arranged in the vertical direction, supplies glass raw material particles to the uppermost heated gas phase atmosphere, and passes the glass raw material particles through the two or more heated gas phase atmospheres
  • grains by providing is provided.
  • the first heated vapor phase atmosphere is formed in the uppermost stage among the two or more heated vapor phase atmospheres, and the last heating is performed in the lowermost stage among the two or more heated vapor phase atmospheres.
  • the glass raw material particles preferably contain a fining agent component.
  • the temperature of the first heated gas phase atmosphere is preferably not less than the vitrification start temperature of the glass raw material particles and not more than 1500 ° C.
  • the temperature of the final heated gas phase atmosphere is preferably not less than the clarification start temperature of the fining agent component in the glass raw material particles and not more than 20000 ° C.
  • the tip of the heat source generating part of the heating means for forming the first heated vapor phase atmosphere and the liquid level of the molten glass that stores the molten glass particles to form molten glass When the vertical distance is H, the last heated gas phase atmosphere is preferably formed within 0.5H above the liquid surface of the molten glass.
  • the present invention includes a furnace body that contains molten glass, a glass raw material particle introduction portion that is disposed on the upper portion of the furnace body, and that introduces glass raw material particles inside the furnace body, and a lower portion of the glass raw material particle introduction portion.
  • a glass melting furnace provided with heating means for forming two or more heated gas phase atmospheres for heating and melting the glass raw material particles into molten glass particles so as to be arranged in the vertical direction.
  • the heating means includes first heating means for forming a heated gas phase atmosphere for first melting glass raw material particles in the uppermost stage of the two or more heated gas phase atmospheres; It is preferable to include a last heating unit that forms a heated gas phase atmosphere for melting glass raw material particles at the bottom of the two or more heated gas phase atmospheres.
  • the first heating means may be a combustion burner.
  • the last heating means may be a multi-phase arc plasma generator comprising a combustion burner and / or a plurality of electrodes.
  • the first heating means may be disposed downwardly on the top of the furnace body.
  • the vertical distance between the tip of the heat source generating portion of the first heating means and the liquid level of the molten glass that stores the molten glass particles in the furnace body to form molten glass is H.
  • the last heating means is preferably arranged such that the last heated gas phase atmosphere is within 0.5H above the liquid surface of the molten glass.
  • the present invention includes a step of producing a molten glass using the method for producing a molten glass according to any one of the above, a step of forming the molten glass, and a step of gradually cooling the glass after forming.
  • a method for manufacturing an article is provided.
  • the present invention provides a glass article comprising: the glass melting furnace according to any one of the above; a forming means for forming the molten glass produced by the glass melting furnace; and a slow cooling means for gradually cooling the glass after forming. Providing manufacturing equipment.
  • the method for producing molten glass and the glass melting furnace of the present invention have a configuration in which glass raw material particles are passed through two or more heated gas phase atmospheres to form molten glass particles. Therefore, the temperature of each heated gas phase atmosphere is adjusted, the upper heated gas phase atmosphere is set to a temperature at which the fining agent in the glass raw material particles does not disappear, and the lower heated gas phase atmosphere is the molten glass in which the molten glass particles are stored. Immediately after falling, it can be set to a temperature at which the fining effect of the fining agent is well expressed. Thereby, defoaming of a molten glass particle is accelerated
  • the glass raw material particles can be sequentially passed through two or more heated gas-phase atmospheres, after melting the glass raw material particles in the upper heated gas-phase atmosphere, the melting is further promoted in the lower heated gas-phase atmosphere.
  • the lack of melting can be resolved and the molten glass particles having a higher specific gravity can be obtained. Therefore, in the method for producing molten glass of the present invention, the molten glass particles are less scattered and the vitrification rate is improved.
  • the method for producing molten glass of the present invention can reduce molten glass particles that fly down and scatter and adhere to the wall of the furnace body, so that damage to the furnace material is reduced.
  • the manufacturing method of the glass article of this invention can provide a high quality glass article by using the manufacturing method of the above-mentioned molten glass.
  • the apparatus for producing a glass article of the present invention can produce a high-quality glass article by including the glass melting furnace described above.
  • FIG. 1 is a cross-sectional view schematically showing a first embodiment of a glass melting furnace according to the present invention.
  • FIG. 2 is a sectional view schematically showing a second embodiment of the glass melting furnace according to the present invention.
  • FIG. 3 is a sectional view schematically showing a third embodiment of the glass melting furnace according to the present invention.
  • FIG. 4 is a flowchart showing an example of a method for producing a glass article using the method for producing molten glass according to the present invention.
  • FIG. 5 is a schematic cross-sectional view showing the glass melting furnace described in Patent Document 1. As shown in FIG.
  • the first heating means for forming the first heated vapor atmosphere (hereinafter referred to as “first heated vapor atmosphere”) is a combustion burner. More specifically, it comprises an oxyfuel burner.
  • the first heated gas phase atmosphere is formed from a high temperature atmosphere in and near the oxyfuel flame of the oxyfuel burner.
  • a glass raw material particle charging portion for supplying glass raw material particles to a heated gas phase atmosphere in the furnace body is integrated with an oxyfuel burner as a first heating means, and a tube for supplying combustion gas in the vicinity of the oxyfuel burner outlet.
  • a tube for supplying oxygen and a tube for supplying glass raw material particles are configured coaxially.
  • the combination of the glass raw material particle charging portion and the oxygen combustion burner is referred to as a glass raw material particle heating unit.
  • the last heating means (that is, the lowest heating means on the molten glass side) that forms the lowest heated gas phase atmosphere generates a combustion burner (more specifically, an oxyfuel combustion burner) and / or a thermal plasma.
  • a multi-phase arc plasma generator comprising a plurality of electrodes.
  • the last heating means is an oxyfuel combustion burner
  • the last heated gas phase atmosphere is formed from a high temperature atmosphere in the oxyfuel combustion flame of the oxyfuel combustion burner and in the vicinity of the oxyfuel combustion flame.
  • the last heating means is a thermal plasma generator
  • the last heated vapor phase atmosphere is formed from thermal plasma and a high temperature atmosphere near the thermal plasma.
  • the heated gas phase atmosphere refers to a gas combustion region if it is an oxyfuel burner, and refers to a region where plasma is generated if it is thermal plasma. If it is by other heating means, the area has a temperature sufficient to melt the glass raw material particles or further melt the molten glass particles that have not been melted compared to the surrounding atmosphere by that means.
  • FIG. 1 is a cross-sectional view schematically showing a first embodiment of a glass melting furnace according to the present invention.
  • the glass melting furnace shown in FIG. 1 is used in the method for manufacturing molten glass and the method for manufacturing glass articles according to the present invention.
  • a glass melting furnace 30 shown in FIG. 1 is a furnace for forming a first heated gas-phase atmosphere K1 by ejecting a hollow box-shaped furnace body 1 and glass raw material particles GM and an oxyfuel flame F1.
  • the glass raw material particle heating unit 10 disposed downward through the furnace wall portion 1A of the upper portion of the body 1 and the oxyfuel combustion flame F2 are ejected to form the second heated vapor phase atmosphere K2 as the first heated vapor phase atmosphere.
  • An oxyfuel combustion burner 20 that is disposed obliquely downward through the side wall 1C of the furnace body 1 and a storage portion 1B for molten glass G formed at the bottom of the furnace body 1 is provided to form the bottom of K1.
  • the glass raw material particle heating unit 10 can form a first heated gas-phase atmosphere K1 on the front end side in the injection direction of the combustion flame (lower side in FIG. 1).
  • the oxyfuel burner 20 as the second heating means penetrates the central portion in the height direction of the side wall 1C so that the second heated gas phase atmosphere K2 can be formed below the first heated gas phase atmosphere K1. It is provided diagonally downward.
  • the oxyfuel burner 20 as the second heating means is the last heating means, and the second heated vapor phase atmosphere K2 is the last heated vapor phase atmosphere.
  • the glass raw material particle heating unit 10 will be described later.
  • the upper part of the furnace body 1 means a range including the upper part of the furnace wall 1A and the side wall 1C of the furnace body 1.
  • the shape of the furnace body 1 is not limited to the box-shaped rectangular parallelepiped shape shown in FIG. 1, and may be configured in a cylindrical shape.
  • the glass raw material particle heating unit 10 is installed in the vertical direction downward in FIG. 1, the present invention is not limited to this, and the glass raw material particle heating unit 10 may be installed inclined if it is downward.
  • the furnace wall part 1A of the furnace body 1 was made into a flat shape, not only this but shapes, such as an arch shape and a dome shape, may be sufficient.
  • the oxyfuel burner 20 is installed obliquely downward.
  • the present invention is not limited to this. If the second heated vapor phase atmosphere K2 can be formed below the first heated vapor phase atmosphere K1, the oxyfuel combustion burner 20 is inclined upward or horizontally laterally. You may install in.
  • the bottom side of the furnace body 1 is a storage part 1B for the molten glass G.
  • the molten glass G is externally supplied from the furnace body 1 through a molten glass discharge port 4 formed on the bottom side of the side wall 1C of the furnace body 1. It is configured so that it can be discharged.
  • the glass article manufacturing apparatus including the glass melting furnace 30 of the present embodiment is connected, as an example, to a molding apparatus 50 including a molding unit on the downstream side in the direction of discharging the molten glass G from the furnace body 1.
  • the molten glass G is formed into a target shape by the forming apparatus 50 so that a glass article can be obtained.
  • a vacuum degassing apparatus may be provided before the molding apparatus 50.
  • the manufacturing apparatus of a glass article has a slow cooling means which anneals the glass after shaping
  • the glass article manufacturing apparatus of the present invention can apply known molding means and slow cooling means, and other known addition means, in addition to using the glass melting furnace according to the present invention described above. it can.
  • the furnace body 1 is made of a refractory material such as a refractory brick, and is configured to store high-temperature molten glass G. Although not shown in the storage part 1B of the furnace body 1, a heater is installed, and the molten glass G stored in the storage part 1B is melted to a target temperature (for example, about 1400 ° C.) as necessary. It is configured so that it can be held.
  • An exhaust gas treatment device 3 is connected to a side wall portion of the storage portion 1B via an exhaust port 2 and an exhaust pipe 2a.
  • an oxyfuel burner 11 in which a glass raw material particle charging portion is integrally formed at the tip portion 12 is applied.
  • this oxyfuel combustion burner 11 an oxyfuel combustion burner known as an inorganic powder heating burner, in which raw materials, fuel gas, and combustion gas supply nozzles are appropriately arranged, can be used.
  • the oxycombustion burner 11 is configured in a straight tube shape, and a tip 12 thereof has a fuel supply nozzle, a primary combustion gas supply nozzle, a glass raw material particle supply nozzle that is a glass raw material particle supply portion from the center to the outer periphery, and Secondary combustion gas supply nozzles are arranged concentrically.
  • the oxyfuel burner 11 is not limited to a structure in which the supply nozzles are arranged concentrically, but may have a structure in which the supply nozzles are simply bundled.
  • a raw material supplier 8 composed of a hopper containing glass raw material particles GM is connected to the upper side of the oxyfuel burner 11 through a supply pipe 9.
  • a carrier gas supply source (not shown) for supplying a carrier gas for conveying the glass raw material particles GM to the glass raw material particle supply nozzle of the oxyfuel combustion burner 11 is connected to the supply pipe 9.
  • the fuel gas supply nozzle, the primary combustion gas supply nozzle, and the secondary combustion gas supply nozzle of the oxyfuel combustion burner 11 are connected to the gas supply device 6 via gas supply pipes 7a, 7b, and 7c, respectively.
  • the oxyfuel burner 20 as the second heating means is an oxyfuel burner known as an oxyfuel burner, in which a fuel and oxygen supply nozzle are appropriately arranged.
  • a fuel supply device (not shown) for supplying fuel to the fuel supply nozzle and a gas supply device (not shown) for supplying combustion gas containing oxygen to the combustion gas supply nozzle are connected to the oxyfuel burner 20.
  • the two oxygen combustion burners 20, 20 pass through substantially the same height positions of the opposing side walls 1 ⁇ / b> C, 1 ⁇ / b> C of the furnace body 1 and eject the oxygen combustion flames F ⁇ b> 2, F ⁇ b> 2 obliquely downward.
  • the present invention is not limited to this, and a plurality of oxygen combustion burners 20 are arranged in a ring shape so as to form a second heated gas phase atmosphere K2 having high symmetry below the first heated gas phase atmosphere K1.
  • a second heated gas phase atmosphere K2 having high symmetry below the first heated gas phase atmosphere K1.
  • it is.
  • three or more oxyfuel combustion burners may be arranged in a ring shape at equal intervals, and a plurality of nozzles for ejecting an oxyfuel combustion flame are arranged in a ring shape. You may apply the ring burner which can eject a combustion flame.
  • the second heated gas phase atmosphere K2 is composed of an arc plasma generation region and a high temperature atmosphere in the vicinity thereof.
  • FIG. 2 which showed the glass melting furnace which concerns on the 2nd Embodiment of this invention, the same code
  • the oxyfuel combustion flame F1 is injected downward from the front end portion 12 of the oxyfuel combustion burner 11, the first heated gas phase atmosphere K1 is formed by the oxyfuel combustion flame F1, and the oxyfuel combustion flame F2 is injected from the oxyfuel combustion burner 20.
  • a second heated gas phase atmosphere K2 is formed below the first heated gas phase atmosphere K1.
  • glass raw material particle GM is supplied from a glass raw material particle supply nozzle. As a result, the glass raw material particles GM charged into the furnace body 1 are melted into the first molten glass particles U1 while passing through the first heated gas phase atmosphere K1.
  • first molten glass particle U1 falls downward and passes through the second heated gas phase atmosphere K2, it is heated to become the second molten glass particle U2, and this second molten glass particle U2 Falls downward and accumulates at the bottom of the furnace body 1 to form molten glass G.
  • the first molten glass particles U1 are heated by the glass raw material particles GM in the first heated gas-phase atmosphere K1 and are liquefied by a chemical reaction such as a reaction of a component that becomes glass called a vitrification reaction and a melting reaction. It shows particles in the middle of becoming glass particles or liquid glass particles.
  • the second molten glass particles U2 are further heated in the second heated gas phase atmosphere K2 by the first molten glass particles U1, and the glass raw material is thermally decomposed (for example, from metal carbonate to metal oxide). Thermal decomposition, etc.), thermal decomposition of the fining agent contained in the glass raw material particles GM, and reaction of the components that become glass called vitrification reaction and melting, which are liquid glass particles.
  • some molten glass particles which have not finished melting may be present in the second molten glass particles U2. This is because most of the molten glass particles have finished melting, and other molten glass particles are immediately melted in the stored molten glass G. Further, the thermal decomposition of the fining agent on the second molten glass particles U2 is limited to such an extent that the effect as the fining agent can be further manifested immediately after falling on the molten glass G stored as the molten glass particles. This is possible by adjusting the temperature of the second heated gas-phase atmosphere K2.
  • the temperature of the heated gas phase atmosphere refers to the temperature near the center of the heated gas phase atmosphere, and is the maximum temperature in this region. It is preferable that the temperature of the first heated gas-phase atmosphere K1 is not less than the vitrification start temperature of the glass raw material particles GM and not more than 1500 ° C.
  • the temperature of the first heated gas phase atmosphere K1 is not less than the vitrification start temperature of the glass raw material particles GM and not more than 1500 ° C.
  • the “vitrification start temperature” refers to a temperature at which the shrinkage of the glass raw material particles GM starts by heating.
  • the vitrification start temperature varies depending on the composition of the glass raw material particles GM, but can be estimated by a temperature gradient furnace.
  • the vitrification start temperature is about 1040 ° C. for a general soda lime composition, and about 1150 ° C. for a non-alkali glass composition.
  • the temperature gradient furnace is described in, for example, Japanese Patent Application Laid-Open No. 2003-40641.
  • the temperature of the second heated gas-phase atmosphere K2 is equal to or higher than the clarification start temperature that is the decomposition start temperature of the clarifier contained in the glass raw material particles GM and the molten glass particles U1.
  • the fining start temperature differs depending on the type of fining agent contained in the glass raw material particles GM and the molten glass particles U1, for example, when the fining agent is SO 3 , 1450 ° C. for soda lime glass, 1250 ° C. for alkali-free glass, Cl
  • the soda-lime glass is 1410 ° C.
  • the alkali-free glass is 1450 ° C.
  • the alkali-free glass is 1500 ° C.
  • the clarification start temperature is a temperature at which the partial pressure of the clarification gas in the glass is remarkably increased by increasing the temperature in SO 3 , Cl, F, etc. (for example, expensive in As 2 O 5 , Sb 2 O 5, etc.). Is a temperature at which the oxide of the oxide begins to decompose and begins to generate oxygen gas), and takes a different value depending on the glass composition. That is, the temperature of the second heated gas-phase atmosphere K2 is higher than the temperature of the first heated gas-phase atmosphere K1.
  • the upper limit of the temperature of the second heated gas-phase atmosphere K2 is not particularly limited, but as described above, it is set to a temperature at which the effect of the fining agent is further manifested immediately after falling on the stored molten glass.
  • the upper limit of the temperature is about 2800 ° C.
  • the second heated gas phase atmosphere K2 is formed by the thermal plasma P of the multiphase plasma arc generator 22 shown in FIG. 2, the upper limit of the temperature is about 20000 ° C.
  • the glass raw material particles GM charged into the furnace body 1 are converted into the first heated vapor phase atmosphere. It becomes the 1st molten glass particle U1 in the state which the fining agent remained without vanishing in K1. And this 1st molten glass particle U1 is heated more than the clarification start temperature in the 2nd heating gaseous-phase atmosphere K2, and becomes the 2nd molten glass particle U2. Defoaming of the second molten glass particles U2 and the molten glass G is promoted by the second molten glass particles U2 heated to a temperature at which the clarification effect of the fining agent appears on the liquid surface of the molten glass G. As a result, it becomes a molten glass having a high bubble quality with few bubbles.
  • the second molten glass particle U2 heated to the clarification start temperature or higher is the temperature of the molten glass G before the temperature drops below the clarification start temperature. It is preferable to reach the liquid level.
  • the second heated gas phase atmosphere K2 is preferably formed in the vicinity of the liquid surface of the molten glass G.
  • the vicinity of the liquid surface of the molten glass G indicates a range that is not more than half of the distance from the liquid surface of the molten glass G to the inner surface of the furnace wall portion 1A of the upper wall of the furnace body 1.
  • the glass melting furnace 30 of the present embodiment can pass the glass raw material particles GM through the first heating vapor phase atmosphere K1 and the second heating vapor phase atmosphere K2 in this order. Therefore, after making the 1st molten glass particle U1 in the 1st heating gaseous-phase atmosphere K1 including the component of a clarifying agent, the 1st molten-glass particle
  • grains are heated by the heating in 2nd heated gaseous-phase atmosphere K2.
  • the melting of U1 can be further promoted to form molten glass particles U2 having a higher specific gravity.
  • the gas stream from the oxygen combustion burner 103 for injecting oxygen combustion flame F 100 downward is changing sideways from downward near the liquid surface of the molten glass G 100
  • the molten glass particles U 100 may be scattered on the side wall side and cannot be deposited on the molten glass G 100 .
  • the glass melting furnace 30 of the present embodiment can apply a downward force to the molten glass particles U1, U2 by the oxyfuel combustion flame F2 of the oxyfuel burner 20 that is inclined downward, so that the molten glass particles U1, It is possible to make the molten glass G land without scattering U2.
  • the vertical distance between the liquid surface of the molten glass G and the tip of the heat source generating part of the oxyfuel burner 11 is set as the second heated gas phase atmosphere K2. Is preferably within 0.5H above the liquid surface of the molten glass G. From the viewpoint of landing the molten glass particles U2 on the molten glass G more effectively, it is more preferable to form the second heated gas phase atmosphere K2 within 0.3H above the liquid surface of the molten glass G.
  • the tip of the heat source generating part of the oxyfuel burner 11 indicates the tip 12 of the oxyfuel burner 7. Even when the heat source generator is not an oxyfuel burner, the tip of the heat source generator is used as a reference when calculating H.
  • the molten glass G manufactured by the glass melting furnace 30 and the manufacturing method of the molten glass of the present embodiment is discharged from the molten glass discharge port 4 at a predetermined speed, introduced into a vacuum degassing apparatus as necessary, and forced in a vacuum state. Further, after defoaming, the glass article can be transferred to the molding apparatus 50 and molded into a desired shape to produce a glass article. Since the glass article manufactured as described above is formed from the molten glass G having a high bubble quality with few bubbles as described above, a high-quality glass article can be obtained.
  • FIG. 3 is a schematic view showing a third embodiment of the glass melting furnace according to the present invention. 3, the same components as those of the glass melting furnace 30 shown in FIG. 1 are denoted by the same reference numerals, and the description of the same components is omitted.
  • the glass melting furnace 30 ⁇ / b> C shown in FIG. 3 has a furnace wall 1 ⁇ / b> C of the furnace body 1 below the oxygen combustion burner 20 that forms the second heated gas phase atmosphere K ⁇ b> 2.
  • an oxyfuel combustion burner 25 that is a third heating means installed obliquely downward.
  • the oxyfuel combustion of the oxyfuel burner 25 is performed below the first heated gas phase atmosphere K1, below the second heated gas phase atmosphere K2, and further below the second heated gas phase atmosphere K2.
  • the third heating vapor phase atmosphere K3 is formed by the flame F3.
  • the oxyfuel burner 25, which is the third heating means is the last heating means
  • the third heated gas phase atmosphere K3 is the last heated gas phase atmosphere.
  • the glass raw material particles GM charged into the furnace body 1 are melted first by one while passing through the first heated gas phase atmosphere K ⁇ b> 1. It becomes the glass particle U1. Further, the first molten glass particle U1 falls downward and passes through the second heated gas phase atmosphere K2, and is heated to become the second molten glass particle U2. Thereafter, while the second molten glass particle U2 falls downward and passes through the third heated gas phase atmosphere K3, the second molten glass particle U2 is further heated to become the third molten glass particle U3 and accumulates at the bottom of the furnace body 1. Then, a molten glass G is formed.
  • the formation position of the third heating vapor phase atmosphere K3 closest to the molten glass G side is set to the same position as the second heating vapor phase atmosphere K2 in the glass melting furnace 30 shown in FIG. It is preferable to do. Further, the temperature of the third heated vapor phase atmosphere K3 can be set to the same level as the second heated vapor phase atmosphere K2. In the case of the configuration of FIG. 3, when the vertical distance between the liquid surface of the molten glass G and the tip of the heat source generating portion of the oxyfuel burner 11 is H, the third heated gas phase atmosphere K3 is the liquid surface of the molten glass G.
  • the third heated gas phase atmosphere K3 is formed upward from the liquid surface of the molten glass G. More preferably, it is formed within 0.15H.
  • the third heating means in addition to the oxyfuel burner 25, the arc plasma generator 22 shown in FIG. 2 may be applied, or the oxyfuel burner 25 and / or the arc plasma generator 22 may be applied.
  • the glass raw material particles GM may not be able to contain a large amount of fining agent.
  • it is possible to pass through three or more heated gas phase atmospheres so that the molten glass particles By staying for a long time in a temperature range lower than that of the conventional air melting method and gradually heating, molten glass particles that preserve the effect of the fining agent can be obtained even if the amount of the fining agent is small.
  • the glass melting furnace of the present invention is not limited to the examples shown in FIGS.
  • Four or more heating means may be provided so that four or more heating gas phase atmospheres arranged in the vertical direction can be formed in the atmosphere in the furnace body 1. In that case, it is preferable to set the temperature and position of the heating vapor phase atmosphere formed in the lowermost stage similarly to the second heating vapor phase atmosphere K2 formed in the glass melting furnace of the first embodiment shown in FIG. .
  • the molten glass G produced by the present invention is not limited in terms of composition as long as it is a glass produced by an air melting method. Therefore, any of soda lime glass, mixed alkali glass, borosilicate glass, or non-alkali glass may be used. Moreover, the use of the manufactured glass article is not limited to architectural use or vehicle use, and examples include flat panel display use and other various uses.
  • soda-lime glass used for plate glass for buildings or vehicles, it is expressed in terms of mass percentage on the basis of oxide, SiO 2 : 65 to 75%, Al 2 O 3 : 0 to 3%, CaO: 5 to 15%, MgO: 0 to 15%, Na 2 O: 10 to 20%, K 2 O: 0 to 3%, Li 2 O: 0 to 5%, Fe 2 O 3 : 0 to 3%, TiO 2 : 0 to 5%, CeO 2 : 0 to 3%, BaO: 0 to 5%, SrO: 0 to 5%, B 2 O 3 : 0 to 5%, ZnO: 0 to 5%, ZrO 2 : 0 to 5 %, SnO 2 : 0 to 3%, SO 3 : 0 to 0.5%.
  • SiO 2 39 to 75%
  • Al 2 O 3 3 to 27%
  • B 2 O 3 0 to 20%
  • SrO: 0 to 20% BaO: 0 to 30% are preferable.
  • a mixed alkali glass used for a substrate for plasma display it is expressed in terms of mass percentage on the basis of oxide, and SiO 2 : 50 to 75%, Al 2 O 3 : 0 to 15%, MgO + CaO + SrO + BaO + ZnO: 6 to 24 %, Na 2 O + K 2 O: preferably 6 to 24%.
  • one or more kinds of fining agents such as SO 3 , Cl, F, SnO 2 , As 2 O 3 , Sb 2 O 3 , CeO 2 are contained at 1% or less.
  • colorants, melting aids, opacifiers and the like can be included as auxiliary materials.
  • glass raw material particles GM are prepared by mixing and assembling the glass raw materials having any of the above-described compositions, for example, the particulate raw material powder particles of the above-described components in accordance with the composition ratio of the target glass.
  • the air melting method is a method of manufacturing glass by melting glass raw material particles GM in order to manufacture glass composed of a plurality of (usually three or more components) components.
  • the glass raw material particles GM when an example of an alkali-free glass is applied as an example of the glass raw material particles GM, silica sand, alumina (Al 2 O 3 ), boric acid (H 3 BO 3 ), magnesium hydroxide (Mg (OH 2 ), raw material powder particles such as calcium carbonate (CaCO 3 ), strontium carbonate (SrCO 3 ), barium carbonate (BaCO 3 ) are blended so as to match the composition ratio of the target glass, for example, spray dry granulation method As a result, the glass raw material particles GM can be obtained as a granulated body of about 30 to 1000 ⁇ m.
  • the glass raw material particles GM As a method of preparing the glass raw material particles GM from the glass raw material powder particles, a method such as a spray dry granulation method can be used, and granulation in which an aqueous solution in which the glass raw material is dispersed and dissolved is sprayed in a high temperature atmosphere and dried and solidified.
  • the method is preferred.
  • the glass raw material particles may be composed only of raw materials having a mixing ratio corresponding to the target glass component composition, but the glass raw material particles are further mixed with glass cullet powder having the same composition, and this is mixed with glass. It can also be used as raw material particles GM.
  • a glass slurry powder in the range of 2 to 500 ⁇ m is dispersed in a solvent such as distilled water as a glass raw material powder particle of each of the above components to form a slurry. Then, the slurry is stirred for a predetermined time by a stirring device such as a ball mill, mixed, pulverized, and then spray-dried granulated, whereby the glass raw material powder particles GM of the above-mentioned components are dispersed almost uniformly. Is obtained.
  • the glass raw material particles GM used in the present embodiment can be formed by a dry granulation method such as a tumbling granulation method or a stirring granulation method in addition to the above-mentioned spray dry granulation method.
  • the average particle diameter (weight average) of the glass raw material particles GM is preferably in the range of 30 to 1000 ⁇ m. More preferably, glass raw material particles GM having an average particle diameter (weight average) in the range of 50 to 500 ⁇ m are used, and glass raw material particles GM in the range of 70 to 300 ⁇ m are more preferable. An example of the glass raw material particles GM is enlarged and shown in FIG. 1, but it is preferable that one glass raw material particle GM substantially matches the composition ratio of the final target glass or has an approximate composition ratio.
  • the average particle diameter (weight average) of the molten glass particles U1, U2, and U3 in which the glass raw material particles GM are melted is usually about 80% of the average particle diameter of the glass raw material particles GM.
  • the particle size of the glass raw material particles GM is preferably selected from the above-mentioned range from the viewpoint that it can be heated in a short time, the generated gas can be easily diffused, and the composition variation between the particles is reduced.
  • FIG. 4 is a flowchart showing an example of a method for producing a glass article using the method for producing molten glass according to the present invention.
  • the molten glass G is obtained by the glass melting step S ⁇ b> 1 by the molten glass manufacturing method according to the present invention using the glass melting furnaces 30, 30 ⁇ / b> B, 30 ⁇ / b> C described above.
  • the glass article G5 can be obtained by passing the molten glass G to the molding apparatus 50 and performing the molding step S2 in which the molten glass G is molded into the target shape and then slowly cooling in the slow cooling step S3. As shown in FIG.
  • the manufacturing method of the glass article of the present invention uses a known molding step and slow cooling step, and other known additional steps, in addition to utilizing the glass melting step S1 according to the above-described molten glass manufacturing method of the present invention. Can be applied.
  • the glass raw material particle GM in this invention does not exclude what is not contained in a glass raw material particle about a part of glass raw material (henceforth a "partially granulated body").
  • the glass raw material (hereinafter referred to as “partial glass raw material”) that is not contained in a part of the granulated material is a gas phase heated from the same or different inlet from the part of the granulated body. Put it in the atmosphere.
  • the partially granulated body and the partially glass raw material may be deposited at least in the same region on the glass melt to form molten glass particles. Specifically, both may be allowed to coexist within 10 square millimeters of the glass melt surface.
  • the partial glass raw material and the partial granulated body can be obtained by adjusting the density and particle size of the partial granule with respect to the partial glass raw material or by devising the method of charging the partial glass raw material.
  • the flight trajectory should be close. Some melts hardly aggregation prone components of the glass raw material (silica sand, alumina or the like) had better form part granule with components for lowering the melting point (boric acid (H 3 BO 3), an alkali, etc.).
  • the component that lowers the melting point of a part of the glass raw material is easy to form molten glass particles integrally with the part of the granule, even if it is added separately from the part of the granule containing the silica sand that is difficult to dissolve, for example Boric acid, alkali, etc. (excess thereof) can be added separately.
  • a coloring component may be used as a part of the glass raw material. In this case, it is preferable to stir the molten glass after landing on the glass melt.
  • the advantage of using a partly granulated body is that it is not always necessary to make all the glass raw materials into granulated bodies, and there is a point that cost can be reduced because the necessary amount of granulated bodies to be prepared can be reduced.
  • most of the glass raw material particles GM in the present invention are supplied to the uppermost heated gas phase atmosphere, a part thereof is supplied from a heated gas phase atmosphere other than the uppermost layer as necessary. It is not excluded. In this case, the amount of the glass raw material particles supplied to the heated gas phase atmosphere other than the uppermost layer should be suppressed to such an extent that it becomes molten glass particles.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Plasma & Fusion (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)

Abstract

L'objectif de la présente invention est de pourvoir à : un procédé de production de verre fondu qui permet d'obtenir un verre fondu contenant peu de bulles et une qualité de bulles élevée ; un four de fusion pour verre ; et autre. Le procédé de production de verre fondu selon l'invention crée au moins deux atmosphères gazeuses chauffées (K1, K2) alignées verticalement, introduit les particules de verre de départ (GM) en un point situé au-dessus de la plus haute desdites atmosphères gazeuses chauffées (K1, K2), et forme les particules de verre fondu (U2) par passage des particules de verre de départ (GM) dans lesdites au moins deux atmosphères gazeuses chauffées (K1, K2).
PCT/JP2012/061269 2011-05-17 2012-04-26 Procédé de production de verre fondu, four de fusion pour verre, procédé de production d'un article en verre et dispositif afférent Ceased WO2012157432A1 (fr)

Priority Applications (3)

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KR1020137027054A KR101965003B1 (ko) 2011-05-17 2012-04-26 용융 유리의 제조 방법, 유리 용융로, 유리 물품의 제조 방법 및 유리 물품의 제조 장치
CN201280022826.7A CN103534214B (zh) 2011-05-17 2012-04-26 熔融玻璃的制造方法、玻璃熔融炉、玻璃物品的制造方法及玻璃物品的制造装置
JP2013515065A JP5971241B2 (ja) 2011-05-17 2012-04-26 溶融ガラスの製造方法およびガラス物品の製造方法

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CN109399637A (zh) * 2018-11-02 2019-03-01 大连理工大学 一种金刚线切割硅粉的高温非转移电弧造粒设备和方法

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JP2007297239A (ja) * 2006-04-28 2007-11-15 Tokyo Institute Of Technology ガラスの原料溶解方法および溶解装置ならびにガラス製造装置
WO2007129509A1 (fr) * 2006-05-01 2007-11-15 Asahi Glass Company, Limited Procédé de production de verre
JP2010515646A (ja) * 2007-01-15 2010-05-13 ロックウール インターナショナル アー／エス 鉱物繊維の製造方法及び製造装置

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JP4761575B2 (ja) 2007-05-28 2011-08-31 大同特殊鋼株式会社 ガラス製品の製造装置

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JP2006199549A (ja) * 2005-01-21 2006-08-03 Tokyo Institute Of Technology ガラス原料の溶解方法および溶解装置、ならびにガラス製造装置
JP2007297239A (ja) * 2006-04-28 2007-11-15 Tokyo Institute Of Technology ガラスの原料溶解方法および溶解装置ならびにガラス製造装置
WO2007129509A1 (fr) * 2006-05-01 2007-11-15 Asahi Glass Company, Limited Procédé de production de verre
JP2010515646A (ja) * 2007-01-15 2010-05-13 ロックウール インターナショナル アー／エス 鉱物繊維の製造方法及び製造装置

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WO2024047238A1 (fr) * 2022-09-02 2024-03-07 Rockwool A/S Procédé de recyclage de déchets minéraux

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CN103534214B (zh) 2016-10-26
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KR101965003B1 (ko) 2019-04-02
CN103534214A (zh) 2014-01-22
JP5971241B2 (ja) 2016-08-17

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