WO2017179364A1 - Procédé de fabrication d'un produit en verre - Google Patents

Procédé de fabrication d'un produit en verre Download PDF

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Publication number
WO2017179364A1
WO2017179364A1 PCT/JP2017/011008 JP2017011008W WO2017179364A1 WO 2017179364 A1 WO2017179364 A1 WO 2017179364A1 JP 2017011008 W JP2017011008 W JP 2017011008W WO 2017179364 A1 WO2017179364 A1 WO 2017179364A1
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WIPO (PCT)
Prior art keywords
glass
volatiles
raw material
exhaust gas
melting
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PCT/JP2017/011008
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English (en)
Japanese (ja)
Inventor
繁 瀬良
健史 北島
成田　利治
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日本電気硝子株式会社
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Publication of WO2017179364A1 publication Critical patent/WO2017179364A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/02—Plant or installations having external electricity supply
    • B03C3/16—Plant or installations having external electricity supply wet type
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting 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

Definitions

  • the present invention relates to a technique for manufacturing a glass product, and more specifically, collects volatiles contained in exhaust gas generated when an alkali-containing glass raw material is melted in a melting furnace, and is contained in the volatiles. It is related with the technique for collect
  • a glass product manufacturing process powdery or granular glass raw material is put into a melting furnace, and the glass raw material is heated into molten glass in the melting furnace, followed by press molding and blow molding.
  • Glass products are obtained by molding methods such as float molding and overflow molding.
  • the volatile matter contains various components derived from the glass raw material.
  • the boron component is contained in the volatile matter.
  • the exhaust gas is released into the atmosphere, and the collected volatiles are returned to the melting furnace and reused (recycled).
  • a technique for this is disclosed in, for example, “Patent Document 1”.
  • Patent Document 1 in a glass melting method in which a glass raw material is heated by a burner flame in a glass melting furnace to obtain molten glass, on the other hand, substantially as a fuel for the burner flame.
  • a fuel that does not contain water to obtain molten glass and on the other hand, contacting gaseous useful components and particulate useful components contained in the exhaust gas discharged from the glass melting furnace with water
  • the neutralized collected liquid is subjected to solid-liquid separation to obtain useful components that can be used as a glass raw material.
  • a technique relating to a glass melting method characterized by collecting is disclosed.
  • the present invention has been made in view of the above-described current problems, and collects volatiles from exhaust gas generated when melting glass raw materials, and collects recycled raw materials containing the volatiles.
  • An object of the present invention is to provide a glass product manufacturing method having a step of reusing and capable of improving recovery efficiency.
  • the glass product manufacturing method is a glass product manufacturing method including a step of collecting volatiles from exhaust gas generated when melting a glass raw material, collecting the volatiles, and reusing them.
  • a raw material melting step for melting a glass raw material of alkali-containing glass, and a volatile matter that collects the volatile matter by bringing water into contact with an exhaust gas containing volatile matter generated when the glass raw material is melted in the raw material melting step A collection step, a magnesium compound addition step of adding a magnesium compound to the volatile matter collected in the volatile matter collection step to form a mixed solution, and a recycled material containing the volatile matter by drying the mixed solution And a drying step of recovering.
  • the magnesium compound is added to the collected liquid (including volatile substances) collected in the volatile matter collecting step, and then collected by drying. Recycled raw materials including volatiles in the liquid are to be recovered.
  • the dry state of the volatiles recovered by subsequent drying is good, and there is hardly any solid state that contains moisture, which will be described later. It is clarified by the verification experiment. Therefore, according to the glass product manufacturing method of the present invention, the recovered recycled material is in a dry state, the weight of the finally obtained recycled material is increased, and the recovery efficiency of the glass material can be improved. .
  • the exhaust gas is introduced into a water spray tower, the exhaust gas is brought into contact with mist water in the water spray tower, and the volatile matter is obtained. It is preferable to collect the volatile matter remaining in the tower exhaust gas that has passed through the water spray tower with an electric dust collector.
  • the electrostatic precipitator is a wet electrostatic precipitator, and the admixture is spray-dried in the drying step.
  • cleaning water is always supplied inside the electrostatic precipitator, and a water film is formed on the surface of the dust collecting electrode by the cleaning water. It is possible to prevent re-scattering of objects.
  • the volatile aqueous solution is sent back to the water spray tower.
  • the water spray tower it is preferable to circulate the collected liquid to which the volatile aqueous solution has been added a predetermined number of times, and then introduce the collected liquid into the magnesium compound addition step.
  • the collected liquid generated in the water spray tower and the volatile aqueous solution generated in the electrostatic precipitator are contained in the water spray tower. After being sufficiently stirred, it is sent to the next magnesium compound addition step. Therefore, the concentration of the collected liquid (including the volatile aqueous solution) in the magnesium compound addition step is uniform, and the chemical reaction with the added magnesium compound can be promoted.
  • the alkali-containing glass is preferably a glass for chemical strengthening.
  • the glass product manufacturing method of the present invention is effective for chemically strengthening glass having a glass composition with a relatively small calcium compound content.
  • the alkali-containing glass contains MgO or 0.5 wt%, it is preferred that the Na 2 O and containing at least 5 wt%, also containing CaO less 5 wt%.
  • the recycled material can be effectively recovered by the glass product manufacturing method of the present invention.
  • the admixture in the magnesium compound addition step, is settled and separated into a supernatant and a slurry body, and the supernatant is returned to the water spray tower and reused. It is preferable.
  • the supernatant liquid is circulated again in the water spray tower, and is used for collecting volatiles in the exhaust gas. is there. Moreover, since the density
  • the recycled raw material is recovered in a powder form in the drying step and then sent again to the raw material melting step.
  • the recovered recycled raw material is in the form of powder, so that it is easy to handle even when it is sent again to the raw material melting step.
  • the following effects can be obtained. That is, according to the glass product manufacturing method according to the present invention, it is possible to improve the recovery efficiency when recovering the recycled material from the exhaust gas generated when the glass material is melted, particularly in the alkali-containing glass.
  • the alkali-containing glass produced by the present embodiment is a chemically strengthened glass and has the following glass composition.
  • SiO 2 is 50 to 80 wt%
  • Al 2 O 3 is 5 to 25 wt%
  • B 2 O 3 is 0 to 15 wt%
  • Na 2 O is 1 to 20 wt%
  • K 2 O Is preferably prepared so as to contain 0 to 10 wt%.
  • SiO 2 is a component for forming a glass network. If the content of SiO 2 is too small, vitrification becomes difficult, and the thermal expansion coefficient becomes too high, so that the thermal shock resistance tends to decrease. On the other hand, if the content of SiO 2 is too large, the meltability and the formability tends to decrease. Therefore, the content of SiO 2 is preferably 50 to 80 wt%, 52 to 75 wt%, 55 to 70 wt%, particularly 55 to 67.5 wt%.
  • Al 2 O 3 is a component for increasing ion exchange performance, and is a component for increasing the strain point and Young's modulus.
  • the content of Al 2 O 3 is preferably 5 to 25 wt%. If the content of Al 2 O 3 is too small, the thermal expansion coefficient becomes too high, and the thermal shock resistance tends to be lowered, and in addition, prisoners who cannot sufficiently exhibit the ion exchange performance are generated. Therefore, a preferable lower limit range of Al 2 O 3 is preferably 7 wt% or more, 8 wt% or more, 10 wt% or more, 12 wt% or more, 14 wt% or more, 15 wt% or more, particularly 16 wt% or more.
  • a preferable upper limit range of Al 2 O 3 is preferably 22 wt% or less, 20 wt% or less, 19 wt% or less, 18 wt% or less, particularly 17 wt% or less.
  • B 2 O 3 is a component that lowers the high temperature viscosity and density, stabilizes the glass, makes it difficult to precipitate crystals, and lowers the liquidus temperature. It is also a component for increasing crack resistance. However, if the content of B 2 O 3 is too large, the ion exchange treatment may cause coloring of the surface called burnt, decrease in water resistance, decrease in the compressive stress value of the compressive stress layer, The stress depth of the force layer tends to be small. Therefore, the content of B 2 O 3 should be 0 to 15 wt%, 0.1 to 12 wt%, 1 to 10 wt%, more than 1 to 8 wt%, 1.5 to 6 wt%, particularly 2 to 5 wt%. preferable.
  • Na 2 O is an primary ion exchange component, also lowers the high temperature viscosity, is a component for enhancing the meltability and formability. Na 2 O is also a component for improving devitrification resistance.
  • the content of Na 2 O is preferably 1 to 20 wt%. When Na 2 O content is too small, or reduced meltability, lowered coefficient of thermal expansion tends to decrease the ion exchange performance. Therefore, when Na 2 O is introduced, the preferred lower limit range of Na 2 O is preferably 5 wt% or more, 11 wt% or more, particularly 12 wt% or more.
  • a preferable upper limit range of Na 2 O is preferably 17 wt% or less, particularly preferably 16 wt% or less.
  • K 2 O is a component for promoting ion exchange, and is a component that has a large effect of increasing the stress depth of the compressive stress layer in the alkali metal oxide. Moreover, it is also a component for reducing high temperature viscosity and improving meltability and moldability. Furthermore, it is also a component that improves devitrification resistance.
  • the content of K 2 O is preferably 0 to 10 wt%. When the content of K 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance becomes difficult to match or decreased, the thermal expansion coefficient with those of peripheral materials. Moreover, there is a tendency that the strain point is excessively lowered, the component balance of the glass composition is lacking, and the devitrification resistance is lowered.
  • Li 2 O is an ion exchange component and a component for decreasing the high temperature viscosity and improving the meltability and moldability. It is also a component for increasing the Young's modulus. Furthermore, the effect of increasing the compressive stress value is large among alkali metal oxides. However, when the content of Li 2 O is too large, and decreases the liquidus viscosity, it tends glass devitrified. In addition, the thermal expansion coefficient becomes too high, so that the thermal shock resistance is lowered or it is difficult to match the thermal expansion coefficient of the surrounding material. Furthermore, if the low-temperature viscosity is too low and stress relaxation is likely to occur, the compressive stress value may be reduced. Therefore, the content of Li 2 O is preferably 0 to 3.5 wt%, 0 to 2 wt%, 0 to 1 wt%, 0 to 0.5 wt%, particularly 0.01 to 0.2 wt%.
  • a preferable content of Li 2 O + Na 2 O + K 2 O is 5 to 25 wt%, 10 to 22 wt%, 15 to 22 wt%, particularly preferably 17 to 22 wt%.
  • Li 2 O + Na 2 O + K content of 2 O is too small, the ion exchange performance and meltability is liable to decrease.
  • the content of Li 2 O + Na 2 O + K 2 O is too large, the glass tends to be devitrified, the thermal expansion coefficient becomes too high, the thermal shock resistance decreases, and the peripheral materials It becomes difficult to match the thermal expansion coefficient of In addition, the strain point may be excessively lowered and it may be difficult to obtain a high compressive stress value.
  • Li 2 O + Na 2 O + K 2 O is the total amount of Li 2 O, Na 2 O, and K 2 O.
  • MgO is a component for decreasing the high-temperature viscosity to increase meltability and moldability, and to increase the strain point and Young's modulus.
  • MgO has a large effect of improving ion exchange performance. It is an ingredient. Therefore, the preferred lower limit range of MgO is preferably 0.5 wt% or more, 1 wt% or more, particularly 2 wt% or more. Since MgO is contained in an amount of 0.5 wt% or more, a magnesium compound can be used to recover the recycled raw material.
  • CaO Compared with other components, CaO has a large effect of lowering the high temperature viscosity and improving the meltability and moldability, and increasing the strain point and Young's modulus without deteriorating devitrification resistance.
  • the content of CaO is preferably 0 to 10 wt%.
  • the CaO content is preferably 0 to 5 wt%, 0.01 to 4 wt%, 0.1 to 3 wt%, particularly 1 to 2.5 wt%.
  • SrO is a candy component that lowers the high-temperature viscosity without increasing devitrification resistance, thereby improving meltability and moldability, and increasing the strain point and Young's modulus.
  • the content of SrO is preferably 0 to 5 wt%, 0 to 3 wt%, 0 to 1 wt%, particularly preferably 0 to less than 0.1 wt%.
  • BaO is a component for decreasing the high temperature viscosity without increasing the devitrification resistance, increasing the meltability and moldability, and increasing the strain point and Young's modulus.
  • the BaO content is preferably 0 to 5 wt%, 0 to 3 wt%, 0 to 1 wt%, particularly preferably 0 to less than 0.1 wt%.
  • ZnO is a component for enhancing ion exchange performance, and is a component that is particularly effective in increasing the compressive stress value. Moreover, it is also a component for reducing high temperature viscosity without reducing low temperature viscosity.
  • the content of ZnO is preferably 0 to 6 wt%, 0 to 5 wt%, 0 to 1 wt%, 0 to 0.5 wt%, and particularly preferably 0 to less than 0.1 wt%.
  • ZrO 2 is a component for remarkably enhancing the ion exchange performance, and also a component for increasing the viscosity and strain point in the vicinity of the liquid phase viscosity. However, if its content is too large, the devitrification resistance is remarkably increased. There are prisoners that decline and those who become too dense. Therefore, the upper limit range of ZrO 2 is preferably 10 wt% or less, 8 wt% or less, 6 wt% or less, and particularly preferably 5 wt% or less. In order to improve ion exchange performance, it is preferable to introduce ZrO 2 into the glass composition. In this case, the lower limit range of ZrO 2 is 0.001 wt% or more, 0.01 wt% or more, 0.5 wt%. As mentioned above, it is preferable to set it as 1 wt% or more especially.
  • P 2 O 5 is a component for enhancing ion exchange performance, and in particular, is a component for increasing the stress depth of the compressive stress layer.
  • the upper limit range of P 2 O 5 is preferably 10 wt% or less, 8 wt% or less, 6 wt% or less, 4 wt% or less, 2 wt% or less, 1 wt% or less, and particularly preferably less than 0.1 wt%.
  • one or more selected from the group of As 2 O 3 , Sb 2 O 3 , SnO 2 , F, Cl, and SO 3 are used in an amount of 0 to 30000 ppm (3 wt%) may be introduced.
  • the content of SnO 2 + SO 3 + Cl is preferably 0 to 10,000 ppm, 50 to 5000 ppm, 80 to 4000 ppm, 100 to 3000 ppm, particularly 300 to 3000 ppm, from the viewpoint of accurately enjoying the clarification effect.
  • “SnO 2 + SO 3 + Cl” refers to the total amount of SnO 2 , SO 3 , and Cl.
  • the SnO 2 content is preferably 0 to 10000 ppm, 0 to 7000 ppm, particularly 50 to 6000 ppm.
  • the Cl content is preferably 0 to 1500 ppm, 0 to 1200 ppm, 0 to 800 ppm, 0 to 500 ppm, particularly 50 to 300 ppm.
  • the content of SO 3 is preferably 0 to 1000 ppm, 0 to 800 ppm, particularly 10 to 500 ppm.
  • Rare earth oxides such as Nd 2 O 3 and La 2 O 3 are components for increasing the Young's modulus, and are components that can be erased and control the color of glass when a complementary color is added. is there.
  • the cost of the raw material itself is high, and if it is introduced in a large amount, the devitrification resistance tends to decrease. Therefore, the rare earth oxide content is preferably 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, and particularly preferably 0.5 wt% or less.
  • the glass for chemical strengthening in the present embodiment does not substantially contain As 2 O 3 , F, PbO, or Bi 2 O 3 from the viewpoint of the environment.
  • substantially does not contain As 2 O 3 means that the glass component does not positively add As 2 O 3 but allows mixing at the impurity level. This means that the content of As 2 O 3 is less than 500 ppm.
  • substantially free of F means that F is not actively added as a glass component but is allowed to be mixed at an impurity level. Specifically, the content of F is less than 500 ppm. It points to something.
  • substantially no PbO means that although PbO is not actively added as a glass component, it is allowed to be mixed at an impurity level. Specifically, the PbO content is less than 500 ppm. It points to something. By “substantially free of Bi 2 O 3", but not added actively Bi 2 O 3 as a glass component, a purpose to allow the case to be mixed with impurity levels, specifically, Bi 2 It indicates that the content of O 3 is less than 500 ppm.
  • the alkali-containing glass product manufacturing method embodied by the present embodiment collects volatiles from the exhaust gas G1 generated when the glass raw material M is melted, for example, in the manufacturing process of the alkali-containing glass products. This is a method for collecting the recycled raw materials that are contained and reusing (recycling) the collected recycled raw materials R.
  • the alkali-containing glass product manufacturing method in the present embodiment mainly includes a raw material melting step S01, a volatile matter collecting step S02, an exhaust gas releasing step S03, a magnesium compound adding step S04, and spray drying as an example of a drying step. It is comprised by process S05 and raw material input process S06.
  • the raw material melting step S01 is a step for heating and melting the glass raw material M of the alkali-containing glass charged into the melting furnace 10 described later. When the glass raw material M is melted, exhaust gas G1 containing reusable volatile matter is generated. The glass raw material M melted in the raw material melting step S01 is then supplied to a forming step such as pressing or blowing, and is formed into an alkali-containing glass product having a desired form.
  • the volatile matter collecting step S02 is a step for collecting the volatile matter by bringing the exhaust gas G1 containing the volatile matter generated when the glass raw material M is melted in the raw material melting step S01 into contact with the washing water. More specifically, in the volatile matter collecting step S02, the exhaust gas G1 containing volatile matter generated when the glass raw material M is melted in the raw material melting step S01 is introduced into the spray tower 20 described later, and the spray tower 20 By spraying cleaning water L (spray water) onto the exhaust gas G1, the volatile matter solution is collected as the collected liquid La, and the volatile matter remaining in the tower exhaust gas G2 that has passed through the spray tower 20 is collected. It is a process for collecting by the electric dust collector 30 mentioned later.
  • the exhaust gas release step S03 is a step for releasing the clean exhaust gas G3 that has become clean in the volatile matter collection step S02 through the chimney 40 into the atmosphere.
  • the magnesium compound addition step S04 the mixed liquid Lc is generated by adding the magnesium compound X to the collected liquid La collected in the volatile matter collecting step S02, and this mixing is performed using the concentration tank 60 described later.
  • This is a process for generating the slurry Ld from the liquid Lc.
  • the mixed liquid Lc contains an insoluble magnesium salt produced by causing a chemical reaction between a part of the volatile substances contained in the collected liquid La and the magnesium compound X, and the remaining volatile substances.
  • the concentration of the magnesium salt and the remaining volatile matter is gradually increased by sedimentation separation.
  • the spray drying step S05 is a step for generating a recycled material R by spray drying the slurry Ld produced in the magnesium compound addition step S04 using a spray dryer 70 described later. By this step, the operation of collecting the recycled raw material R contained in the exhaust gas G is temporarily terminated.
  • the raw material charging step S06 is a step for charging the glass raw material M and the recovered recycled raw material R into the melting furnace 10 and returning them again using a raw material charging device 80 described later.
  • the volatile matter is collected by performing the volatile collection step S02 on the exhaust gas G1 generated in the raw material melting step S01, Thereafter, the recycled raw material containing the volatile matter is recovered by sequentially performing the magnesium compound addition step S04 and the spray drying step S05.
  • the recovered recycled material R is again input into the melting furnace 10 and reused (recycled) by performing the material input process S06.
  • each of these steps S01 to S06 is performed by the melting facility 1 described later.
  • the melting facility 1 is mainly composed of a melting furnace 10, a spray tower 20 as an example of a water spray tower, an electric dust collector 30, a chimney 40, a mixing tank 50, a concentration tank 60, a spray dryer 70, a raw material charging apparatus 80, and the like.
  • the melting facility 1 is mainly composed of a melting furnace 10, a spray tower 20 as an example of a water spray tower, an electric dust collector 30, a chimney 40, a mixing tank 50, a concentration tank 60, a spray dryer 70, a raw material charging apparatus 80, and the like.
  • the melting furnace 10 is for heating and melting the glass raw material M adjusted to have a desired glass composition.
  • the melting furnace 10 is provided with a burner (not shown) using, for example, LPG or the like as fuel, and the glass raw material M introduced into the melting furnace 10 is heated by the burner while generating exhaust gas G1. Is done.
  • the exhaust gas G ⁇ b> 1 generated in the melting furnace 10 is sent to the spray tower 20.
  • the spray tower 20 is for spraying the cleaning water L on the exhaust gas G1 introduced from the melting furnace 10 and collecting volatile substances contained in the exhaust gas G1.
  • the cleaning water L is intermittently supplied and the supplied cleaning water L is always circulated while being circulated.
  • the exhaust gas G1 introduced into the spray tower 20 comes into contact with the sprayed cleaning water L (spray water), and the volatile substances contained in the exhaust gas G1 are collected. Thereby, the collected volatiles are dissolved or dispersed in the washing water L, and the collected liquid La is generated. Thus, in the spray tower 20, the solution containing a volatile matter is collected as the collection liquid La by spraying the cleaning water L on the introduced exhaust gas G1.
  • the spray tower 20 has means capable of repeatedly circulating the collected liquid La, whereby the concentration of volatile substances contained in the collected liquid La is gradually increased. . For example, when the number of circulations reaches a predetermined number, the concentrated collection liquid La1 is supplied to a mixing tank 50 described later.
  • the tower exhaust gas G ⁇ b> 2 that has collected most of the volatiles by the wash water L is sent to the electric dust collector 30, which will be described later, and the volatiles that could not be recovered by the spray tower 20 in the electric dust collector 30. Is collected.
  • the spray tower 20 is mainly set up for the purpose of collecting dust and volatiles having high water solubility (water-soluble volatiles), for example, an apparatus.
  • the spray tower 20 can be replaced by a scrubber or the like.
  • the electrostatic precipitator 30 performs corona discharge on the tower exhaust gas G2 introduced from the spray tower 20, gives electric charges to volatiles floating in the tower exhaust gas G2, and attaches them to a dust collection electrode (not shown). This is for collecting volatile substances contained in the tower exhaust gas G2. That is, in the electrostatic precipitator 30, the volatile matter remaining in the tower exhaust gas G2 that has passed through the spray tower 20 is collected.
  • the electrostatic precipitator 30 in the present embodiment is a wet electrostatic precipitator, and the cleaning water L is always supplied therein, and a water film is formed on the surface of the dust collecting electrode by the cleaning water L. The prevention of re-scattering of volatile substances and the like adhering to the dust collecting electrode is achieved.
  • the electrostatic precipitator 30 is comprised so that the volatile matter contained in tower exhaust gas G2 may be collected on the dust collecting electrode electrically charged by the corona discharge, and the collected volatile matter will use the water film of a dust collecting electrode. It is washed away by the wash water L that forms. Thereby, the volatile-solution aqueous solution Lb containing the volatile matter which could not be collect
  • the generated volatile aqueous solution Lb is added to the collected liquid La and returned to the spray tower 20 again. Then, the volatile aqueous solution Lb is supplied to the mixing tank 50 described later together with the collected liquid La.
  • the electric dust collector 30 collects the volatile aqueous solution Lb containing the volatiles remaining in the tower exhaust gas G2 that has passed through the spray tower 20, and then collects the volatilization.
  • the aqueous solution Lb is sent back to the spray tower 20 added to the collected liquid La.
  • it is the structure which introduce
  • the concentrated collection liquid La1 generated by the spray tower 20 and the electrostatic precipitator 30 is sufficiently stirred in the spray tower 20 and then sent to the next magnesium compound addition step. Will be. Therefore, the concentration of the concentrated collection liquid La1 in the magnesium compound addition step is uniform, and the chemical reaction with the added magnesium compound can be promoted.
  • the clean exhaust gas G3 that has finished collecting volatiles by corona discharge and has become sufficiently clean is discharged from the electrostatic precipitator 30 and released into the atmosphere via the chimney 40.
  • the apparatus is configured by a wet electric dust collector because volatile substances in the exhaust gas G1 generated in the melting furnace 10 are collected and then a collected liquid is generated.
  • the mixing tank 50 adds a magnesium compound X to the concentrated collection liquid La1 supplied from the spray tower 20 to cause a chemical reaction.
  • a magnesium compound X is added to the concentrated collection liquid La1 supplied from the spray tower 20 to cause a chemical reaction.
  • alkali-containing glass is added. This is for precipitating volatiles useful as a recycling raw material R as magnesium salts.
  • a stirring mechanism is provided inside the mixing tank 50, and the concentrated collection liquid La1 supplied from the spray tower 20 is sufficiently stirred together with the added magnesium compound X by the stirring mechanism. And it becomes mixed liquid Lc containing the volatile matter in concentration collection liquid La1, and the reaction product (magnesium salt) of magnesium compound X, and is supplied to the concentration tank 60.
  • FIG. 1 A stirring mechanism is provided inside the mixing tank 50, and the concentrated collection liquid La1 supplied from the spray tower 20 is sufficiently stirred together with the added magnesium compound X by the stirring mechanism. And it becomes mixed liquid Lc containing the volatile matter in concentration collection liquid La1, and the reaction product (magnesium salt) of magnesium compound X, and is supplied to the concentration tank 60.
  • magnesium compound X may be either solid or liquid (including a slurry state).
  • the concentration tank 60 is for increasing the concentration of volatiles in the admixture Lc.
  • the concentration tank 60 includes a settling tank 61, a slurry tank 62, and the like.
  • the mixed liquid Lc supplied to the concentration tank 60 is first stored in a settling tank 61, and volatiles dissolved in the mixed liquid Lc are settled and separated. Specifically, in the sedimentation tank 61, the volatile substances contained in the mixed liquid Lc cause a chemical reaction with the magnesium compound X added in the mixing tank 50 and precipitate as a magnesium salt, and precipitate at the bottom. To be separated.
  • the volatile magnesium salt precipitated at the bottom of the settling tank 61 is extracted as a slurry Ld and supplied to the slurry tank 62.
  • the supernatant liquid Le in the settling tank 61 is added to the collected liquid La and returned to the spray tower 20 again.
  • the supernatant liquid Le is circulated again in the spray tower 20 and used for collecting the volatiles in the exhaust gas G1, which is economical. Further, since the concentration of the volatile magnesium salt precipitated at the bottom by sedimentation becomes a slurry body Ld and the concentration is further increased, it is possible to improve the recovery efficiency of the recycled raw material R in the subsequent spray drying step S05. .
  • the slurry body Ld supplied to the slurry tank 62 is temporarily stored in the slurry tank 62. And when the capacity
  • the spray dryer 70 sprays the slurry body Ld supplied from the slurry tank 62 into the air (inner space of the spray dryer 70) to rapidly dry (spray drying), and the volatilization contained in the slurry body Ld. This is for producing a magnesium salt of the product as a powdered recycled raw material R.
  • the recycled raw material R generated by the spray dryer 70 is once deposited at the bottom of the spray dryer 70 and then supplied to a raw material charging device 80 described later.
  • the raw material charging device 80 is a device for charging the powdered recycled raw material R supplied from the spray dryer 70 into the melting furnace 10 again as a glass raw material.
  • the inventors of the present invention use a spray tower 20 and an electric dust collector 30. What kind of additive is most effective for collecting the volatiles contained in the concentrated collection liquid La1 by spray drying with the spray dryer 70 later on the concentrated collection liquid La1 collected by A verification experiment was conducted. Specifically, 100 ml of collected liquid La collected by the spray tower 20 and the electrostatic precipitator 30 is collected, and for example, dredged sand, slaked lime (calcium hydroxide), magnesium hydroxide is collected from the collected collected liquid La. In addition, 2000 ppm each of various additives consisting of magnesium oxide and magnesium nitrate were added, and then naturally dried, and each state was visually confirmed.
  • magnesium hydroxide when “magnesium hydroxide”, “magnesium oxide”, and “magnesium nitrate” were added, the dry state after natural drying was good, and almost no moisture was fixed. . Among them, especially “magnesium hydroxide” was not sticky even when touched by hand, showed a light touch feeling and was confirmed to be very dry. Therefore, it was determined that “magnesium hydroxide” is optimal as an additive to be added to the collected liquid La.
  • the present inventors actually recovered volatiles from the exhaust gas G1 using “magnesium hydroxide” as an additive in the case of handling alkali-containing glass (chemical strengthening glass) by the melting equipment 1 and obtained it.
  • the weight and composition of the recycled material R thus obtained were confirmed. Specifically, 60 kg / day of magnesium hydroxide was added in the mixing tank 50, and then the weight and composition of the recycled raw material R finally obtained by spray drying with the spray dryer 70 were confirmed.
  • the weight of the recycled raw material was considerably higher in the case of the melting facility 1 than in the case of the conventional melting facility. This is considered to be because, in the case of the melting facility 1, the recycled material R is in a dry state and is less likely to adhere to the inner wall surface of the spray dryer 70. Thus, it was confirmed that the recovery efficiency of the recycled raw material R was higher in the case of the melting facility 1 than in the case of the conventional melting facility.
  • the content of calcium oxide (CaO) is 29.1 wt% in the case of the conventional melting equipment, whereas 1.08 wt in the case of the melting equipment 1 of the present embodiment. %.
  • the melting equipment 1 in the present embodiment is preferable because a large amount of recycled raw materials can be reused.
  • the additive added to the collected liquid La is “ It was confirmed that “magnesium hydroxide” is optimal.
  • the content of magnesium oxide (MgO) is 0.35 wt% in the case of the conventional melting equipment, and 19.9 wt in the case of the melting equipment 1 of the present embodiment. %.
  • the recycled material of the comparative example has too much calcium oxide content, so that only a small amount can be reused.
  • the recycled raw materials of the examples have a low calcium oxide content, they can be reused in large quantities.
  • the case of the melting facility 1 in the present embodiment is more preferable than the case of the conventional melting facility, and “magnesium hydroxide” is the most suitable additive to be added to the collected liquid La. It was confirmed that there was.
  • the glass product manufacturing method embodied by the present embodiment it is possible to effectively recover the recycling raw material for the alkali-containing glass (chemical strengthening glass) having the glass composition described above. It became clear that we could do it.
  • the glass product manufacturing method collects volatiles contained in exhaust gas generated when melting an alkali-containing glass raw material in a melting furnace, and the alkali-containing glass raw material contained in the volatile matter. Can be recovered in a recyclable (recyclable) state and used as a technique for returning the raw material (recycled raw material) to the melting furnace again.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Separation Of Particles Using Liquids (AREA)
  • Electrostatic Separation (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un procédé de fabrication de produits en verre qui comprend une étape de collecte de matières volatiles à partir d'un effluent gazeux qui est généré lors de la fusion d'un matériau de départ en verre et de récupération et de réutilisation d'un matériau recyclé comprenant les matières volatiles, le procédé permettant d'améliorer l'efficacité de récupération. Le procédé de fabrication de produits en verre comprend : une étape S01 de fusion du matériau de départ consistant à faire fondre un matériau de départ en verre M d'un verre contenant un alcali ; une étape S02 de collecte de matières volatiles consistant à collecter des matières volatiles par mise en contact avec un effluent gazeux aqueux qui comprend les matières volatiles et qui est généré lors de la fusion du matériau de départ de verre M ; une étape S04 d'addition de composé de magnésium consistant à ajouter un composé de magnésium X aux matières volatiles collectées par un liquide de collecte La et un dépoussiéreur électrostatique 30 pour produire un liquide de mélange Lc ; et une étape S05 de séchage par pulvérisation consistant à sécher le mélange liquide Lc et à récupérer un matériau recyclé R qui comprend les matières volatiles.
PCT/JP2017/011008 2016-04-15 2017-03-17 Procédé de fabrication d'un produit en verre WO2017179364A1 (fr)

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JP2016082059A JP2017190273A (ja) 2016-04-15 2016-04-15 ガラス製品製造方法
JP2016-082059 2016-04-15

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Publication number Priority date Publication date Assignee Title
CN110917790A (zh) * 2019-12-12 2020-03-27 西安诺博尔稀贵金属材料股份有限公司 一种真空熔炼炉的炉气处理装置及处理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS48104345A (fr) * 1972-04-14 1973-12-27
JP2000079320A (ja) * 1998-09-07 2000-03-21 Kureha Kankyo Kk 焼却炉排ガスの高度処理方法
JP2004238236A (ja) * 2003-02-05 2004-08-26 Nippon Electric Glass Co Ltd ガラス溶融方法およびガラス溶融設備
WO2012161274A1 (fr) * 2011-05-25 2012-11-29 旭硝子株式会社 Procédé de fabrication d'un corps granulé, procédé de fabrication de verre fondu, et procédé de fabrication d'un article en verre
WO2014077114A1 (fr) * 2012-11-15 2014-05-22 旭硝子株式会社 Procédé de fabrication de verre sans alcali

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS48104345A (fr) * 1972-04-14 1973-12-27
JP2000079320A (ja) * 1998-09-07 2000-03-21 Kureha Kankyo Kk 焼却炉排ガスの高度処理方法
JP2004238236A (ja) * 2003-02-05 2004-08-26 Nippon Electric Glass Co Ltd ガラス溶融方法およびガラス溶融設備
WO2012161274A1 (fr) * 2011-05-25 2012-11-29 旭硝子株式会社 Procédé de fabrication d'un corps granulé, procédé de fabrication de verre fondu, et procédé de fabrication d'un article en verre
WO2014077114A1 (fr) * 2012-11-15 2014-05-22 旭硝子株式会社 Procédé de fabrication de verre sans alcali

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