KR101203153B1 - A glass powder manufacturing method for recyling cullet - Google Patents

Abstract

PURPOSE: A glass material manufacturing method using waste glass is provided to cost-effectively remove network-modifying oxide from waste glass. CONSTITUTION: A glass material manufacturing method includes the following steps: foreign materials are removed from waste glass and coarsely crushed(S1); the crushed coarse waste glass particles are melted until a temperature gradient exists between the surface and the center of the waste glass particles(S2); the molten waste glass particles are gradually cooled to coagulate network-modifying oxide on the surface of a glass lump(S3); the glass lump is dropped to separate the coagulated network-modifying oxide from the surface of the glass lump(S4); the separated network-modifying oxide is removed(S5); the glass lump is re-crushed to form glass materials(S6); and the glass lump dropping process is repeated. [Reference numerals] (AA) Start; (BB) End; (S1) Pulverizing step; (S2) Melting step; (S3) Precipitating step; (S4) Separating step; (S5) Removing step; (S6) Re-pulverizing step

Description

A glass powder manufacturing method for recyling cullet

The present invention relates to a method for producing a glass material for raw materials using waste glass, and to a method for producing a glass material which can be used as a raw material for various products by efficiently removing the mesh wood oxide (網 目 修飾 酸化 物) and improving physical properties. It is about.

Waste glass means defective glass, shattered glass, glass chips or crushed products of glass products, etc., which occur in the production and processing of glass-based products and from used glass products. And the like can be recycled through appropriate recycling processing.

With the recent increase in the use of TFT-LCD and PDP panels, the generation of waste glass in the production process of such panels is increasing. TFT-LCDs and PDP panels play a role in delivering images, so even small defects should not occur. Therefore, compared with general glass products, the manufacturing process or quality control is very strict, which inevitably generates a large amount of waste glass.

In addition, the glass is beautiful in appearance and can be molded into various forms, so it is widely used in various building materials, ornaments, household goods, tableware, bottles, etc. It is used as a raw material for various products.

For example, Korean Patent Registration Publication No. 10-0917269 (September 16, 2009) describes a "badge composition of borosilicate long fiber glass made from cullet of a thin film transistor liquid crystal display glass substrate". Disclosed is a method of processing waste glass generated in the production process and recycling it as a raw material of long fiber glass.

By the way, the conventional waste glass has been determined that the electrical, thermal, and chemical properties are determined by the mesh wood oxide originally retained in the recycling process, there is a problem that the recycling use is limited.

That is, the components of the waste glass resulting from the above-described TFT-LCD include SiO ₂ and B ₂ O ₃ as a mesh forming oxide, and in addition, Al ₂ O ₃ , CaO, SrO, BaO and Na ₂ O etc., and other oxides include trace amounts of MnO, Cr ₂ O ₃ , ZnO, CoO, Li ₂ O, As ₂ O ₃ , PbO, Bi ₂ O ₃ and P ₂ O ₅ The waste glass is processed and recycled to the minimum standard to meet the minimum ratio of B ₂ O ₃ , which is necessary to use as a raw material for long fiber glass.

This was absurd both in the recycling of waste glass and in social and long term terms. This is because the use of a variety of mesh wood oxides affecting the physical properties has been limited to use if the mesh wood oxides affect the use or properties of products produced by recycling waste glass. Particularly, even though the amount of net wood oxide is contained in a large amount, even if there is a limit to completely remove the component, even if a small amount of the component is not removed, the effect of the component may have to be limited, thereby limiting the use range.

For example, PbO (lead oxide), which is one of the tree oxides, is highly toxic and may affect the human body. Therefore, its presence is fatal in products requiring strict human toxicity. Therefore, the use of the raw material for manufacturing non-toxic products of the human body is limited.

For this reason, it is necessary to control the components of the oxide contained in the waste glass to remove or at least contain the components of the mesh oxide. This is the same when recycling waste glass from various sources as well as waste glass caused by TFT-LCD. As a result, the glass material is finally produced by reducing the net wood oxide component as much as possible in the process of processing waste glass. It was necessary to be able to be used as a raw material for various glass products.

On the other hand, in order to remove or reduce the net oxides to a minimum, to remove the net oxides to a higher degree requires a larger process and equipment. This may eventually increase the cost of the glass material produced through the recycling process. Therefore, there was a need for a method for cost effective removal of mesh wood oxide in the process of recycling waste glass.

In the present invention, the purpose of the present invention is to efficiently remove the mesh wood oxide as much as possible in the process of recycling the waste glass, thereby increasing the purity to be used for various purposes. In addition, the purpose is to be able to remove the mesh wood oxide from the waste glass easily and conveniently at low cost.

In the present invention, after the removal of foreign matter in the waste glass crushing step (조립) to crush; A melting step of applying heat from the surface of the granulated particles pulverized in the pulverizing step to melt in a state where a temperature gradient exists on the surface and the center before being completely melted to the center; A precipitation step of gradually cooling the molten waste glass through the melting step so that the mesh fluid having high fluidity is agglomerated on the glass lump surface due to its low melting point compared to the mesh forming oxide; A separation step of dropping the cooled glass mass to separate the mesh wood oxides agglomerated on the surface by friction; A removal step of removing the separated mesh oxide from the glass mass; And a regrinding step of regrinding the glass cake from which the mesh tree oxide has been removed to form a glass material.

According to the present invention, by removing the mesh wood oxide from the waste glass as efficiently as possible to increase the relative purity can be recycled for various uses.

1 is a process diagram showing a manufacturing process of the glass material for the raw material according to the present invention;
Figure 2 is a schematic view showing an apparatus for producing a raw material glass material according to the present invention,
3 is an exemplary photograph of a glass material for a raw material according to the present invention.

In the present invention, in order to be able to remove the mesh wood oxide from the waste glass as much as possible, the grinding step of removing the foreign matter from the waste glass and then crushed; Melting step of melting by applying heat to the waste glass pulverized in the crushing step; A precipitation step of gradually cooling the molten waste glass through the melting step to form a glass lump having an irregular size in which mesh tree oxide is agglomerated on the surface; A separation step of separating the aggregated mesh oxide on the surface of the glass mass; A removal step of removing the separated mesh oxide from the glass mass; And a regrinding step of regrinding the glass cake from which the mesh wood oxide has been removed to form a glass material.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

As shown in FIG. 1, the glass material manufacturing method according to the present invention includes a grinding step (S1), a melting step (S2), a precipitation step (S3), a separation step (S4), and a removal step (S5). Through the step (S6) is removed by removing the mesh wood oxide from the waste glass.

Grinding step (S1) is a step of forming the granulated (Coarse Grain, 粗粒) by crushing the waste glass, and removes the foreign matter and water from the waste glass and then crushed. The particle size of the pulverized waste glass granules is determined in consideration of the size that can be appropriately melted in the melting step described later, it is preferable to be about 1mm or less, the pulverization method is not specified and known Can be adopted.

Melting step (S2) is a step of melting by applying heat to the pulverized waste glass granulator (粗 粒子). In the melting step, the pulverized waste glass assembly is supplied to the conveyor 10 to be transported and melted by applying heat. At least one heating device 20 is formed on the conveyor 10 to melt the pulverized waste glass. To achieve through.

When heat is applied to the waste glass assembly in the melting step, melting starts from the surface and becomes a round lump by surface tension.

The proper temperature condition for melting the waste glass assembly is to adopt the temperature at which the assembled waste glass begins to melt from the surface but is present in a uniform size in a round shape before being completely melted. It is determined that heat at a temperature in the range of C is applied to the waste glass over 3 to 15 seconds.

If the waste glass is exposed to heat for less than 3 seconds, there is not enough melting from the surface, and if it is exposed to heat for more than 15 seconds, it is difficult to melt completely and maintain a lump state.

Various methods can be adopted for heating the pulverized waste glass. Preferably, the waste glass assembly is melted by applying heat by direct heating while transferring it through the conveyor 10 line. That is, heating by installing a device for injecting sparks in the heating device 20, the reason for applying heat by direct weaving is because the waste glass is crushed and assembled to form a heat, so the heat is easily transferred evenly. This is because the melting easily occurs in a short time by simply doing, and also because it is easy to directly heat the surface of the waste glass assembly for a short time.

On the other hand, if the waste glass assembly pulverized in the process of melting by direct fire while moving along the conveyor 10 is stacked too thick, proper melting does not occur. Therefore, in order to allow proper melting, it is desirable that the thickness of the pulverized waste glass granules stacked is not more than 1 mm. In particular, if more than 1mm heat transfer is not evenly made, so that proper melting does not occur, it is determined in the above range.

Precipitation step (S3) is a rounded lump formed by melting the waste glass assembly through the melting step is allowed to crystallize slowly cooling to room temperature over about 5 to 30 minutes to agglomerate the mesh wood oxide on the surface Forming a glass gob. So-called slow cooling precipitation.

When heat is applied to the glass assembly through the melting step, since the center is not sufficiently heat exchanged as compared to the surface directly exposed to heat, the core is melted at a relatively low temperature, and the surface and the center have a slight temperature gradient.

Eventually, the center is somewhat viscous, whereas the surface is melted and maintained in a lump state by the surface tension, which is a state in which the lumps are gathered in a circular shape gradually and uniformly on the conveyor 10.

In this state, if the glass liquid moves slowly along the conveyor 10 and cooled sufficiently slowly to ensure the time for free movement of the glass liquid component inside the mass, the composition ratio of the component phase is adjusted according to the position of the mass so that CaO, SrO, BaO, MnO, Low melting point, such as Cr ₂ O ₃ , ZnO, CoO, As ₂ O ₃ , PbO, Bi ₂ O ₃ , the relatively low viscosity and high fluidity mesh wood oxide aggregates on the surface than other components.

That is, the melting point of the oxide depends on the material that combines with oxygen, and the smaller the atomic radius, the higher the melting point. In this case, the atomic radius on the periodic table becomes larger toward the left and toward the bottom.

Therefore, Si, B, Al, Na elements, such as Al ₂ O ₃ and Na ₂ O, among the mesh forming oxides, SiO ₂ and B ₂ O ₃ , which are included in the waste glass, are included in CaO and SrO. , BaO, MnO, Cr ₂ O ₃ , ZnO, CoO, As ₂ O ₃ , PbO, Bi ₂ O ₃ The melting point of oxides is relatively high because they belong to a smaller axis of atomic change than elements such as Ca, Sr, Ba, Mn, Cr, Zn, Co, As, Pb, Bi, and the like.

Therefore, when the glass liquid originating from the waste glass is gradually cooled, the network oxide having lower melting point than that of the mesh forming oxide is formed in the process of slowly solidifying the surface having the lower temperature and the surface having the higher temperature by the temperature gradient. Because of its relatively high fluidity, it maintains a relatively high temperature and continuously pushes it toward the surface with high fluidity.In the end, when the slow cooling is completed, the ratio of the mesh tree oxides having such a low melting point on the surface is relatively agglomerated. Will be.

In order to prevent the rapid temperature drop in the process of slowly cooling the glass liquid as described above, a slow cooling apparatus 30 is installed to gradually cool the glass liquid while gradually applying heat from a high temperature to a low temperature along the conveyor 10. The slow cooling device is installed to heat the conveyor 10 from the rear of the heating device 20 by a predetermined length, and is installed below the conveyor 10 to apply heat to the conveyor 10 with electricity or gas flame, but to the rear. Increasingly, the heating temperature is lowered so that the temperature is lowered as the conveyor 10 proceeds backward, so that the glass liquid is gradually cooled to form a glass mass in which the mesh tree oxide is agglomerated on the surface.

On the other hand, the vibrating means is preferably provided on the conveyor 10 so as to provide an additional external force that becomes a driving force when the mesh fluid having high fluidity is pushed toward the surface while the glass liquid is gradually cooled. For example, the vibration means is a rotor provided on the conveyor 10 equipped with a slow cooling device 30, by providing a fine circular motion vibration to the conveyor belt, the mesh liquid having a relatively high fluidity by vibrating the glass liquid finely It helps the oxide to condense towards the highly fluid surface.

Separation step (S4) is a step of separating the mesh wood oxide aggregated on the glass lump surface. By causing the glass lumps to fall and rubbing so that the mesh wood oxides agglomerated on the surface are separated from the glass lumps and separated into powder. The conveyor 10 is formed stepwise at the rear of the cooling apparatus to form the drop 40. The chunks of glass will fall down vertically at a height as if a waterfall would fall.

At this time, the falling height can be adjusted according to the need, because the glass is not easily broken, but the strength of the coagulated tree oxide aggregated on the surface of the glass agglomerate is not too large, so it is easily broken and select from the range of 20 ~ 70cm.

Preferably, the dropping of the glass mass in the separating step is repeated a plurality of times. When the conveyor 10 is formed in a stepped manner, the plurality of falling parts 40 are formed by forming the multi-stage. This allows the drop to repeat so that the mesh wood oxide is separated as much as possible.

When the drop portion 40 is formed in multiple stages so that the drop of the glass lump is repeated a plurality of times, the drop height is preferably increased toward the rear. The lower the drop height, the smaller the impact amount. At first, the components aggregated on the outermost part of the glass mass are separated, and the higher the drop height, the more components are required to be separated. Therefore, by adjusting the number of drops and the height can be adjusted to the components that are separated from the glass mass.

Removal step (S5) is a step of removing the mesh wood oxide separated from the glass mass. The mesh wood oxide separated in the separation step (S4) is sucked into the inhaler 50 to remove as much as possible leaving only the glass mass. Since the glass mass is heavier than the separated mesh wood oxide powder, when the inhaler 50 is inhaled, only the mesh wood oxide can be sucked out and removed. At this time, by placing a plurality of inhalers 50 on the conveyor 10 and gives a small drop between the inhalers 50 so that the glass chunks fall while flipping to be able to inhale more smoothly. After the inhalation of the mesh tree oxide, only the glass lumps are left, and the purity increases around the mesh forming oxide.

Removing the network receiving oxide in the removal step is an example of a method of removing by inhalation with the inhaler 50, but is not limited thereto, and may adopt a variety of configurations, such as to filter and separate the network tree oxide, such as sieve. Of course it can.

The regrinding step (S6) is a step of regrinding the glass cake from which the mesh tree oxide has been removed to form a glass material. Glass chunks formed by slowly cooling the glass liquid are larger than the original waste glass assembly. Therefore, after removing the mesh wood oxide, it is pulverized once again with a grinder 60 to form a fine powder or granulated form suitable for raw materials. Through this it is possible to obtain a glass powder for the raw material in the form of a fine powder as illustrated in FIG.

As described above, the method for manufacturing the glass material for the raw material according to the present invention can be performed through a relatively simple facility without a large-scale facility, thereby effectively removing the mesh wood oxide at low cost.

Hereinafter, preferred embodiments of the present invention as described above will be described.

LCD waste glass was pulverized to 1 mm or less and granulated, and the waste glass powder was fed to the conveyor 10 in a thickness of 1 mm, and then moved along the conveyor 10, and melted so that direct flame at 800 ° C. was applied for 15 seconds. . After 30 minutes, gradually cooled to room temperature to form agglomerated glass aggregates of mesh wood oxide on the surface, while moving along the conveyor 10 in order to drop at 20cm, 40cm, 60cm agglomerated mesh wood oxide on the surface Was separated and then removed by suction. Thereafter, the remaining glass mass was pulverized to obtain a finely ground glass powder for the raw material as illustrated in FIG. 3.

Samples were taken from the glass powders for the raw materials prepared as described above, and the components were requested to the Korea Institute of Ceramic Technology to obtain the results shown in Table 1 below. The test environment is temperature (25 ± 1) ℃, relative humidity (40 ± 1)% R.H., and the test method is KS L 3128: 2004, KS L 3316: 2009, KS L 2512: 2004.

Name of sample Test Analysis Items Test analysis result (wt%) Test Analysis Method








Glass material for raw materials










SiO ₂ 61.3








KS L 3128: 2004
KS L 3316: 2009
KS L 2512: 2004










Al ₂ O ₃ 18.2 Na ₂ O 0.19 Fe ₂ O ₃ 0.03 CaO 7.67 MgO 1.49 K ₂ O 0.05 TiO ₂ 0.01 P ₂ O ₅ 0.03 BaO 0.01 ZrO ₂ 0.02 MnO <0.01 Cr ₂ O ₃ <0.01 ZnO <0.01 CoO <0.01 Li ₂ O <0.01 SrO 0.78 As ₂ O ₃ <0.01 PbO <0.01 Bi ₂ O ₃ <0.01 B ₂ O ₃ 10.2

As confirmed in Table 1, the glass material for the raw material formed by the method according to the present invention includes TiO ₂ , BaO, MnO, Cr ₂ O ₃ , ZnO, CoO, Li ₂ O, As ₂ O ₃ , PbO , Bi ₂ 0 _{3 It} can be seen that almost completely removed to 0.01% by weight or less. And only a few of the remaining mesh oxides can be seen. Therefore, according to the present invention, a considerable portion of the mesh wood oxide is removed, thereby ensuring a relatively high purity glass material for the raw material.

10: conveyor, 20: heating device,
30: slow cooling device, 40: falling portion,
50: inhaler, 60: grinder.

Claims (5)

Grinding step (S1) of removing the foreign matter from the waste glass and then granulated (하게);
A melting step (S2) of applying heat from the surface of the waste glass granulator (粗 粒子) pulverized in the crushing step (S1) to melt in a state where a temperature gradient exists on the surface and in the center before being completely melted to the center;
Precipitating step (S3) to gradually cool the waste glass melted through the melting step (S2) to agglomerate on the surface of the glass mass with a high fluidity low melting point compared to the mesh forming oxide;
A separation step (S4) of dropping the cooled glass mass to separate the mesh wood oxides agglomerated on the surface by friction;
A removing step (S5) of removing the separated mesh oxide from the glass mass; And
Regrinding step (S6) of regrinding the glass mass from which the mesh tree oxide has been removed to form a glass material;
In the separation step (S4), the falling of the glass mass is repeated a plurality of times in a stepwise manner, and the repeated height to adjust the components to be separated by increasing the drop height,
The removing step (S5) includes a plurality of suction process for sucking and removing the separated mesh wood oxide oxide with a plurality of inhalers, the separated mesh by further comprising a drop process for dropping the glass mass between the plurality of suction processes Method for producing a glass material for raw materials using waste glass, characterized in that to facilitate the inhalation of modified oxides.
The method according to claim 1,
The melting step (S2) is a glass material manufacturing method using the raw glass, characterized in that for melting by applying heat to the crushed waste glass by direct fire.
The method according to claim 1,
The precipitation step (S3) is to provide an additional external force that the driving force (Driving Force) to provide a vibration by providing additional vibration to the mesh wood oxide surface toward the surface (S3). delete delete

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