KR101226625B1 - Manufacturing method of the glass tile by using refused coal ore - Google Patents

Abstract

The present invention is a raw material mixing step of mixing coal waste-rock, soda ash, silica, cullet, calcium-based material and magnesium-based material to make a mixture; A melting step of melting the mixture; Molding the mixture into plate glass; Glaze coating step of applying a glaze on the plate-shaped glass; And it provides a glass tile manufacturing method using coal waste-rock comprising a firing step of firing the plate-shaped glass. As such, by manufacturing the glass tile using coal waste-rock, not only can resources be recycled, but the manufacturing process can be simplified and the manufacturing cost can be reduced compared to the conventional glass tile manufacturing.

Description

MANUFACTURING METHOD OF THE GLASS TILE BY USING REFUSED COAL ORE}

The present invention relates to a method of manufacturing a glass tile using coal waste-rock, and more particularly, by manufacturing a glass tile using coal waste-rock, it not only recycles resources but also simplifies the manufacturing process and reduces manufacturing costs than conventional glass tile production. It relates to a glass tile manufacturing method using coal waste-rock that can be reduced.

In general, the coal industry, which has been the basis of Korea's energy resource industry, has greatly reduced its role due to the improvement of the standard of living and the supply of clean fuel. As a result, the number of currently run coal mines decreased by 97.4% from 347 in 1988 to 9 in 2004. In addition, a large amount of coal waste-rock generated as a result of the development of coal mines has been generated in the past, but proper recycling methods have not been developed and simple landfilling is difficult. Because it is not done, it is acting as a detrimental factor of the natural environment with the damage of the surrounding landscape today.

According to domestic coal waste-rock data collected and analyzed by the Coal Rationalization Project, about 200 million tons of waste-rock has been generated in coal mines that were abandoned from 1989 to 1993, and there have been 9 coal mines available. It has been reported that 36 million tonnes of coal waste-rock has been generated and deposited.

In the meantime, the recycling of waste resources has been limited to the study of manufacturing artificial light aggregate using coal ash and sewage sludge from coal-fired power plant. Has problems such as;

On the other hand, the conventional tile products are mostly products of the simple mosaic form produced by coating or printing a color pigment on the back of the plate glass. In addition, in order to manufacture such a tile, a color raw material is mixed with a glass raw material and melted at a high temperature to make a colored glass, and then molded, which requires a high temperature melting of 1500 ° C. or higher in a melting furnace, which is expensive and manufactured. The process had a complicated problem.

The present invention, in order to solve the problems of the prior art, by producing a glass tile using coal waste-rock, not only to recycle resources but also to simplify the manufacturing process and reduce the manufacturing cost than conventional glass tile production An object of the present invention is to provide a glass tile manufacturing method.

In order to achieve the above object, the glass tile manufacturing method using coal waste-rock according to the present invention, a raw material mixing step of mixing the coal waste-rock, soda ash, silica sand, cullet, calcium-based material and magnesium-based material to make a mixture; A melting step of melting the mixture; Molding the mixture into plate glass; Glaze coating step of applying a glaze on the plate-shaped glass; And a firing step of firing the plate glass.

In the present invention, the coal waste-rock may be a hard coal.

In the present invention, the pulverized coal stone may be a normal coal ore or shell ore.

In the present invention, the calcium-based material may be any one of calcium carbonate, calcium sulfate, calcium oxide, calcium hydroxide or limestone.

In the present invention, the magnesium-based material may be any one of magnesium sulfate, magnesium carbonate, magnesium oxide, magnesium hydroxide or dolomite.

In the present invention, the coal waste-rock, the soda ash, the calcium-based material, the magnesium-based material, the silica sand and the cullet, respectively, 5% to 70% by weight, 5% to 30% by weight, 5% by weight to 20 wt%, 0 wt% to 10 wt%, 5 wt% to 15 wt%, and 10 wt% to 80 wt%.

In the present invention, the melting step may be 0.5 hours to 5 hours at 1300 ℃ to 1700 ℃ and then slowly cooled.

In the present invention, the plate-shaped glass may be made by slow cooling after heating to 600 ℃ to 900 ℃ using a fireproof plate.

In the present invention, the fireproof plate may be formed with irregularities on the bottom surface.

In the present invention, the glaze may be applied by a spray coating method.

In the present invention, it may further comprise a drying step of drying the applied glaze.

In the present invention, the glaze may be naturally dried.

In the present invention, the firing step is to put the plate-shaped glass in the kiln and heat treatment, the process of raising the temperature to 700 ℃ to 1000 ℃ for 30 minutes to 3 hours and the process of maintaining the temperature for 10 minutes to 150 minutes after the temperature increase Can be.

In the present invention, the firing step may further include a slow cooling for 10 minutes to 150 minutes after the process of maintaining the temperature.

According to the present invention, a glass tile can be produced by vitrifying coal waste-rock and then molding it.

In addition, according to the present invention, by using coal waste-rock instead of the original glass made by melting the glass raw material and molded into plate glass, it is possible to simplify the glass tile manufacturing process than conventional, thereby reducing the manufacturing cost.

In addition, according to the present invention, by producing a glass tile using the discarded coal waste-rock, there is an effect of recycling the resources.

In addition, according to the present invention, it is possible to solve the problem of environmental damage, environmental damage due to coal waste-rock.

Moreover, according to this invention, the glass tile of various shapes can be manufactured easily simply.

1 is a process flow chart showing a process for manufacturing a glass tile using coal waste-rock according to an embodiment of the present invention,
Figure 2 is a graph showing the TG / DTA measurement results for the hard coal pumice according to an embodiment of the present invention,
3 is a photograph showing a molten glass manufactured according to an embodiment of the present invention,
Figure 4 is a graph showing the X-ray diffraction pattern for the molten glass prepared according to an embodiment of the present invention,
5 and 6 are graphs showing the results of measurement of transmittance of glass prepared by using the general pumice pumice and cell pumice pumice according to the blending ratio of the cullet according to an embodiment of the present invention,
7 and 8 are graphs showing the results of measuring the transmittance of the glass prepared using the chemical raw materials and mineral raw materials according to the mixing ratio of the cullet according to an embodiment of the present invention,
9 is a graph showing a result of measuring transmittance according to the type of cullet according to an embodiment of the present invention,
10 is a color coordinate of the glass manufactured using the normal keel pumice stone according to an embodiment of the present invention,
11 is a color coordinate of the glass prepared using the cell hard pumice pumice according to an embodiment of the present invention,
12 is a graph showing the thermal expansion coefficient of the glass prepared according to an embodiment of the present invention,
13 is a photograph showing a molding step according to an embodiment of the present invention,
14 is a photograph showing the glaze application step according to an embodiment of the present invention,
15a to 15b is a photograph showing a glass tile manufactured according to an embodiment of the present invention,
16 is a graph showing the measurement results of the thermal properties of the glass tile manufactured according to an embodiment of the present invention.

The objects, features and advantages of the present invention will be more readily understood by reference to the accompanying drawings and the following detailed description.

Specific structural or functional descriptions are merely illustrated for the purpose of describing embodiments in accordance with the concepts of the present invention, and embodiments in accordance with the concepts of the present invention may be embodied in various forms and described in the specification or the application. It should not be construed as limited to these.

The embodiments according to the concept of the present invention can make various changes and have various forms, so that specific embodiments are illustrated in the drawings and described in detail in this specification or application. However, it should be understood that the embodiments according to the concept of the present invention are not intended to limit the present invention to specific modes of operation, but include all changes, equivalents and alternatives included in the spirit and scope of the present invention.

The terms first and / or second etc. may be used to describe various components, but the components are not limited to these terms. The terms are for the purpose of distinguishing one component from other components only, for example, without departing from the scope of the rights according to the inventive concept, the first component may be named a second component, Similarly, the second component may also be referred to as the first component.

When a component is referred to as being connected or connected to another component, it should be understood that there may be a direct connection or connection to that other component, but there may be other components in between. On the other hand, when a component is mentioned as being directly connected to or directly connected to another component, it should be understood that there is no other component in between. Other expressions for describing relationships between components, such as between and immediately between, or neighboring to and directly neighboring to, should be interpreted as well.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. The terms including or having herein are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof that is implemented, one or more other features or numbers, steps, actions, It should be understood that it does not exclude in advance the possibility of the presence or addition of components, parts or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art, and are not construed in ideal or excessively formal meanings unless expressly defined herein. Do not.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Like reference symbols in the drawings denote like elements.

Referring to Figure 1, the glass tile manufacturing method using coal waste-rock according to an embodiment of the present invention, a method for producing a glass tile using coal waste-rock generated when coal is collected from coal mines, raw material mixing step ( S1), melting step (S2), forming step (S3), glaze applying step (S4) and firing step (S5).

First, the raw material mixing step (S1) is a step of making a mixture by mixing soda ash, silica sand, cullet, calcium-based material and magnesium-based material in coal waste-rock to vitrify coal waste-rock. The coal waste-rock that is used in this step may be a bituminous waste-rock.

Here, the coal waste-rock is divided into digging refuse from the excavation process and coal-preparation refuse generated from the process of coal mining. Pumice and carbon content is higher than this and there is a shell type of hard pumice (hereinafter, shell pumice pumice) which is commonly called a shell. In one embodiment of the present invention was used a normal hard pumice and shell hard pumice.

Table 1 shows the chemical component analysis of the normal keel and pumice pumice pumice according to one embodiment of the present invention. Here, since the abbreviations shown in the tables and drawings are as follows, the following abbreviations will be described below.

(CN: General Pelletite, CS: Shell Pelletite, CM: Chemical Raw Material, NM: Natural Mineral Raw Material, W20: 20% by weight of white cullet, W40: 40% by weight of white cullet, G20: 20% by weight of Green cullet, G40: 40% by weight green cullet, B20: 20% by weight brown cullet, B40: 40% by weight brown cullet)

As can be seen in Table 1, the content of SiO ₂ is 81.1% and Al ₂ O ₃ is 12.0%, and the content of SiO ₂ is 70.7%, Al in the case of ordinary pumice pumice. The content of ₂ O ₃ was found to be 18.5%. The content of Fe ₂ O ₃ is 0.51% compared to that of ordinary pumice pumice, which is 3.37% in the case of shell pumice pumice. This is due to the relatively high coal, ie carbon content, in the minerals. In addition, in order to determine the thermal characteristics of the hard coal pumice, a graph of the change in temperature rise from room temperature to 1500 ° C. using TG-DTA is shown in FIG. 2. In the case of general pumice pumice, the weight change due to the temperature increase is very small within 2% up to 1500 ° C, whereas in the case of shell pumice pumice, the weight loss is about 13% in the 500 ° C ~ 1100 ° C range. It is judged to be due to oxidation of the carbon component contained therein.

In addition, the calcium-based material may be used as a raw material for constituting the calcium component in the glass, but calcium carbonate may be used. In addition, any one of calcium sulfate, calcium oxide, calcium hydroxide or limestone may be selected.

The magnesium-based material may be used as a raw material for constituting the magnesium component in the glass, and magnesium sulfate may be used. In addition, any one of magnesium carbonate, magnesium oxide, magnesium hydroxide, or dolomite may be selected.

In addition, soda ash and silica sand, which are mineral raw materials, are ground to a thickness of 0.7 mm or less, preferably 0.5 mm or less, in order to uniformly control the particle size.

In addition, the cullet used as the flux of the glass uses a cullet of white, green and brown, and all use a commercially available soda-lime bottle and table glass cullet.

In the raw material mixing step (S1), 5% by weight to 70% by weight, 5% by weight to 30% by weight, 5% to 20% by weight of the coal waste-rock, soda ash, calcium-based material, magnesium-based material, silica sand and cullet, respectively , 0 wt% to 10 wt%, 5 wt% to 15 wt%, 10 wt% to 80 wt%, and may be blended, and more specifically, the mixture may be blended at a blending ratio shown in Table 2.

Next, the melting step (S2) is a step of melting the mixture made through the raw material mixing step (S1). In this step, the mixture blended at the above compounding ratio is placed in, for example, an alumina crucible, melted at 1300 ° C. to 1700 ° C., preferably 1550 ° C. for 0.5 hour to 5 hours, preferably 1 hour, and then slowly cooled.

Figure 3 is a photograph showing the molten glass produced by the melting step (S), when using the normal pumice pumice as a raw material was made of transparent glass, when using the shell pumice pumice, vitrification was well achieved due to excessive coloring The lower transmittance resulted in black glass that appeared almost opaque to the naked eye. In addition, as shown in FIG. 4, as a result of XRD analysis to determine the degree of vitrification and recrystallization of these glasses, a graph of an amorphous phase in which crystalline peaks do not appear in glass of all compositions was obtained. Through this, it can be seen that complete vitrification proceeded in all compositions, and that no special recrystallization occurred during slow cooling, that is, cooling.

And, as shown in Figure 5, the visible light transmittance of the molten glass using the normal keel pumice is 85.66% in the molten glass by mixing 40% white glass, 72.28% in the molten glass by mixing 40% green glass, The molten glass produced by using the shell keel pumice showed much lower transmittance values of 35.03%, 29.98%, and 32.60%, respectively, compared to 80.41% in the molten glass with 40% mixed brown cullet. This is because the shell and the pumice pumice have a higher content of carbon and iron oxide (Fe ₂ O ₃ ) than the general pumice pumice, so that the coloring and light blocking effect by these components is increased during vitrification, in particular, as shown in FIG. 6. As shown, when 20% of cullet was used, the effect of waste-rock material was significantly increased, indicating a greater transmittance difference.

FIG. 7 is a graph showing the transmittance characteristics according to the types of additives. When calcium carbonate was used, the transmittances of white, green, and brown were 82.35%, 71.32%, and 78.19% under 20% cullet mixing conditions. In the molten glass using limestone, which is a mineral raw material, 79.72%, 71.87%, and 75.06% of color values were shown, respectively, but there was a slight tendency difference depending on the color, but almost similar values were shown at ㅁ 3% level. As can be seen, a similar tendency is shown in 40% of the cullet mixture. That is, even if the limestone, which is a mineral material, is used instead of the calcium carbonate, which is a chemical material, there is no significant difference in the optical properties of the glass. Therefore, it is possible to secure economic feasibility by using a relatively inexpensive mineral material in the future.

In addition, as shown in Figure 9 (a), (b) looking at the transmittance characteristics according to the type of cullet, when the crushed glass is mixed 40% by using ordinary keel pumice, the transmittance of the white cullet is 85.66%, green The transmittance of the cullet was 72.28%, the transmittance of the brown cullet was 80.41%, and when 20% of the cullet was mixed, the transmittance values were 82.35%, 71.32%, and 78.19%, respectively. The transmittance difference was shown in the range of% to 86%, and the order of white cullet> brown cullet> green cullet was used. The self-transmittance of the cullet alone used in the present invention was 93.06% white, 42.25% green, and brown. As it is 31.11%, the decrease in transmittance of about 10% is observed in white cullet compared with the visible light transmittance of molten glass manufactured using 20% of these cullet in ordinary keel pumice, but green cullet and brown cullet Use In the case of the molten glass manufactured by, it can be seen that the transmittance of about 30% or more is increased. That is, since all visible light transmittances are at least 70% in all compositions using ordinary pumice pumice as raw materials, when general waste cullet is mixed, it is worth using as a commercial glass product in terms of transmittance, especially white cullet. In the case of using a high transmittance of 80% or more, it is possible to manufacture other color glass of various colors by adding another colorant. In addition, the transmittance value according to the mixing amount of the cullet was observed to show a higher transmittance value when the mixing amount of the cullet is 40% in most conditions than 20%.

Meanwhile, as shown in FIGS. 9C and 9D, the transmittances of the glass manufactured for each cullet using the shell pumice pumice show a low transmittance of 0% to 35% compared to when using the normal pumice pumice. In particular, in the case of molten glass using a mineral raw material, it is impossible to compare the characteristics because the visible light transmittance is almost zero in all compositions regardless of the mixing amount of the cullet. Therefore, when the glass is manufactured using shell hard pumice stone, the glass produced may be utilized as an opaque molding glass having a black color.

Table 3 is another optical property of the glass prepared according to the present invention is to measure the chromaticity (chromaticity) using the UV / VIS / NIR Spectrometer to know the color change according to the use of each composition and color wave glass.

10 and 11 show chromaticity characteristics of the glass using the normal pumice pumice and the glass using the shell pumice pumice, respectively, in a chromaticity diagram. As a result of analyzing the difference of the color difference according to each mixing condition, molten glass using ordinary hard pumice pumice according to the type of coal waste-rock is located in the white area which is almost the center of the color coordinate and shows 'lightness'. Most of the Y 'values are also higher than 80%. This is because, as can be seen from the transmittance measurement results, the glass made of ordinary keel pumice has a high transmittance regardless of the type of the cullet. On the other hand, in the case of the molten glass using the shell pumice pumice, it is distributed in each direction centering on the white area of the center according to the kind and mixing amount of a cullet on a color coordinate. The 'Y' value also varies from 0 to 48 depending on the composition. Therefore, color glasses of various colors may be manufactured based on the measured color coordinate values.

In addition, Figure 12 is a thermal expansion coefficient of the thermal properties of the glass prepared according to the present invention was measured using a TMA (Thermo mechanical Analyzer), the thermal expansion coefficient of the molten glass using a normal keel hard pumice is 8.273 × 10 ^-6 / ℃ The coefficient of thermal expansion of the molten glass using, shell and pumice pumice was 8.972 × 10 ^-6 / ℃, which was slightly lower than that of general soda-lime glass, which is 9 ~ 10 × 10 ^-6 / ℃. However, it did not show a big difference. In addition, as a result of measuring the softening point (softening point), the softening point of the glass using the normal keel hard pumice was found to be 750 ℃, the softening point of the glass using the shell keel hard pumice showed similar values to 746 ℃. In general, the softening point of the general soda lime glass shows a value of about 10 ° C. to 15 ° C. as high as compared with the softening point of 725 ° C. to 735 ° C., but did not show a significant difference. This thermal property is because the alumina content of the glass composition according to the present invention is about 10%, which is relatively high compared to 2% to 3% of the general soda lime composition. In general, aluminosilicate glass applied to low-expansion heat-resistant glass has an alumina content of about 15%, and the glass having this composition has a coefficient of thermal expansion of 4 × 10 ⁻⁶ / ° C. and a softening point of 900 ° C. Therefore, although not a big difference, a low coefficient of thermal expansion and a high softening point may be desirable characteristics in terms of increasing the heat resistance of the glass.

Next, the molding step (S3) is a step of molding the molten mixture, that is, the molten glass into a plate-shaped glass. As shown in the photo shown in Fig. 13, in this step, the molten glass is placed in a fireproof plate and heat treated to form a solid plate-like glass. At this time, the heat treatment conditions are elevated to 600 ℃ to 900 ℃, preferably 800 ℃ and then cooled slowly. Here, in order to diversify the shape of the plate-shaped glass to be made, a variety of irregularities may be formed on the bottom surface of the fireproof plate, through which the curved plate-shaped glass, mosaic-like plate-shaped glass may be made. . At this time, in order to form a desired curved shape on the surface of the plate-shaped glass, it is necessary to accurately measure the softening temperature of the glass, for this softening point measuring instrument can be used.

On the other hand, when mass production of plate-shaped glass may be used instead of a metal mold such as a refractory plate forming roller, in which case the molten glass may be introduced into the forming roller through a conveying means such as a conveyor.

Next, glaze application step (S4) is a step of applying the glaze on the molded plate-shaped glass. As shown in the photograph shown in Figure 14, this step can be applied to the glaze by spray coating method.

On the other hand, after the glaze application step (S4), the drying operation for the applied glaze may be in progress. In this case, the applied glaze is preferably completely dried at approximately 50 ° C. to 60 ° C., and may be naturally dried in mass production.

Finally, the firing step (S5) is a step of firing the plate-shaped glass coated with glaze on one side or both sides. Firing step (S5) is a heat treatment process to remove the impurities contained in the glass and glaze to improve the bonding between the molecules or the adhesion of the glass and glaze. In this case, in order to heat-treat the coating of the color glaze on the plate glass, the coefficient of thermal expansion of the plate glass and the glaze should be applied equally. Otherwise, the coated glaze may peel off or crack due to the difference in expansion and contraction with each other during the heat treatment.

In the firing step (S5), the plate-shaped glass is put into a kiln, for example, and heated to 700 ° C to 1000 ° C. At this time, the time until reaching the above temperature may be set to 30 minutes to 3 hours. Then, the temperature is maintained for 10 to 150 minutes at the above temperature. And then slowly cooled for 10 to 150 minutes to prevent the glass and glaze from being damaged by thermal shock due to rapid temperature changes.

As such, when the firing step (S5) is completed, a glass tile using coal waste-rock according to the present invention is made, the photo of such a glass tile is shown in Figures 15a to 15b. And Figure 16 is a graph showing the thermal properties of the glass tile produced according to the present invention, it can be seen that the glass tile produced according to the present invention has a high softening point.

As described above, the present invention produces a glass tile by vitrifying the coal waste-rock to be discarded and then molded. That is, the present invention by using coal waste-rock instead of the original glass made by melting the glass raw material and molded into plate glass, it is possible to simplify the glass tile manufacturing process than the conventional, thereby reducing the manufacturing cost, recycling resources It works. In addition, the present invention can solve the problem of environmental damage due to the coal waste-rock, environmental pollution, as well as easy to manufacture a variety of glass tiles, it is possible to customize the interior glass tiles.

As described above, with reference to the preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the present invention described in the claims below. It will be appreciated that it can be changed.

Claims (15)

Raw material mixing step of mixing coal waste-rock, soda ash, silica sand, cullet, calcium-based material and magnesium-based material to make a mixture;
Placing the mixture in an alumina crucible and melting at 1550 ° C. for 1 hour;
Forming the molten glass in a fireproof plate and heating it to a temperature of up to 800 ° C., heat-forming and solidifying a plate-like vitrified material, followed by slow cooling to form a plate-shaped glass;
Glaze application step of applying a glaze on the plate-shaped glass using a spray method; And
Firing the plate-shaped glass by putting the plate-shaped glass in a kiln and heat-treating the same, heating the plate-shaped glass through a process of raising the temperature to 700 ° C. to 1000 ° C. for 30 minutes to 3 hours and maintaining the temperature for 10 minutes to 150 minutes after the temperature increase;
Glass tile manufacturing method using coal waste-rock comprising a.
The method of claim 1,
The coal waste-rock is a glass tile manufacturing method using a coal waste-rock coal.
The method of claim 2,
The coal hull is a method of manufacturing a glass tile using coal coal, which is a general coal ore or shell ore.
The method of claim 1,
The calcium-based material is a glass tile manufacturing method using the coal waste-rock which is any one of calcium carbonate, calcium sulfate, calcium oxide, calcium hydroxide or limestone.
The method of claim 1,
The magnesium-based material is a method for producing a glass tile using coal waste-rock which is any one of magnesium sulfate, magnesium carbonate, magnesium oxide, magnesium hydroxide or dolomite.
The method of claim 1,
The coal waste-rock, the soda ash, the calcium-based material, the magnesium-based material, the silica sand and the cullet, respectively, 5% to 70% by weight, 5% to 30% by weight, 5% to 20% by weight, Glass tile manufacturing method using coal waste-rock compounded in the proportion of 0% to 10% by weight, 5% to 15% by weight, 10% to 80% by weight.
delete delete delete delete The method of claim 1,
Glass tile manufacturing method using coal waste-rock further comprising a drying step of drying the coated glaze.
The method of claim 11,
The glaze is a glass tile manufacturing method using coal-dried rock is naturally dried.
delete The method of claim 1,
The firing step,
Glass tile manufacturing method using coal waste-rock further comprising the step of slow cooling for 10 minutes to 150 minutes after the process of maintaining the temperature.
A glass tile using coal waste-rock prepared according to any one of claims 1 to 6, 11 or 12 and 14.

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