KR101102607B1 - Manufacturing method of the soda-lime glass by using refused coal ore - Google Patents

Abstract

The present invention relates to a method for producing soda-lime-based glass using coal waste-rock, comprising: mixing a mixture containing coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, and cullet in a predetermined ratio; Melting the blended mixture; Shaping the molten mixture; And slow cooling the shaped mixture; It provides a soda-lime-based glass manufacturing method using coal waste-rock containing.
According to the present invention, it is possible to manufacture glass secondary applications such as building glass tiles and announcement glass panels using coal waste-rock, and to produce glass by using coal waste-rock generated when coal is collected from coal mines. Use resources and protect the environment.

Description

Manufacturing method of the soda-lime glass by using refused coal ore}

The present invention relates to a method for producing soda-lime-based glass using coal waste-rock. More specifically, the present invention relates to a manufacturing method for producing soda-lime glass using coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, cullet and the like.

In general, the coal industry, which has been the foundation 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. Currently, the number of coal mines is 9 from 2004 to 347 in 2004. This reduced about 97.4%. In addition, a large amount of coal waste-rock generated as a result of the development of coal mines has been generated in the meantime, but proper recycling methods have not been developed, and simple landfill treatment is difficult, so it has been left unattended around the coal mine area for a long time. Because it is not done, it is acting as a hazard of the natural environment with the damage of the surrounding landscape today.

According to the 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 3,600 in nine coal mines that have been available. It is reported that 10,000 tons have been generated and accumulated.

Until now, 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 plants. In the case of abandoned coal waste rocks, the surrounding landscape is damaged, environmental pollution, and its disposal cost. Has problems.

Therefore, the present invention is to solve the above-mentioned problems, using a coal waste-rock that is generated when coal is collected from coal mines using soda-lime-based glass manufacturing method using coal waste-rock that can utilize the waste resources and protect the environment. to provide.

In order to achieve the above object, a soda-lime-based glass manufacturing method using coal waste-rock according to the present invention comprises: mixing a mixture containing coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, and cullet in a predetermined ratio; Melting the blended mixture; Shaping the molten mixture; And slow cooling the shaped mixture.

In addition, the coal waste-rock is a hard coal, and the hard coal is a general hard coal or shell hard coal.

In addition, the calcium carbonate is any one of calcium sulfate, calcium oxide, calcium hydroxide, limestone as a raw material for constituting the calcium component in the glass, the magnesium sulfate is magnesium carbonate, oxide as a raw material for constituting the magnesium component in the glass Use either magnesium, magnesium hydroxide or dolomite.

In the soda-lime-based glass manufacturing method using the coal waste-rock, the weight percent of the coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, cullet is 5 to 70% by weight, 5 to 30% by weight, 5 to 20, respectively Embodiments may be made of weight percent, 0 to 10 weight percent, 5 to 15 weight percent, and 10 to 80 weight percent.

In addition, in the soda-lime-based glass manufacturing method using the coal waste-rock, the melting can be configured to an embodiment performed for 0.5 to 5 hours at 1300 ~ 1700 ℃.

In addition, the soda-lime-type glass using the coal waste-rock manufactured by the said method can be comprised in an Example.

As described above, the present invention provides an effect of providing a method for producing soda-lime-based glass using coal waste-rock, which can be utilized to manufacture glass secondary applications such as architectural glass tiles and glass substrates using coal waste-rock. Have

In addition, the present invention provides the effect of utilizing the waste resources and environmental protection by manufacturing glass using coal waste-rock that is generated when coal is collected from coal mines.

1 is a process chart of the glass manufacturing method using coal waste-rock.
2 is a TG / DTA graph of the hard coal pumice.
3 is a photograph of a molten glass produced using coal waste-rock.
4 is an X-ray diffraction pattern of molten glass prepared using coal waste-rock.
FIG. 5 is a graph of the transmittance of glass having 40% by weight of cullet and manufactured using ordinary keel and pumice pumice, respectively.
FIG. 6 is a graph of the transmittance of glass having 20% by weight of cullet and manufactured using ordinary keel and pumice pumice, respectively.
7 is a graph of transmittance of glass using coal waste-rock having 20% by weight of cullet and manufactured using chemical and mineral raw materials, respectively.
8 is a graph of the transmittance of glass using coal waste-rock having 40% by weight of cullet and manufactured using chemical and mineral raw materials, respectively.
FIG. 9 is a graph of the transmittance of glass prepared using coal waste-rock having 20% by weight and 40% by weight.
FIG. 10 is a color coordinate of glass prepared using a normal hard pumice stone.
FIG. 11 is a color coordinate of glass manufactured using cell hard pumice stone.
12 is a graph of the thermal expansion coefficient of the glass prepared using coal pebbles.

The foregoing objects, features, and advantages will become more apparent from the following examples taken in conjunction with the accompanying drawings. Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the abbreviations shown in the table and the drawings are as follows.

(CN: General Pelletite, CS: Shell Pelletite, CM: Chemical Raw Material, NM: Natural Mineral Raw Material, W20: 20% Percent White Pale, W40: 40% Percent White Pale, G20: 20% Percent Green cullet, G40: 40 weight percent green cullet, B20: 20 weight percent brown cullet, B40: 40 weight percent brown cullet.)

1 is a process diagram of a soda-lime-based glass manufacturing method using coal waste-rock according to an embodiment of the present invention, the present invention includes coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, cullet Blending the mixture to a predetermined ratio; Melting the blended mixture; Shaping the molten mixture; And it provides a soda-lime-based glass manufacturing method using coal waste-rock comprising the step of slow cooling the molded mixture.

Coal wastes are divided into digging refuses from the drilling process and coal-preparation refuses from the process of coal mining. There is more carbon content and there is a shell type pumice pumice (hereinafter referred to as shell pumice pumice), which is commonly called a shell. In the present invention, as a method for producing soda-lime-based glass using coal waste-rock, preferably, it is used in the case of pulverized coal, more preferably in the general pulverized pumice and shell pulverized pumice. Table 1 shows the chemical component analysis values of ordinary pumice pumice and shell pumice pumice used in the present invention.

As can be seen in Table 1, in the case of ordinary pumice pumice, the content of SiO ₂ is 81.1%, The content of Al ₂ O ₃ was 12.0%, and the content of SiO ₂ was 70.7%, The content of Al ₂ O ₃ was found to be 18.5%. The content of Fe ₂ O ₃ is 0.51% in general keel pumice, whereas in shell pumice pumice, the difference is 3.37%, especially in the case of shell pumice pumice, it is much blacker than naked 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, in the present invention, the calcium carbonate may be used as a raw material for constituting the calcium component in the glass, in addition to calcium carbonate, calcium sulfate, calcium oxide, calcium hydroxide, limestone, and the like. As a raw material, magnesium carbonate, magnesium oxide, magnesium hydroxide, dolomite and the like can be used in addition to magnesium sulfate.

The mineral raw materials used in the present invention are ground to 0.7 mm or less, preferably 0.5 mm or less, as a trigger to uniformly control the particle size.

In the present invention, the cullet used as the flux of the glass is a cullet of white, green and brown, and all of the soda-lime jars and tableware cullet that are easily available on the market.

Coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand, cullet in the mixture of the present invention is 5 to 70% by weight, 5 to 30% by weight, 5 to 20% by weight, 0 to 10% by weight, 5 to 15 Percentage by weight, 10 to 80 percent by weight. More preferably, the mixture may be blended in a blending ratio as shown in Table 2.

The blended mixture is placed in an alumina crucible and melted at 1300 to 1700 ° C for 0.5 to 5 hours, more preferably at 1550 ° C for 1 hour.

According to the present invention, a picture of the molten glass prepared by melting at 1550 ° C. for 1 hour with the compounding material of each composition is shown in FIG. 3, and as shown in FIG. Regardless of the type, clear and transparent glass was rolled, but the case of using shell ore pumice was vitrified well, but due to excessive coloring, the transmittance was lowered, making the black glass appear almost opaque to the naked eye. In addition, as a result of XRD analysis to determine the degree of vitrification and recrystallization of these glasses, as shown in FIG. 4, a graph of an amorphous phase in which crystalline peaks do not appear in the glass of all compositions was obtained. Accordingly, it can be seen that complete vitrification proceeded in all compositions and no special recrystallization occurred during cooling.

As can be seen in Figure 5, the visible light transmittance of the molten glass using the normal pumice pumice is a glass wave glass composition is 85.66%, green green glass glass composition 72.28%, brown green glass composition Is 80.41%, but in molten glass made using shell pumice pumice, it shows much lower transmittance values of 35.03%, 29.98%, and 32.60%, respectively. This is because the Fe ₂ O ₃ ) content is relatively high, and the coloring and light blocking effects of these components are increased during the vitrification process. Especially, as shown in FIG. This was much weighted, indicating a larger transmittance difference.

As shown in Figure 7, as the transmittance characteristics according to the type of additive material, when the CaO source of the glass component using calcium carbonate as the chemical material, the white cullet composition is 82.35%, green cullet glass at 20% mixing conditions of cullet 71.32% of the composition and 78.19% of the brown wave glass composition showed 79.72%, 71.87%, and 75.06% of the molten glass using the limestone, which is a mineral raw material, respectively. Almost similar values were observed at the ± 3% level, which shows a similar tendency even under 40% mixed cullet as shown in FIG. 8. Therefore, there is no significant difference in the optical properties of glass even when limestone, which is a mineral material, is used instead of calcium carbonate as a chemical material, and this may be economical by using relatively inexpensive mineral material.

In addition, as shown in Figure 9 (a), (b) to look at the transmittance characteristics according to the type of the cullet, when mixing the cullet 40% using the normal keel pumice, the composition of the white cullet glass is 85.66%, green wave The glass composition was 72.28% and the brown cullet composition was 80.41%, and when 20% of the cullet was mixed, the transmittance values were 82.35%, 71.32%, and 78.19%, respectively. The difference in transmittance of 71 ~ 86% was shown, and the order of white wave glass> brown wave glass> green wave glass was used. The self-transmittance of only wave glass used in the present invention was 93.06% white, 42.25% green, and 31.11% brown. Compared with the visible light transmittance of molten glass manufactured by using 20% of these cullet in general pumice pumice, it can be seen that the decrease in transmittance of about 10% occurred in white cullet, but green cullet and brown cullet are used. Manufactured by For the melting glass, it can be seen that more than about 30% transmittance hayeoteum rise. In other words, the visible light transmittance of at least 70% is shown in all compositions using ordinary keel pumice as raw material, so when general waste leek glass is mixed, it is useful as a commercial glass product in terms of transmittance, especially white wave glass. When used, it shows a high transmittance of 80% or more, so that other colorants of various colors may be prepared by adding another colorant.

And the transmittance value according to the mixing amount of the cullet was observed to show a higher transmittance value than when the mixing amount of the cullet is 40% under most conditions.

As shown in (c) and (d) of FIG. 9, the transmittance of the glass manufactured by each cullet using the shell pumice pumice showed a lower transmittance of 0 to 35% than that of ordinary pumice pumice, especially minerals. In the case of the molten glass using the raw material, the comparative analysis of the characteristics is impossible because the visible light transmittance is almost zero (zero) in all compositions regardless of the mixing amount of the cullet. Therefore, in the case of manufacturing the glass using shell hard pumice, it may be used for the 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 color difference (chromaticity) using the UV / VIS / NIR Spectrometer to know the color change according to the composition and color wave glass use.

10 and 11 show the color difference 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 color difference according to each mixing condition, molten glass using ordinary hard pumice ore 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 hard pumice stone has a high transmittance regardless of the type of the cullet. On the other hand, in the case of molten glass using shell hard pumice, it is distributed in each direction centering on the white region of the center according to the kind and mixing amount of the cullet on the 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.

12 is a thermal expansion coefficient of the thermal properties of the glass prepared according to the present invention was measured using a TMA (Thermomechanical Analyzer), the thermal expansion coefficient of the molten glass using a normal keel hard pumice is 8.273x10 ^-6 / ℃, shell keel pumice The thermal expansion coefficient of the molten glass was 8.972x 10 ^-6 / ℃, which was slightly lower than that of general soda-lime glass, which was 9 ~ 10x10 ^-6 / ℃. Did. In addition, the softening point (softening point) of the measurement results, the softening point of the glass using the normal keel hard pumice was found to be 750 ℃, the softening point of the glass using shell keel pumice pumice showed similar values to 746 ℃. In general, the softening point of general soda lime glass shows a high value of about 10 to 15 ° C., compared with that of 725 to 735 ° C., but it did not show a big 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 the 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 4x10 ^-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.

As described above, the present invention can be utilized in various secondary glass products such as glass tiles or foam glass panels having high heat resistance and various colors using waste stones discarded.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various permutations and modifications can be made without departing from the spirit of the present invention. It will be obvious to him.

CN: Normal Pelletite, CS: Shell Pelletite, CM: Chemical Raw Material, NM: Natural Mineral Raw Material, W20: 20% Percent White Wave Glass, W40: 40% Percent White Wave Glass, G20: 20% Percent Green Cullet, G40: 40 percent by weight green cullet, B20: 20 percent by weight brown cullet, B40: 40 percent by weight brown cullet.

Claims (8)

Blending a mixture including coal waste-rock, soda ash, calcium component raw material, magnesium component raw material, silica sand and cullet in a predetermined ratio;
Melting the blended mixture;
Shaping the molten mixture; And
Slow cooling the shaped mixture;
Including;
The calcium component raw material is any one of calcium carbonate, calcium sulfate, calcium oxide, calcium hydroxide, limestone,
The magnesium component raw material is a soda-lime-based glass manufacturing method using coal waste-rock which is any one of magnesium sulfate, magnesium carbonate, magnesium oxide, magnesium hydroxide, dolomite.
The method of claim 1,
The coal waste-rock is
Method for producing soda-lime glass using coal waste-rock.
The method of claim 2,
The pulverized stone is a normal ore or shell ore
Method for producing soda-lime glass using coal waste-rock.
delete delete The method of claim 1,
The calcium component raw material is calcium carbonate, the magnesium component raw material is magnesium sulfate,
5 to 70% by weight, 5 to 30% by weight, 5 to 20% by weight, 0 to 10% by weight, 5 to 15% by weight of coal waste-rock, soda ash, calcium carbonate, magnesium sulfate, silica sand and cullet, respectively Included in proportion of 10-80% by weight
Method for producing soda-lime glass using coal waste-rock.
The method of claim 1,
The melting is performed at 1300-1700 ° C. for 0.5-5 hours
Method for producing soda-lime glass using coal waste-rock.
A soda-lime-based glass produced by the method according to any one of claims 1 to 3, 6 and 7.

Images