KR100436203B1 - foam glass and method for manufacture of it - Google Patents

Abstract

The present invention disclosed is to be able to increase the foamability, to make a homogeneous foaming action, to be able to manufacture a large block and to expect the effect of energy saving.

In order to achieve this, the present invention includes a first pretreatment step of pulverizing a pure glass powder from which impurities such as mercury are removed from a waste fluorescent lamp to a particle size of 150 mesh or less to be prepared as a mother material; A second pretreatment step of applying an appropriate amount of slurry-like powder release agent that is not sintered at a high temperature of 1200 ° C. or higher to the wall surface of the formwork; A charcoal step of preparing a first mixture by adding 0.5 wt% of unoxidized graphite carbon to 100 wt% of the glass powder prepared by the first pretreatment step and then heated to a temperature of about 720 ° C .; After the execution of the above-described charcoal step, any one or more components selected from the group of potassium sulfate (K2SO4), sodium sulfate (Na2SO4) and iron oxide (Fe2O3) are added to the first mixture in a trace amount to supply oxygen to form the second mixture. step; A temperature raising step of putting the second mixture into a form prepared through the second pretreatment step and heating at an elevated temperature rate of 3 to 5 ° C. per minute in an electric furnace; A primary heating step of maintaining this state for 30 minutes when the temperature is raised to 730˜780 ° C. through the temperature raising step; A second heating step of heating the second mixture in which the first heating step is performed at a temperature of 930 to 980 ° C. for 30 minutes; Provided is a method for producing a foamed glass using a waste fluorescent lamp comprising a slow cooling step of allowing the second mixture, which has been performed in the second heating step, to be naturally cooled in air.

Description

Foam glass and method for manufacture of it

The present invention relates to a method for producing foamed glass using waste fluorescent glass, and more specifically, to use an industrial waste, in particular waste fluorescent glass, so as to have excellent insulation, plastering, sound insulation, processability, rigidity, etc. It relates to a method for producing a foamed glass using a waste fluorescent glass produced in the form having.

In general, the foamed glass is made of a heat insulating material or a sound absorbing material depending on the shape of the independent bubble structure, it is also called foam glass, foam glass, polyfoam (多 泡) glass.

In general, when glass powder is mixed with a blowing agent such as carbon paper and put into a mold having a fire resistance, and heated to about 800 ° C., the glass melts, causing foaming and expansion. After cooling, the foamed glass is produced.

Foam glass has a specific gravity of 0.16 to 0.4, is light, has excellent acid and alkali resistance, and has no physical absorption. Therefore, it is widely used as a heat insulating material for building walls and ceilings.

On the other hand, the foamed glass used as the material of the tableware is small and independent of the bubbles, and has a unique beauty shining white, and is widely used as a material of the tableware.

On the other hand, the composition consists of a mixture of soda-lime glass powder or glass polishing sludge and calcium phosphate as a blowing agent, or a mixture of soda-lime glass powder, calcium carbonate and glass.

In addition, the manufacturing method is 100 parts by weight of soda lime glass crushed or waste glass crushed or glass abrasive sludge of 1 mm or less, as in the invention described in the Republic of Korea Patent Publication No. 10-0194107 After molding a composition mixed with 2 to 40 parts by weight of the calcium phosphate compound, heat treatment at 800 to 1000 ℃ to sinter and foam to prepare a foamed glass.

In addition, in the invention described in Korean Patent Application Publication No. 1994-0000722, 100 parts by weight of soda-lime glass crushed matter and 0.3-0.4 parts by weight of calcium carbonate were mixed with 3.0-5.0 parts by weight of water glass to produce a particle diameter of 3 mm or less. The granular base foam layer and 100 parts by weight of soda-lime glass, 0.2-0.3 parts by weight of calcium carbonate, 0.5-2.0 parts by weight of inorganic pigment, 1.0-2.5 parts by weight of clay and alumina 3.0-4.0 parts by weight of water glass The granular color foam layer and the glass coating layer having a particle size of 1-3 mm in size were sequentially laminated in the guide mold, press-molded, fired and melt-foamed to produce a multilayer foam glass, or in the thickness of the entire foam glass. The base foam layer is laminated to 65-70%, the color foam layer 20-25%, and the transparent glass coating layer 10% thick, or the melt-foaming treatment in the kiln is heated up to 720 ° C. by 10 ° C. per minute, 720 ° C. After holding stand 15-20 minutes, the temperature was raised up to 850 per minute by 5 ℃ ℃, kept at 850 ℃ 30 bungan provides a method of manufacturing a multi-layer foam glass to be cooled by 3-5 ℃ per minute after the treatment foam.

In addition, in the invention described in Korean Patent Application Publication No. 10-0262623, the final glass component is 60 to 75 parts by weight of SiO2, 0.5 to 3 parts by weight of Al2O3, and B2O35 to 15 weights, regardless of the starting material, as the glass for producing foamed glass. Parts, CaO 3-15 parts by weight, MgO 3-10 parts by weight, Na 2 O 7-17 parts by weight, As 2 O 3 (or Sb 2 O 3 or Fe 2 O 3 or TiO 2 or manganese oxide, copper oxide or nickel oxide or chromium oxide or As 2 O 3 and Sb 2 O 3 Fe 2 O 3 and TiO2, manganese oxide, copper oxide, nickel oxide and chromium oxide mixtures) 0.5 to 4 parts by weight of the foamed glass, and a glass composition of 100 to 20 parts by weight of pulverized matter of less than 210㎛ (70 mesh) carbon 0.05 ~ 5 parts by weight is mixed well and put in a heat-resistant die, and using a tunnel kiln or shuttle kiln to provide a method for producing by firing under conditions maintained for 10 minutes to 60 minutes at 800 ℃ ~ 980 ℃.

In addition, in the invention described in the Republic of Korea Patent Publication No. 10-0246755, the step of hydrolyzing the waste glass powder at a temperature of 200oC ~ 300oC and pressure conditions of 50Kg / cm2 ~ 70Kg / cm2; Adding a foaming aid to the hydrated glass powder to control the pulverization to have a particle size of -325 mesh; Placing the particle size controlled hydrated glass raw material in a container and adjusting the density so that its apparent density is 0.8 or more; And, through the normal plastic foaming step, stabilization step and annealing step for the density-controlled glass raw material powder to obtain a foamed glass having a density of less than 0.3g / cm3 and thermal conductivity of less than 0.05 Kcal / hmoC It provides a foamed glass manufacturing method.

In addition, in the invention described in Korean Patent Application Publication No. 10-0281793, a mixture of carbon and fine glass powder uniformly is put in a metal mold coated with a release agent, and the first temperature increase rate is 5 to 8 in an electric muffle furnace. The method and the glass powder 150-200mesh to maintain the temperature rise at ℃ / min 30 minutes at 730 ° ~ 780 ° C. for 30 minutes and the second temperature increase rate 1 ° ~ 5 ° C. There is provided a manufacturing method.

However, the conventional methods of manufacturing the foamed glass as described above, because there is no way to recycle the waste of glass, especially waste fluorescent glass, there is no choice but to avoid the problem of environmental pollution caused by waste fluorescent glass, In addition, since waste glass cannot be recycled, wastewater is required to devise a way to recycle the glass of waste fluorescent light.

In addition, the conventional foamed glass and its manufacturing method, do not contain a lot of gas components in the composition to reduce the foamability, thus maximizing the thermal insulation, plastering, sound insulation, workability, stiffness, etc. that are characteristics as foamed glass There was a disadvantage that you can not.

The present invention is to be able to meet the conventional needs as described above, and to be able to solve the disadvantages of the conventional, the object of the present invention is to increase the foaming properties, which is characterized as a foam glass, heat insulation, plasticity It is to provide a method for producing foam glass using the waste fluorescent lamp glass that can maximize the sound insulation, processability, rigidity, and the like.

1 is a diagram for showing a heat treatment temperature process of the foamed glass produced according to the method according to the invention,

Figure 2 is a microscopic observation photograph showing the fracture surface of the glass block prepared in the state that does not add,

Figure 3 is a microscopic observation to show the fracture surface of the foamed glass block is made according to the addition, the addition is not made, and the oxygen supply action of K2SO4 contained in the waste soda lime glass powder,

Figure 4 is a microscopic picture for showing the fracture surface of the foamed glass block produced under the addition and the action of the carbonization.

In order to achieve the above object, the present invention, the first pre-treatment step to grind the pure glass powder from which impurities such as mercury are removed from the waste fluorescent lamp to a particle size of less than 150 mesh to be prepared as a parent material, and at a high temperature of 1200 ℃ or more Graphite not oxidized to 100% by weight of the glass powder prepared by the second pretreatment step of applying a slurry release agent which is not sintered to the formwork and the first pretreatment step as described above and heated to a temperature of about 720 ° C. One or more components selected from the group of potassium sulfate (K2SO4), sodium sulfate (Na2SO4), and iron oxide (Fe2O3) after the above-described carbonization step is carried out to produce the first mixture by adding 0.5% by weight of carbon of quality A small amount of oxygen is added to the first mixture to form a second mixture, and the die is prepared through the second pretreatment step. The heating step to put the second mixture in the furnace at a heating rate of 3 ~ 5 ℃ per minute, and the first heating to maintain this state for 30 minutes when the temperature is raised to 730 ~ 780 ℃ through the temperature rising step And a second heating step of heating the second mixture on which the first heating step is performed to a temperature of 930 to 980 ° C. for 30 minutes, and the second mixture in which the second heating step is completed, in air. It provides a method for producing a foamed glass using a waste fluorescent lamp comprising a slow cooling step to be naturally air-cooled.

Hereinafter, a preferred embodiment of the present invention described above will be described in detail.

The present invention relates to a method for producing foamed glass comprising a first and second pretreatment step, a charcoal step, an oxygen supply step, a temperature raising step, a primary heating step, a secondary heating step, and a slow cooling step.

That is, in the first pretreatment step, pure glass powder from which impurities such as mercury are removed from the waste fluorescent lamp is collected and ground to a particle size of 150 mesh or less to be prepared as a mother material.

Further, in the second pretreatment step, by applying an appropriate amount of slurry-like powder release agent that is not sintered at a high temperature of 200 ° C. or higher on the wall surface of the formwork, it is possible to prevent the glass powder during sintering from sticking to the formwork.

In addition, the glass powder prepared through the first pretreatment step as described above is added to the mold prepared by the second pretreatment step based on 100% by weight of the glass powder and heated to a temperature of about 720 ° C. 0.5 wt% of carbon is added to prepare a first mixture.

In this carbonation step, the carbon powder is oxidized to generate gas, and in particular, the decomposition of the carbon powder is known to be started at around 720 ° C.

After the above-described carbonization step is performed, a second mixture is formed by adding a small amount of one or more components selected from the group of potassium sulfate (K 2 SO 4), sodium sulfate (Na 2 SO 4), and iron oxide (Fe 2 O 3) in the oxygen supplying step.

In the above temperature raising step, the second mixture contained in the formwork prepared through the second pretreatment step is heated in an electric furnace at a temperature increase rate of 3 to 5 ° C. per minute, and the temperature is raised to 730 to 780 ° C. through the temperature rising step. When this is done to maintain the state as described above in the first heating step for 30 minutes.

As a result, carbon is not decomposed in a state where the temperature increase to 730 to 780 ° C is not completed.

That is, since the decomposition of carbon starts at about 680 ° C., if the temperature increase rate is slower than 3 to 5 ° C. per minute, carbon is decomposed in a state in which the glass is not softened yet, thereby making it impossible to generate bubbles.

Therefore, in the glass powder undergoing the temperature raising step according to the present invention, the surface is first vitrified, and in this state, the first and second heating steps are sequentially performed, thereby generating sufficient and uniform bubbles.

On the other hand, the heat holding time in the first heating step as described above has a temperature difference of less than 10 ℃ inside and outside the glass when maintained for 30 minutes at 730 ~ 780 ℃ as a result of analysis by the heat tracking device.

In addition, after the first heating step is performed, the second mixture is heated for 30 minutes at a temperature of 930 to 980 ° C. in the second heating step, and the second mixture after the completion of the second heating step is slowly cooled. Allow natural air cooling in the air through the steps.

Example 1

A first pretreatment step;

Pure glass powder from which impurities such as mercury were removed from the waste fluorescent lamp was pulverized with a jaw crusher to prepare a particle having a particle size of 150 mesh or less.

A second pretreatment step;

The slurry-like powder releasing agent which was not sintered at a high temperature of 1200 ° C. or higher was appropriately applied to a formwork wall of 300 mm × 300 mm × 200 mm, thereby allowing a smooth separation between the glass and the formwork.

A peat step;

100 wt% of the glass powder prepared through the first pretreatment step was placed in the formwork prepared through the second pretreatment step, and heated to a temperature of about 720 ° C., and 0.5 wt% of the carbon of the non-oxidized graphite was added using a V-mixer. The first mixture was prepared by uniformly mixing.

Temperature increase step;

The above-mentioned second mixture was placed in a die prepared through the second pretreatment step, and was heated in an electric furnace at a temperature increase rate of 3 to 5 ° C. per minute (see FIG. 1).

First heating step;

When the temperature was raised to 730 to 780 ° C. through the temperature raising step, this state was maintained for 30 minutes (see FIG. 1).

Secondary heating step;

The first mixture in which the first heating step was carried out was heated to a temperature of 940 ° C. for 30 minutes.

Slow cooling step;

After completion of the second heating step, the second mixture was allowed to naturally cool in air (see FIG. 1).

That is, foamed glass was manufactured by heating and calcining according to the schedule as shown in FIG. 1, and the physical properties of the foamed glass manufactured through these steps were tested according to the American Material Testing Standard (ASTM C552-91). .

- next -

1) Density: 400 ㎏ / ㎥

2) Compressive strength: 800 ㎪

3) bending strength: 600 ㎪

4) Absorption rate: 2.5%

5) Thermal Conductivity: 0.085 W / mK (38 ℃)

6) On the other hand, when the fractured surface of the foam glass was observed under a microscope, as shown in FIG. 2, relatively uneven pores were generated, which was presumed to be a lack of oxygen content.

In addition, the block was partially destroyed even when the cooling rate was slowed down during the manufacture of foamed glass into large blocks. When the soda-lime glass was melted using fossil fuel as a heat source, about 0.3 Wt% of SO 3 was contained in the glass. Therefore, the supply of sufficient component is not made.

Example 2

A first pretreatment step;

Pure glass powder from which impurities such as mercury were removed from the waste fluorescent lamp was pulverized with a jaw crusher to prepare a particle having a particle size of 150 mesh or less.

A second pretreatment step;

The slurry-like powder releasing agent which was not sintered at a high temperature of 1200 ° C. or higher was appropriately applied to a formwork wall of 300 mm × 300 mm × 200 mm, thereby allowing a smooth separation between the glass and the formwork.

A peat step;

100 wt% of the glass powder prepared through the first pretreatment step was placed in the formwork prepared through the second pretreatment step and heated to a temperature of about 720 ° C., and 0.3 wt% of the carbon of the non-oxidized graphite was added using a V-mixer. The first mixture was prepared by uniformly mixing.

Oxygen supply step;

After the above-described carbonization step was performed, 1% by weight of sodium sulfate (Na 2 SO 4) selected from the group of potassium sulfate (K 2 SO 4), sodium sulfate (Na 2 SO 4), and iron oxide (Fe 2 O 3) was added to the first mixture to form a second mixture. .

Temperature increase step;

The above-mentioned second mixture was placed in a form prepared through the second pretreatment step, and heated in an electric furnace at a temperature increase rate of 3 to 5 ° C. per minute (see FIG. 1).

First heating step;

When the temperature was raised to 730 to 780 ° C. through the temperature raising step, this state was maintained for 30 minutes (see FIG. 1).

Secondary heating step;

The second mixture in which the first heating step was carried out was heated to a temperature of 860 ° C. for 30 minutes.

Slow cooling step;

After completion of the second heating step, the second mixture was allowed to naturally cool in air (see FIG. 1).

The physical properties of foamed glass manufactured through these multiple steps were tested in accordance with the American Material Testing Standard (ASTM C552-91).

- next -

1) Density: 210 ㎏ / ㎥

2) Compressive strength: 730 ㎪

3) Bending Strength: 570 ㎪

4) Absorption rate: 0.3%

5) Thermal Conductivity: 0.067 W / mK (38 ℃)

6) On the other hand, when the fracture surface of the foam glass was observed under a microscope, as shown in Fig. 3, the bubbles were uniformly formed as compared to the foam glass as in Example 1 without adding sodium sulfate (Na 2 SO 4). Able to know.

Example 3

A first pretreatment step;

Pure glass powder from which the impurities such as mercury were removed from the waste fluorescent lamp was pulverized with a jaw crusher and prepared with a particle size of 150 mesh or less. Also, K2SO4 component was contained, and the physical properties were compared with those obtained from the waste fluorescent lamp. The glass powder obtained from the slightly high soda-lime waste glass was prepared.

A second pretreatment step;

The slurry-like powder releasing agent which was not sintered at a high temperature of 1200 ° C. or higher was appropriately applied to a formwork wall of 300 mm × 300 mm × 200 mm, thereby allowing a smooth separation between the glass and the formwork.

50 wt% of the glass powder obtained from the waste fluorescent lamp prepared through the first pretreatment step and 50 wt% of the glass powder obtained from the waste soda lime glass are mixed and placed in a form prepared through the second pretreatment step, and the temperature is about 720 ° C. Heated to.

Oxygen supply step;

1 weight% of sodium sulfate (Na2SO4) selected from the group of potassium sulfate (K2SO4), sodium sulfate (Na2SO4), and iron oxide (Fe2O3) was added to the mixed glass powder as mentioned above.

Temperature increase step;

The above-mentioned second mixture was placed in a form prepared through the second pretreatment step, and heated in an electric furnace at a temperature increase rate of 3 to 5 ° C. per minute (see FIG. 1).

First heating step;

When the temperature was raised to 730 to 780 ° C. through the temperature raising step, this state was maintained for 30 minutes (see FIG. 1).

Secondary heating step;

The second mixture in which the first heating step was carried out was heated to a temperature of 880 ° C. for 30 minutes.

Slow cooling step;

After completing the second heating step, the glass was naturally cooled in air to be fired into blocks (see FIG. 1).

The physical properties of foamed glass manufactured through these multiple steps were tested in accordance with the American Material Testing Standard (ASTM C552-91).

- next -

1) Density: 220 ㎏ / ㎥

2) Compressive strength: 720 ㎪

3) Bending Strength: 580 ㎪

4) Absorption rate: 0.3%

5) Thermal Conductivity: 0.068 W / mK (38 ℃)

6) On the other hand, when the fracture surface of the foam glass was observed under a microscope, as shown in Fig. 4, the bubbles were uniformly formed as compared to the foam glass as in Example 1 without adding sodium sulfate (Na 2 SO 4). It can be seen that it has a denser structure than the foamed glass as in Example 2 so that the breakage of the block does not occur.

Comparison of the manufacturing conditions and physical properties of each embodiment of the present name is shown in Table 1.

Table 1

The foamed glass production method according to the present invention as described above can not only maximize the thermal insulation, plastering, sound insulation, workability, stiffness, etc. that are characteristics of the foamed glass by increasing the foamability, but also sufficient oxygen into the foamed component. As a result of supplying a homogeneous foaming effect, it is possible to prevent the destruction of the block due to K2SO4 components, additionally to manufacture a large block, and to lower the heat treatment temperature to expect energy saving effect It has the advantage.

Claims (6)

A first pretreatment step of pulverizing the pure glass powder from which impurities such as mercury are removed from the waste fluorescent lamp to a particle size of 150 mesh or less to prepare as a mother material; A second pretreatment step of applying an appropriate amount of slurry-like powder release agent that is not sintered at a high temperature of 1,200 ° C. or higher to the wall surface of the formwork; A charcoal step of preparing a first mixture by adding 0.5 wt% of unoxidized graphite carbon to 100 wt% of the glass powder prepared through the first pretreatment step and heated to a temperature of about 720 ° C .; After the carbonization step is performed, any one or more components selected from the group consisting of potassium sulfate (K ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), and iron oxide (Fe ₂ O ₃ ) are added to the first mixture in a small amount. An oxygen supplying step of forming a second mixture; A temperature increase step of placing the second mixture in a form prepared through a second pretreatment step and heating the electric mixture at a temperature increase rate of 3 to 5 ° C. per minute in an electric furnace; A primary heating step of maintaining this state for 30 minutes when the temperature is raised to 730˜780 ° C. through the temperature raising step; A second heating step of heating the second mixture in which the first heating step is performed at a temperature of 930 to 980 ° C. for 30 minutes; And a slow cooling step of naturally cooling the second mixture in air after completion of the second heating step. The method of claim 1, In the first pretreatment step, the parent material is prepared by mixing 50% by weight of pure glass powder obtained from waste fluorescence lamp and 50% by weight of waste soda lime glass powder. The method of claim 1, The method of producing a foamed glass using a waste fluorescent lamp, characterized in that the amount of the added carbon to the glass powder in the step of carbonization is 0.3% by weight of carbon of the unoxidized graphite. The method of claim 1, The method of producing a foamed glass using a waste fluorescent lamp, characterized in that sodium sulfate (Na ₂ SO ₄ ) is added to the glass powder in the oxygen supply step in 1% by weight as an oxygen supply component. The method of claim 1, Method for producing a foamed glass using a waste fluorescent lamp, characterized in that the heating temperature of the glass powder in the secondary heating step is 860 ℃. The method of claim 1, Method for producing a foamed glass using a waste fluorescent lamp, characterized in that the heating temperature of the glass powder in the secondary heating step is 880 ℃.