KR20090014963A - Method for manufacturing zeolitic foamed glass and equipment for manufacturing zeolitic foamed glass - Google Patents

Abstract

An apparatus for manufacturing zeolitic foamed glass is provided to cut down energy needed in manufacture of the zeolitic foamed glass and to obtain the zeolitic foamed glass of high quality. An apparatus for manufacturing zeolitic foamed glass contains a plasticity unit(A) for heating and foaming glass powder in which foaming agent is added and forming the foamed glass, a break unit(B1) granulating the foamed glass foam formed with the plasticity unit, a solution penetration unit(B2) dipping a zeolite solution into granularity foamed glass, a heating unit(C) changing the granularity foamed glass dipping the zeolite solution into zeolite and a microwave reviewing unit(D). The plasticity unit contains a preheating part(52), a kiln(53) and a cooling part(54) arranged along a returning direction of a roller conveyer(51).

Description

METHOD FOR MANUFACTURING ZEOLITIC FOAMED GLASS AND EQUIPMENT FOR MANUFACTURING ZEOLITIC FOAMED GLASS}

TECHNICAL FIELD This invention relates to the technique which uses powder glass as a raw material and manufactures the foamed glass whose surface was zeolite.

As a technique related to the present invention, various research and developments have been conducted on the technology for producing zeolitic foamed glass having an adsorption function or an ion exchange function by zeolitizing the surface of the foamed glass. There is a method of zeolitizing the surface by irradiating microwaves to the immersed foam glass (see Patent Document 1, for example).

Patent Document 1 Japanese Patent Application Laid-Open No. 2005-145807

In the "manufacturing method of surface zeolitic glass" of patent document 1, since microwave is irradiated in the state which immersed the glass raw material in the sodium aluminate aqueous solution or the said aqueous solution was apply | coated to the glass raw material, it requires a long time to zeoliteize. do. In addition, in the case of aqueous sodium aluminate solution having a high concentration, since it is difficult to penetrate into the pores inside the foamed glass, there are many parts which are not zeolitized, and the cation exchange capacity (CEC value) may be lowered. On the other hand, in the case of an aqueous sodium aluminate solution having a low concentration, the permeability into the foam glass is good, but the zeolitization reaction does not proceed, and the CEC value cannot be lowered.

Then, the problem to be solved by this invention is to reduce the energy required for manufacture of a zeolitic foamed glass, and to obtain a high quality zeolitic foamed glass.

The zeolitic foamed glass production method of the present invention comprises a firing step of forming a foamed glass by heating and foaming a glass powder to which a blowing agent is added, a crushing step of granulating the foamed glass formed in the firing step, and the crushing step At least one of a solution infiltration step of impregnating the granulated foamed glass with the zeolitic solution and a heating step and a microwave irradiation step of zeoliticizing the granular foamed glass impregnated with the zeoliticized solution,

At least one of the heating step and the microwave irradiation step is characterized by using the excess heat generated in the firing step.

With such a configuration, since part of the heat required for the zeolitization reaction of the granulated foamed glass impregnated with the zeolitized solution can be supplemented by the excess heat generated in the manufacturing process of the foamed glass, the energy consumption required for the zeolitized reaction It can reduce, and the energy required for manufacture of a zeolitic foamed glass can be reduced. As the blowing agent, calcium carbonate, silicon carbide, dolomite, sodium borate and the like are suitable, but they are not limited to these.

Here, when the sodium aluminate aqueous solution is used as the zeolitization solution, the alkali component, alumina component and water required for the zeolitization reaction are supplied from the zeolitization solution, and the silica component is supplied from the granular foamed glass. For this reason, it is not necessary to supply a silica component newly, and since an alkali component, an alumina component, and water are mixed in the sodium aluminate solution, the operation | work like mixing a new drug is also unnecessary, and a working process can be shortened.

When the mixed solution of sodium hydroxide and aluminum hydroxide is used as the zeolitic solution, the alkali component, alumina component and water required for the zeolitization reaction are supplied from the zeolitication solution, and the silica component is reacted by the strong alkali action of sodium hydroxide. It is supplied from the softened granular foam glass surface. For this reason, the zeoliteization rate of a granular foamed glass can be raised.

When the mixed aqueous solution of the glass powder and sodium aluminate is used as the zeolitic solution, the silica component can be eluted from the glass powder into the zeolitic solution by mixing the glass powder in advance with an aqueous sodium aluminate solution. Moreover, the glass powder which is a raw material of the manufacturing process of foam glass can be used effectively as a silica component, and since it is a glass powder, the solubility of the silica component in the sodium aluminate aqueous solution is favorable.

On the other hand, when the mixed aqueous solution of water glass and sodium aluminate is used as the zeolitization solution, the silica component and water required for the zeolitization reaction are supplied from the water glass, and the alumina component, the alkali component and water are supplied from the sodium aluminate. For this reason, the molar ratio of the alkali source, alumina source, silica source, and water required for zeolitization can be adjusted. For this reason, as needed, zeolites of various structures, such as A-type zeolite, X-type zeolite, and Y-type zeolite, can be formed.

Next, the zeolitic foamed glass manufacturing equipment of the present invention is a firing means for heating and foaming the glass powder to which the blowing agent is added to form a foamed glass, crushing means for granulating the foamed glass formed by the firing means, and the crushing At least one of a solution penetrating means for impregnating a zeolitic solution in the granular foamed glass formed by the means, and a heating means and a microwave irradiation means for zeolitizing the granular foamed glass in which the zeolitic solution is impregnated,

The heat transfer means which supplies the excess heat which generate | occur | produces with the said baking means to at least one of the said heating means and the said microwave irradiation means is provided, It is characterized by the above-mentioned.

With such a configuration, it becomes possible to carry out the above-described method of manufacturing the zeolitized glass according to the present invention, to reduce the energy required for the production of the zeolitic foamed glass, and to obtain a high-quality zeolitic foamed glass. .

Here, when the solution penetration means is provided with an airtight container containing the zeolitized solution in which the granular foamed glass is immersed, and a pressure reducing means for lowering the air pressure in the airtight container, the pores of the granular foamed glass, in particular, Since the zeolitization solution can penetrate into the micropores of the microscopic size, the zeolitization rate of the granular foamed glass can be increased.

The zeolite foamed glass production method and zeolitic foamed glass production equipment of the present invention can reduce the energy required for the production of zeolitic foamed glass, thereby obtaining a high quality zeolitic foamed glass.

(The best mode for carrying out the invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described based on drawing. BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows schematic structure of the zeolitic foamed glass manufacturing equipment which is embodiment of this invention, and FIG. 2 is a figure which shows the manufacturing process in the zeolitic foamed glass manufacturing equipment shown in FIG.

As shown in FIG. 1, the zeolitic foamed glass manufacturing equipment 50 (hereinafter, referred to as "manufacturing equipment 50") heats and foams the glass powder to which the foaming agent is added to form foamed glass. Firing means (A), crushing means (B1) for granulating the foamed glass formed by the calcination means (A), and solution penetrating means (B2) for impregnating a zeolitic solution with the granular foamed glass formed of the crushing means (B1). And a heating means (C) and a microwave irradiation means (D) for zeoliteizing the granular foamed glass impregnated with the zeolitication solution.

In the baking means A, the preheating stand 52, the baking furnace 53, and the cooling stand 54 are arrange | positioned according to the conveyance direction of the roller conveyor 51 which conveys a foamed glass raw material. Downstream of the preheating zone 52 and the cooling zone 54, intake apparatuses 55 and 56 for heat recovery are arranged. The intake apparatus 55, 56 is a heat transfer means which respectively sucks in high temperature air above the roller conveyor 51 by the fan F, and supplies it to another place.

In the crushing means B1, the crushing 57 and classification 58 of the foamed glass formed in the baking means A are performed. In the solution penetrating means B2, the zeolite solution immersion 59 of the foamed glass crushed 57 and classified 58 is performed by the crushing means B1, and then the extra zeolitized solution adhering to the foamed glass is removed. The zeolitic solution liquid removal 60 is performed.

The roller means 61 and the heating furnace 62 are provided in the heating means C, and below the roller conveyor 61 in the heating furnace 62, the intake apparatus 55, 56 of the baking means A is carried out. The heater 63 which generate | occur | produces with the hot air supplied from the is arrange | positioned.

The microwave irradiation means D is provided with a roller conveyor 64 and a heating furnace 66 for irradiating microwaves generated by the microwave oscillator 65, and below the roller conveyor 64 in the heating furnace 66. The heater 67 which generates heat by the hot air supplied from the intake apparatus 55 and 56 which is a heat transfer means is arrange | positioned.

Next, based on FIG. 2, the manufacturing process of the zeolitic foamed glass in the manufacturing installation 50 shown in FIG. 1 is demonstrated.

As shown in FIG. 2, the pretreatment 1 is performed to the waste glass used as a raw material. In the pretreatment 1, metal and labels, such as a cap mixed in waste glass, are removed. Although waste glass is used as a raw material in this embodiment, since it is not limited to this, a general glass material can be used as a raw material.

When the waste glass which passed through the pretreatment process (1) is crushed to a particle diameter of about 2-5 mm in the 1st grinding process (2), and becomes a glass powder of about 30-100 micrometers in particle size in the secondary grinding (3) process then, After pulverized until, it is stored in the glass powder raw material storage (4). And the blowing agent mixing 5 is performed to the glass powder supplied to the glass powder raw material storage part 4. In this embodiment, although about 0.5-15 mass% of calcium carbonate which is a foaming agent is added to glass powder, it is not limited to this.

The glass powder having passed through the foaming agent mixture 5 is loaded on the roller conveyor 51 of the baking means A shown in FIG. 1 and fired while passing through the preheating table 52, the firing furnace 53, and the cooling table 54. 6) to form foamed glass. In the present embodiment, the firing temperature is set to 800 to 900 ° C and the baking time is 30 to 120 minutes, but the present invention is not limited thereto. The foamed glass formed through the firing (6) process is crushed in the foamed glass coarse grinding process (7) to form a mass having a particle diameter of about 10 mm, and then stored in the primary storage unit (8).

The massive foamed glass supplied from the primary storage part 8 is pulverized through the foamed glass crushing 9 process in the crushing means B1 shown in FIG. 1 to form a granular body of 50 mm or less, and then foamed glass classification. Classification and bag filling are performed in the bag filling 10 process. At this time, the granular foamed glass having a classified particle size of 2 mm or less is mixed in the glass powder before the foaming agent mixing (5) step.

About the granular foamed glass of the particle size 2-50mm classified at the foaming glass classification and bag filling 10 process, in the solution penetrating means B2 shown in FIG. 1, the solution of the zeoliticization solution immersion 59 and the zeolitization solution Removal 60 is performed. In this embodiment, although the mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as a zeolitization solution, it is not limited to this.

Through the solution penetrating means (B2), the granular foamed glass impregnated with the zeolitized solution passes through at least one of the heating means (C) and the microwave irradiation means (D) shown in FIG. And zeolitic foamed glass is formed. After the zeolitic foamed glass is washed 12 in the next step, and dewatered and dried 13 is performed, the product is shipped 14.

As shown in FIG. 1, in the production facility 50, a part of the heat necessary for the zeolitization reaction of the granular foamed glass impregnated with the zeolitized solution is generated by the manufacturing process (firing means A) of the foamed glass. Since it collect | recovers and supplements, the energy consumption required for a zeolitization reaction is small, and the energy required for manufacture of a zeolitic foamed glass can be reduced.

As described above, in the zeolitization solution immersion step 59 shown in FIGS. 1 and 2, a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolitization solution. Therefore, the alkali component, alumina component and water necessary for the zeolitization reaction are supplied from the zeolitization solution, and the silica component is supplied from the surface of the granular foamed glass softened by the strong alkali action of sodium hydroxide, thereby forming the zeolite of the granular foamed glass. Can increase fire rate. In the production facility 50, when the granular foamed glass having an apparent specific gravity of 1.2 or more is zeolited, a zeolitic foamed glass having a cation exchange capacity (CEC value) of 20 to 60 meq / 100 g can be obtained.

3-9, the structure, function, etc. of the various apparatus which comprise the manufacturing facility 50 are demonstrated. FIG. 3 is a schematic diagram showing the vicinity of a storage silo constituting the manufacturing facility 50 shown in FIG. 1, FIG. 4 is a perspective view showing a part of the roller conveyor constituting the manufacturing facility 50, and FIG. 5 is a manufacturing facility ( The schematic diagram which shows the foamed glass coarse grinder which comprises 50), FIG. 6 is the schematic diagram which shows the solution permeation apparatus which comprises the manufacturing installation 50, FIG. 7: The zeolitic solution liquid removal apparatus which comprises the manufacturing installation 50 It is a side view which shows. 8 is a front view of the zeolitic solution liquid removing apparatus shown in FIG. 7, and FIG. 9 is a perspective view showing a reaction vessel when zeolitic granular foamed glass impregnated with a zeoliticization solution.

The storage silo 20 shown in FIG. 3 is arrange | positioned and prepared in the glass powder raw material storage part 4 shown in FIG. 2 in order to store glass powder GP. The storage silo 20 has a tubular portion 20a having the same inner diameter and a funnel portion 20b that is installed in succession below it, and the funnel portion 20b is gradually reduced in diameter toward the lower end opening 21. . The vibration device MB is arrange | positioned at the outer surface of the funnel part 20b, and the lower end opening 21 of the funnel part 20b is installed in the posture facing the screw conveyor 22. The glass powder GP stored in the storage silo 20 is sent from the lower opening 21 to the screw conveyor 22. By vibrating the storage silo 20 by operating the vibrator MB, the glass powder (GP) can be exported without congestion.

As shown in FIG. 4, the mixture (GPM) of the glass powder and blowing agent conveyed by the roller conveyor 51 (refer FIG. 1) is spread | distributed uniformly in the mesh belt of the kiln 53, and of the mixture (GPM) at that time A thickness of 10 to 20 mm and a plurality of rows of comb marks 26 are formed in the mixture GPM along the conveyance direction by the sawtooth-shaped uniform substrate 25. Thereby, since the heat | fever at the time of baking spreads to the inside of mixture GPM, uniform foaming glass can be formed.

The foamed glass coarse grinding machine 27 shown in FIG. 5 is used in the foamed glass coarse grinding process 7 (see FIG. 2). The foamed glass BG formed in the firing furnace 53 has a plate shape, and cracks are generated by quenching in contact with the outside air. In this state, the foamed glass BG is too large to be transferred to the belt conveyor 28. Coarsely pulverized. The coarse grinding machine 27 is a crushing tool for lifting and lowering the plate-shaped foam glass BG having a crack conveyed to the roller conveyor 51 having the mesh belt 51a rotating in the direction of the arrow by the motor M. FIG. It is crushed by (29). As a result, the foamed glass BG is formed into a bulk body LG having a particle diameter of about 100 mm, and is transferred to the belt conveyor 28 in the next step.

In the zeolitic solution immersion step 59 shown in FIG. 1 and FIG. 2, the solution penetration device 30 shown in FIG. 6 is used. The solution penetration device 30 includes an airtight container 31 for accommodating the zeolitized solution ZL immersed in the granular foamed glass CG, a vacuum pump P for sucking and discharging air in the airtight container 31, The storage tank 32 of the zeolitization solution ZL is provided. Opening / closing valve 34 is provided in the ventilation path 33 which communicates the airtight container 31 and the vacuum pump P, and opens and closes in the fluid path 35 which communicates the airtight container 31 and the storage tank 32. The valve 36 is provided. The airtight container 31 is provided with a drain passage 37 having an on-off valve 38.

When the open / close valves 36 and 38 are closed, and the air in the airtight container 31 containing the granular foamed glass CG is sucked out by the vacuum pump P, the inside of the airtight container 31 is depressurized and granular foaming is carried out. Air present in the plurality of pores of the glass CG is discharged. Next, when the opening / closing valve 34 is closed and the opening / closing valve 36 is opened, the zeolitized solution ZL flows through the liquid passage 35 and flows into the hermetic container 31 to accommodate the granular foamed glass CG. Zeolite solution (ZL) also penetrates into pores, in particular micron-sized pores. Thereby, the zeoliteization rate of the granular foamed glass (CG) in the zeolite heating process 11 (refer FIG. 2) which is a post process can be improved.

The granular foamed glass (CG) infiltrating the zeolitization solution (ZL) in the solution penetrating device (30) is taken out of the zeolitization solution (ZL) in the hermetic container (31), and then the liquid shown in Figs. In the removal device 40, the extra zeolitization solution ZL adhering to the granular foam glass CG is removed. The liquid removal device 40 includes two rotary shafts 43 parallel to the support frame 44, a plurality of rollers 42 attached to the rotary shaft 43, and a motor for rotating the rotary shaft 43 ( M) and the cylindrical net basket 41 detachably mounted on the roller 42 between two rotary shafts 43 are provided.

When the net basket 41 filled with the granular foam glass CG taken out from the airtight container 31 is placed on the roller 42 between the two rotating shafts 43, the motor M is operated. As shown, the rotating shaft 43 and the roller 42 rotate, and the net basket 41 which contacts the roller 42 also rotates. Thereby, the excess zeolitication solution ZL adhering to granular foamed glass CG can be removed quickly.

The granular foamed glass CG after the liquid is removed from the liquid removing device 40 is placed in the ceramic reaction vessel 45 shown in FIG. 9, and the ceramic lid 46 is covered with FIG. 1. It feeds into the heating means C and microwave irradiation means D which are shown to in turn. The granular foamed glass (CG) in the reaction vessel (45) is heated in the heating means (C) to generate a zeolitication reaction, and the zeolitication reaction is promoted by microwave heating in the next microwave irradiation means (D). Since the lid 46 is covered with the reaction vessel 45, it is possible to prevent the water necessary for the zeolitization reaction from evaporating from the granular foamed glass (CG).

The heating temperature in the heating means (C) is 50 to 300 ° C., the heating time is about 1 to 24 hours, the heating temperature in the microwave irradiation means (D) is 50 to 300 ° C., and the heating time is about 0.5 to 30 minutes. It is not limited to this. In addition, in this embodiment, since the granular foamed glass CG put into the reaction container 45 is heated by the heating means C and the microwave irradiation means D, irradiation time in the microwave irradiation means D is shown. Although this shortens | miniaturizes and energy consumption can be suppressed, zeolite heating can also be performed only by either.

The zeolitic foamed glass manufacturing method and zeolitic foamed glass manufacturing equipment of the present invention can be widely used in the industrial field for producing zeolitic foamed glass using powder glass formed from waste glass or the like as a raw material.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows schematic structure of the zeolitic foamed glass manufacturing apparatus which is embodiment of this invention.

It is a figure which shows the manufacturing process in the zeolitic foamed glass manufacturing equipment shown in FIG.

It is a schematic diagram which shows the vicinity of the storage silo which comprises the zeolitic foamed glass manufacturing apparatus shown in FIG.

It is a perspective view which shows a part of roller conveyor which comprises the zeolitic foamed glass manufacturing equipment shown in FIG.

FIG. 5: is a schematic diagram which shows the foaming glass coarse grinder which comprises the zeolitic foaming glass manufacturing equipment shown in FIG.

It is a schematic diagram which shows the solution penetration device which comprises the zeolitic foamed glass manufacturing equipment shown in FIG.

FIG. 7: is a side view which shows the zeolitic solution liquid removal apparatus which comprises the zeolitic foamed glass manufacturing apparatus shown in FIG.

FIG. 8 is a front view of the zeolitic solution liquid removing apparatus shown in FIG. 7. FIG.

FIG. 9 is a perspective view showing a reaction vessel when zeolitic granular foamed glass impregnated with a zeolitized solution. FIG.

(Explanation of the sign)

1 pretreatment 2 primary grinding

3 Secondary grinding 4 Glass powder raw material storage

5 Mixing of blowing agent 6 Firing

7 Coarse grinding glass 8 Primary storage

9 Foamed glass crushing 10 Foamed glass classification and bag filling

11 Zeolite Heating 12 Cleaning

13 Product Shipment 20 Storage Silos

20a cylindrical part 20b funnel

21 Lower opening 22 Screw conveyor

25 Serrated Uniformity Board 26 Comb Marks

27 Foam Glass Grinding Machines 28 Belt Conveyors

29 Shredding Tools 30 Liquid Penetration Devices

31 Airtight Container 32 Storage Tank

33 Ventilation path 35 Passage path

34, 36, 38 closing valve 37 drainage path

40 Liquid Remover 41 Mens Basket

42 rollers 43 axis of rotation

44 Support frame 45 Reaction vessel

46 Cover 50 Zeolited Foam Glass Manufacturing Equipment

51, 61, 64 Roller Conveyor 52 Preheater

53 Firing Furnace 54 Cooling Table

55, 56 Intake System 57 Crushing

58 Classification 59 Immersion of Zeolite Solution

60 Zeolitic Solution Liquid Removal

62 furnace 63 burner

65 Microwave Oscillator 66 Furnace

67 Burner A firing means

B1 shredding means B2 solution penetration means

C heating means D microwave irradiation means

F Fan BG Foam Glass

GP Glass Powder GPM Mixture

Agglomeration M motor of LG foam

MB Vibrator P Vacuum Pump

ZL Zeolitization Solution

CG Granular Foamed Glass

Claims (7)

A firing step of heating and foaming the glass powder to which the blowing agent is added to form a foamed glass, a crushing step of granulating the foamed glass formed in the sintering step, and impregnating a zeolitic solution into the granular foamed glass formed in the crushing step. At least one of a solution penetration step and a heating step and a microwave irradiation step of zeoliteizing the granular foamed glass impregnated with the zeolitic solution, At least one of the said heating process and the said microwave irradiation process uses the excess heat which arises at the said baking process, The zeolite foaming glass manufacturing method characterized by the above-mentioned. The method for producing a zeolitic foam glass according to claim 1, wherein an aqueous sodium aluminate solution is used as the zeolitic solution. The method for producing a zeolitic foamed glass according to claim 1, wherein a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolitized solution. The method of claim 1, wherein a mixed aqueous solution of glass powder and sodium aluminate is used as the zeolitized solution. The method for producing a zeolitic foamed glass according to claim 1, wherein a mixed aqueous solution of water glass and sodium aluminate is used as the zeolitized solution. Impregnating a zeolitic solution with a firing means for heating and foaming the glass powder to which the blowing agent is added to form a foamed glass, crushing means for granulating the foamed glass formed by the sintering means, and granular foamed glass formed by the crushing means. At least one of a solution penetrating means and a heating means and a microwave irradiation means for zeolitizing the granular foamed glass impregnated with the zeolitized solution, The heat transfer means which supplies the excess heat which generate | occur | produces in the said baking means to at least one of the said heating means and the said microwave irradiation means was provided, The zeolitic foamed glass manufacturing equipment characterized by the above-mentioned. 7. The zeolitic foaming according to claim 6, wherein an airtight container containing the zeolitic solution in which the granular foamed glass is immersed, and a pressure reducing means for reducing the air pressure in the gastight container are provided as the solution penetrating means. Glass manufacturing equipment.

Images