KR101471458B1 - Method for manufacturing zeolitic foamed glass and equipment for manufacturing zeolitic foamed glass - Google Patents

Abstract

The present invention provides a zeolitized foamed glass manufacturing technology capable of reducing the energy required for the production of zeolitic foamed glass and obtaining high quality zeolitic foamed glass.

The zeolitized foamed glass manufacturing equipment 50 comprises firing means A for forming a foamed glass by heating and foaming the glass powder to which a foaming agent has been added and crushing means B1 for granulating the foamed glass formed by the firing means A (B2) for impregnating the granular foamed glass formed with the crushing means (B1) with a zeolite solution, a heating means (C) for zeolitizing the granular foamed glass impregnated with the zeolite solution and a microwave irradiation means D). The preheating tray 52, the firing furnace 53 and the cooling stage 54 are disposed along the conveying direction of the roller conveyor 51 and the downstream side of the preheating tray 52 and the cooling stage 54 The intake devices 55 and 56 disposed in the intake path suck high temperature air above the roller conveyor 51 and supply the heated air to the heating means C and the microwave irradiation means D.

Zeolite, foam, glass, foaming agent, powder, calcination, granule, microwave.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a zeolitic foamed glass manufacturing method and a zeolitic foamed glass manufacturing apparatus,

TECHNICAL FIELD The present invention relates to a technique for producing a foamed glass having a zeolite surface with powdery glass as a raw material.

BACKGROUND ART Conventionally, various research and development have been made on techniques for producing a zeolitized foamed glass having an adsorption function or an ion exchange function by zeoliteing the surface of a foamed glass. As a technology related to the present invention, There is a method of zeolite the surface by irradiating microwave to the foamed glass which has been immersed (see, for example, Patent Document 1).

Patent Document 1: JP-A-2005-145807

In the " method for producing surface zeolitized glass " described in Patent Document 1, a microwave is irradiated in a state in which the glass raw material is immersed in an aqueous solution of sodium aluminate or in a state in which the aqueous solution is applied to the glass raw material, do. Further, in the case of an aqueous sodium aluminate solution having a high concentration, it is difficult to penetrate into the pores in the foamed glass, so that portions not to be converted into zeolite are increased and the cation exchange capacity (CEC value) is lowered in some cases. On the other hand, in the case of the sodium aluminate aqueous solution having a low concentration, the permeability into the foamed glass is good, but the zeolite reaction does not proceed and the CEC value can not be avoided.

Therefore, a problem to be solved by the present invention is to reduce the energy required for the production of zeolitized foamed glass, and to obtain high-quality zeolitic foamed glass.

The method for producing a zeolitized foamed glass of the present invention comprises a firing step of heating and foaming a glass powder to which a foaming agent has been added to form a foamed glass, a crushing step of granulating the foamed glass formed in the firing step, A step of impregnating the granular foamed glass with a zeolite solution and a step of heating and microwave irradiation to zeolite the granular foamed glass impregnated with the zeolite solution,

And at least one of the heating step and the microwave irradiation step uses residual heat generated in the firing step.

This configuration makes it possible to supplement a part of the heat required for the zeolite-forming reaction of the granular foamed glass impregnated with the zeolite solution with the residual heat generated in the production process of the foamed glass. Therefore, the energy consumption required for the zeolite- And the energy required for the production of the zeolitic foamed glass can be reduced. Examples of the foaming agent include calcium carbonate, silicon carbide, dolomite, sodium borate, and the like, but are not limited thereto.

Here, when an aqueous sodium aluminate solution is used as the zeolite solution, the alkali component, alumina component and water required for the zeolite reaction are supplied from the zeolite solution, and the silica component is supplied from the granular foamed glass. Therefore, there is no need to newly supply a silica component, and since the sodium aluminate solution contains an alkali component, an alumina component and water, a work such as mixing a new agent is unnecessary, and the work process can be shortened.

When a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolite solution, the alkali component, alumina component and water necessary for the zeolite formation reaction are supplied from the zeolite solution, and the silica component is supplied by the strong alkali action of sodium hydroxide Is supplied from the softened granular foamed glass surface. Therefore, the zeolite ratio of the granular foamed glass can be increased.

When a mixed aqueous solution of glass powder and sodium aluminate is used as the zeolite solution, the silica component can be eluted from the glass powder into the zeolite solution by previously mixing the glass powder with an aqueous solution of sodium aluminate. In addition, glass powder, which is a raw material in the production process of foamed glass, can be effectively used as a silica component, and since it is a glass powder, the solubility of the silica component in an aqueous solution of sodium aluminate is good.

On the other hand, when a mixed aqueous solution of water glass and sodium aluminate is used as the zeolite solution, the silica component and water required for the zeolite reaction are supplied from water glass, and the alumina component, the alkali component and water are supplied from sodium aluminate. Therefore, the molar ratio of the alkaline source, alumina source, silica source and water required for zeolite formation can be adjusted. Therefore, zeolites having various structures such as type A zeolite, type X zeolite, and type Y zeolite can be formed, if necessary.

Next, the zeolitized foamed glass manufacturing facility of the present invention comprises a firing means for firing a glass powder to which a foaming agent has been added to form a foamed glass, a crushing means for granulating the foamed glass formed by the firing means, A means for impregnating the granular foamed glass formed by the means for impregnating the zeolite with the zeolite solution and at least one of heating means and microwave irradiation means for zeolizing the granular foamed glass impregnated with the zeolite solution,

And a heating means for supplying residual heat generated by the firing means to at least one of the heating means and the microwave irradiation means.

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

Here, as the solution impregnating means, there may be provided an airtight container for accommodating the zeolite solution immersed in the granular foamed glass and a pressure reducing means for lowering the air pressure in the airtight container. The pores of the granular foamed glass, Since the zeolite solution can be infiltrated into minute pores of micron size, the zeolite ratio of the granular foamed glass can be increased.

The zeolitic foamed glass manufacturing method of the present invention and the zeolitized foamed glass manufacturing facility can reduce the energy required for the production of the zeolitic foamed glass and obtain a high-quality zeolitic foamed glass.

(Best Mode for Carrying Out the Invention)

Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a view showing a schematic configuration of a zeolitized foamed glass manufacturing equipment according to an embodiment of the present invention, and Fig. 2 is a view showing a production process in the zeolitized foamed glass manufacturing equipment shown in Fig.

1, a zeolitized foamed glass manufacturing facility 50 (hereinafter referred to as "production facility 50") is a device for producing a foamed glass by heating and foaming a glass powder to which a foaming agent has been added (B2) for impregnating the granular foamed glass formed with the crushing means (B1) with a zeolite solution; and a liquid impregnating means (B2) for impregnating the granular foamed glass formed with the crushing means (B1) And a heating means (C) for zeolizing the granular foamed glass impregnated with the zeolite solution and a microwave irradiation means (D).

In the firing unit A, the preheating base 52, the firing furnace 53, and the cooling fence 54 are disposed along the conveying direction of the roller conveyor 51 for conveying the foamed glass raw material. On the downstream side of the preliminary tub 52 and the cooling stand 54, intake devices 55 and 56 for heat recovery are arranged. Each of the intake devices 55 and 56 is a heating means for sucking hot air above the roller conveyor 51 by a fan F and supplying it to another place.

In the crushing means B1, crushing 57 and classification 58 of the foamed glass formed in the firing means A are performed. In the solution penetration means B2, the zeolite solution immersion 59 of the foamed glass subjected to the crushing 57 and the classification 58 is performed by the crushing means B1, and then the excess zeolite solution attached to the foamed glass is removed The removal of the zeolite solution (60) is performed.

The heating means C is provided with a roller conveyor 61 and a heating furnace 62 and is arranged below the roller conveyor 61 in the heating furnace 62 and connected to the intake devices 55 and 56 of the firing means A, And a heater 63 for generating heat by the high-temperature air supplied from the heater 63 is disposed.

The microwave irradiating means D is provided with a roller conveyor 64 and a heating furnace 66 for irradiating microwaves generated from the microwave oscillator 65. Below the roller conveyor 64 in the heating furnace 66, And a heater 67 for generating heat by the high-temperature air supplied from the intake devices 55, 56, which are heat transfer means, are disposed.

Next, a process for producing a zeolite foamed glass in the production facility 50 shown in Fig. 1 will be described based on Fig.

As shown in Fig. 2, pretreatment (1) is performed on the waste glass as a raw material. In the pretreatment 1, a metal such as a cap or the like mixed in the waste glass is removed. In the present embodiment, waste glass is used as a raw material, but since it is not limited to this, a general glass material can be used as a raw material.

The waste glass after the pretreatment process (1) is pulverized to a particle size of about 2 to 5 mm in the first pulverization (2) process and then to a glass powder having a particle size of about 30 to 100 탆 in the second pulverization (3) And then stored in the glass powder stock storage part 4. [ Then, the foaming agent mixture (5) is performed on the glass powder supplied to the glass powder material storage part (4). In the present embodiment, calcium carbonate as a foaming agent is added to the glass powder in an amount of about 0.5 to 15 mass%, but the present invention is not limited thereto.

The glass powder having passed through the foaming agent mixture 5 is carried on a roller conveyor 51 of the firing means A shown in Fig. 1 and passes through the preliminary stage 52, the firing furnace 53 and the cooling fence 54, 6) and becomes a foamed glass. In the present embodiment, the firing temperature is 800 to 900 DEG C and the firing time is 30 to 120 minutes, but the present invention is not limited to this. The foamed glass formed through the firing (6) process is pulverized in the process of pulverizing the foamed glass (7), and is made into an aggregate having a particle size of about 100 mm, and then stored in the primary storage section (8).

The massive foamed glass supplied from the primary storage section 8 is pulverized through the foamed glass pulverization process 9 in the pulverization means B1 shown in FIG. 1 and is converted into a granular material having a size of 50 mm or less, Classification and bag filling are performed in the bag filling (10) process. At this time, the classified granular foamed glass having a particle size of 2 mm or less is incorporated into the glass powder before the mixing step (5) of the foaming agent.

The granulated foamed glass having a particle size of 2 to 50 mm classified in the process of foamed glass classifying and bag filling 10 was subjected to the liquid immersion step (B2) shown in FIG. 1 in which the zeolite solution immersion 59 and the zeolite solution solution Removal 60 is performed. In the present embodiment, a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolite solution, but the present invention is not limited thereto.

The granular foamed glass impregnated with the zeolite solution through the solution penetration means B2 is passed through at least one of the heating means C and the microwave irradiation means D shown in Fig. 1, whereby the zeolite heating 11 And a zeolitic foamed glass is formed. Then, the zeolite foamed glass is cleaned (12) in the next process, dehydrated and dried (13) is performed, and then the product is shipped (14).

1, in the production facility 50, a part of the heat necessary for the zeolite-forming reaction of the granular foamed glass impregnated with the zeolite solution is partially removed by heat of the residual heat generated in the manufacturing process of the foamed glass (the firing means A) The amount of energy consumption required for the zeolite formation reaction is small and the energy required for producing the zeolitic foamed glass can be reduced.

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

Next, the structure, functions, and the like of various devices constituting the manufacturing facility 50 will be described with reference to Figs. 3 to 9. Fig. 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 conveyer constituting the manufacturing facility 50, Fig. 6 is a schematic diagram showing a solution infiltration device constituting the manufacturing facility 50, Fig. 7 is a schematic diagram showing a zeolite solution solution removing device 50 constituting the manufacturing facility 50, Fig. Fig. FIG. 8 is a front view of the apparatus for removing zeolite solution shown in FIG. 7, and FIG. 9 is a perspective view showing a reaction vessel when zeolite is formed into granular foamed glass impregnated with a zeolite solution.

The storage silo 20 shown in Fig. 3 is prepared to be placed in the glass powder stock storage part 4 shown in Fig. 2 in order to store the glass powder GP. The storage silo 20 has a cylindrical portion 20a having the same inner diameter and a funnel portion 20b connected to the lower portion thereof and the funnel portion 20b is gradually reduced in diameter toward the lower end opening 21 . The vibrating device MB is disposed on the outer surface of the funnel portion 20b and the lower opening 21 of the funnel portion 20b is installed in a position facing the screw conveyor 22. The glass powder GP stored in the storage yarn 20 is sent from the lower opening 21 to the screw conveyor 22. The vibration generator MB is operated to vibrate the storage silo 20, (GP) can be exported without congestion.

As shown in Fig. 4, a mixture (GPM) of the glass powder and the foaming agent conveyed from the roller conveyor 51 (see Fig. 1) is uniformly laid on the mesh belt of the firing furnace 53, A plurality of rows of comb marks 26 are formed in the mixture GPM in the conveying direction by the serration uniform plate 25 while the thickness is 10 to 20 mm. As a result, the heat at the time of firing to the inside of the mixture (GPM) spreads, so that a uniform foamed glass can be formed.

5 is used in the foamed glass pre-grinding process 7 (see Fig. 2). The foamed glass BG formed in the firing furnace 53 is in the form of a plate and is rapidly quenched in contact with the outside air to cause cracks. In this state, the foamed glass BG is too large to be conveyed to the belt conveyor 28, Crushed. The coarse crusher 27 is provided with a crushing tool for lifting and lowering the plate-like foamed glass BG having the cracks conveyed to the roller conveyor 51 having the mesh belt 51a rotating in the direction of the arrow by the motor M (29). As a result, the foamed glass BG becomes an agglomerate LG having a particle diameter of about 100 mm, and is conveyed to the next process by the belt conveyor 28.

In the zeolite solution immersion step 59 shown in Figs. 1 and 2, the solution penetrator 30 shown in Fig. 6 is used. The solution impregnation device 30 includes an airtight vessel 31 for containing the zeolitic solution ZL in which the granular foamed glass CG is immersed, a vacuum pump P for sucking and discharging the air in the airtight vessel 31, And a storage tank 32 for storing the zeolite solution ZL. An open / close valve 34 is provided in the vent path 33 for communicating the airtight container 31 with the vacuum pump P and a liquid path 35 for communicating the airtight container 31 and the reservoir tank 32 is opened / A valve 36 is provided. The airtight container 31 is provided with a liquid drainage path 37 having an on-off valve 38. As shown in Fig.

The air in the airtight container 31 containing the granular foamed glass CG is sucked and discharged by the vacuum pump P in the state where the opening and closing valves 36 and 38 are closed so that the airtight container 31 is decompressed, Air existing in the plurality of pores of the glass (CG) is discharged. The zeolite solution ZL is introduced into the gas tight chamber 31 through the liquid passage 35 and the granular foamed glass CG ), In particular, the micropores having a micron size, penetrate into the zeolite solution (ZL). This makes it possible to improve the zeolite ratio of the granular foamed glass (CG) in the zeolite heating step 11 (see FIG. 2) as a post-process.

The granular foamed glass (CG) infiltrated with the zeolite solution (ZL) in the solution penetration device (30) is taken out from the zeolite solution (ZL) in the gas tight chamber (31) In the removal device 40, the excess zeolite solution ZL attached to the granular foamed glass CG is removed. The liquid removing device 40 includes two rotating shafts 43 parallel to the support frame 44, a plurality of rollers 42 attached to the rotating shaft 43, and a motor M and a cylindrical basket basket 41 which is detachably mounted on the roller 42 between the two rotary shafts 43. [

The mesh basket 41 filled with the granular foamed glass CG taken out from the airtight container 31 is placed on the roller 42 between the two rotary shafts 43 and then the motor M is operated. As shown in the figure, the rotating shaft 43 and the roller 42 rotate, and the net basket 41 in contact with the roller 42 also rotates. This makes it possible to quickly remove the excess zeolite solution ZL attached to the granular foamed glass (CG).

The granular foamed glass (CG) after the liquid removal in the liquid removal device 40 is put in the ceramic reaction vessel 45 shown in Fig. 9, and in the state that the lid 46 made of ceramic is covered, The heating means C and the microwave irradiation means D shown in Fig. The granular foamed glass (CG) in the reaction vessel (45) is heated in the heating means (C) to cause a zeolite reaction, and the zeolite reaction is promoted by microwave heating in the subsequent microwave irradiation means (D). Since the reaction vessel 45 is covered with the lid 46, moisture required for the zeolite reaction can be prevented from evaporating from the granular foamed glass (CG).

The heating temperature in the heating means C is about 50 to 300 캜, the heating time is about 1 to 24 hours, the heating temperature in the microwave irradiation means D is about 50 to 300 캜, and the heating time is about 0.5 to 30 minutes , But is not limited thereto. In this embodiment, since the granular foamed glass (CG) put in the reaction vessel 45 is heated by the heating means C and the microwave irradiation means D, the irradiation time of the microwave irradiation means D Can be shortened and energy consumption can be suppressed, but zeolite heating can be performed by either one of them.

The zeolitic foamed glass manufacturing method and the zeolitized foamed glass manufacturing facility of the present invention can be widely used in the industrial field where zeolitized foamed glass is produced from powdery glass formed from waste glass as a raw material.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a schematic configuration of a zeolitic foamed glass manufacturing equipment according to an embodiment of the present invention. Fig.

Fig. 2 is a diagram showing a manufacturing process in the zeolitic foamed glass production equipment shown in Fig. 1. Fig.

Fig. 3 is a schematic diagram showing the vicinity of a storage silo constituting the zeolitic foamed glass production facility shown in Fig. 1. Fig.

Fig. 4 is a perspective view showing a part of a roller conveyor constituting the zeolitic foamed glass manufacturing equipment shown in Fig. 1. Fig.

Fig. 5 is a schematic view showing a foamed glass shredder constituting the zeolitic foamed glass manufacturing equipment shown in Fig. 1. Fig.

Fig. 6 is a schematic diagram showing a solution infiltration device constituting the zeolitic foamed glass production facility shown in Fig. 1. Fig.

Fig. 7 is a side view showing a zeolitic solution liquid removing apparatus constituting the zeolitic foamed glass manufacturing equipment shown in Fig. 1. Fig.

8 is a front view of the zeolite solution removing apparatus shown in Fig.

9 is a perspective view showing a reaction vessel for zeolitizing granular foamed glass impregnated with a zeolite solution.

(Explanation of Symbols)

1 pretreatment 2 primary grinding

3 2nd crushing 4 glass powder raw material storage

5 Blowing agent mixing 6 Sintering

7 Foam glass milling 8 Primary storage

9 Foam glass grinding 10 Foam glass classification · Filling the bag

11 Zeolite heating 12 cleaning

13 Product shipment 20 Storage silo

20a tubular portion 20b funnel portion

21 bottom opening 22 screw conveyor

25 serration uniform plate 26 comb marks

27 Foamed glass grinder 28 Belt conveyor

29 Crushing tool 30 Solution penetrator

31 Airtight container 32 Storage tank

33 Ventilation path 35 Passage path

34, 36, 38 opening / closing valve 37 drainage path

40 liquid removal device 41 mesh basket

42 roller 43 rotary shaft

44 Support frame 45 Reaction container

46 Cover 50 Zeolitized Foamed Glass Manufacturing Facility

51, 61, 64 Roller conveyor 52 Example Tropical

53 Firing furnace 54 Cooling zone

55, 56 Intake device 57 Shredding

58 Class 59 Zeolitization solution immersion

60 Removal of zeolite solution solution

62 heating furnace 63 heater

65 microwave oscillator 66 heating furnace

67 heater A firing means

B1 Crushing means B2 Solution penetration means

C Heating means D Microwave irradiation means

F Fan BG foamed glass

GP glass powder GPM mixture

LG Foam Glass Alloy M Motor

MB Vibration device P Vacuum pump

ZL zeolite solution

CG granulated foam glass

Claims (7)

A method for producing a glass foamed body, comprising: a firing step of heating and foaming a glass powder to which a foaming agent has been added to form a foamed glass; a crushing step of granulating the foamed glass formed in the firing step; a step of impregnating the granulated foamed glass formed in the crushing step with a zeolite solution And at least one of a heating step of micronizing the granular foamed glass impregnated with the zeolite solution and a microwave irradiation step, A mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolite solution, Wherein at least one of the heating step and the microwave irradiation step uses the remaining heat generated in the firing step. delete delete delete delete (B1) for granulating the foamed glass formed by the firing means (A), and the crushing means (B1) for crushing the foamed glass formed by the firing means (A) (B) for impregnating the granular foamed glass formed with the zeolite solution into the zeolite solution, at least one of the heating means (C) for heating the granular foamed glass impregnated with the zeolite solution and the heating means (C) Respectively, Characterized in that the heating means (C) and the microwave irradiation means (D) are provided with heating means (55, 56) for supplying the remaining heat generated in the firing means (A) to at least one of the heating means Equipment (50). The method according to claim 6, wherein the solution penetration means (B2) comprises an airtight vessel (31) for containing the zeolitic solution in which the granular foamed glass is immersed, and a decompression means for reducing the air pressure in the airtight vessel (31) P) is installed on the surface of the zeolitic foamed glass.

Images