JP5008495B2 - Zeolite foamed glass production method and zeolitic foam glass production equipment - Google Patents

Description

  The present invention relates to a technique for producing foamed glass whose surface is zeoliticized from powder glass.

  Various research and development have been conducted on the technology for producing a zeolitic foamed glass having an adsorption function or an ion exchange function by zeolitizing the surface of the foamed glass. There is a method in which the surface of the foamed glass immersed in an aqueous solution of sodium aluminate is irradiated with microwaves so as to be zeolitic (see, for example, Patent Document 1).

JP 2005-145807 A

  In the “method for producing surface zeolitic glass” described in Patent Document 1, microwave irradiation is performed in a state in which a glass raw material is immersed in an aqueous sodium aluminate solution or in a state in which the aqueous solution is applied to the glass raw material. It takes a long time to change. In addition, in the case of a high concentration sodium aluminate aqueous solution, it is difficult to penetrate into the pores inside the foam glass, so that there are many portions that are not zeoliteized, 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, penetrability into the foamed glass is good, but it cannot be avoided that the zeolitization reaction does not proceed and the CEC value becomes low.

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

The method for producing zeolitic foamed glass of the present invention comprises a firing step in which foamed glass is formed by heating and foaming a glass powder added with a foaming agent, and a crushing step in which the foamed glass formed in the firing step is granulated, A solution infiltration step for impregnating the granular foamed glass formed in the crushing step with a zeolitic solution, and the granular foamed glass impregnated with the zeolitic solution were placed in a ceramic reaction vessel and covered with a ceramic lid. the granular foam glass by microwave irradiation and heating as luma microwave irradiation Engineering is zeolite in a state provided with,
Oite to as prior Symbol microwave irradiation Engineering, characterized by the use of waste heat generated in the firing step.

  With this configuration, part of the heat required for the zeolitization reaction of the granular foamed glass impregnated with the zeolitic solution can be supplemented with the residual heat generated in the foamed glass production process. The amount of energy required to reduce the amount of energy required for the production of zeolitic foamed glass can be reduced. As the foaming agent, calcium carbonate, silicon carbide, dolomite, sodium borate and the like are suitable, but not limited thereto.

  Here, if an aqueous sodium aluminate solution is used as the zeolitic solution, the alkali component, alumina component and water necessary for the zeolitic reaction are supplied from the zeolitic solution, and the silica component is supplied from the granular foamed glass. For this reason, there is no need to supply a new silica component, and the sodium aluminate solution contains alkali components, alumina components, and moisture, so there is no need to add new chemicals, shortening the work process. can do.

  If a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolitic solution, the alkali component, alumina component and water necessary for the zeolitic reaction are supplied from the zeolitic solution, and the silica component is hydroxylated. It is supplied from the surface of granular foamed glass softened by the strong alkali action of sodium. For this reason, the zeoliticization rate of granular foamed glass can be raised.

  Moreover, if a mixed aqueous solution of glass powder and sodium aluminate is used as the zeolitic solution, the silica component is eluted from the glass powder into the zeolitic solution by previously mixing the glass powder with the sodium aluminate aqueous solution. Can be made. Moreover, since the glass powder which is a raw material of the manufacturing process of foamed glass can be used effectively as a silica component, and it is a glass powder, the solubility of the silica component in the sodium aluminate aqueous solution is good.

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

Next, the zeolitic foamed glass production facility of the present invention comprises a firing means for heating and foaming a glass powder to which a foaming agent has been added to form foamed glass, and crushing for granulating the foamed glass formed by the firing means. Means, a solution infiltration means for impregnating the granular foamed glass formed by the crushing means, and the granular foamed glass impregnated with the zeolitic solution into a ceramic reaction vessel, and a ceramic lid and microwave radiation heating and a luma microwave irradiation hand stage is zeolite of the granular foam glass in a state covered with,
And wherein providing the Okunetsu means for supplying the residual heat generated by the firing unit Previous Symbol microwave irradiation hand stage.

  With such a configuration, it becomes possible to carry out the above-described method for producing a zeolitic glass according to the present invention, reducing energy required for producing the zeolitic foam glass, and obtaining a high-quality zeolitic foam glass. it can.

  Here, the pores of the granular foamed glass are provided as the solution infiltration means by providing an airtight container for storing the zeolitic solution in which the granular foamed glass is immersed, and a decompression means for reducing the air pressure in the airtight container. In particular, since the zeolitic solution can be permeated into microscopic pores, the zeoliticization rate of the granular foamed glass can be increased.

  With the method for producing zeolitic foamed glass and the equipment for producing zeolitic foamed glass of the present invention, energy required for producing the zeolitic foamed glass can be reduced, and high-quality zeolitic foamed glass can be obtained.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing a schematic configuration of a zeolitic foamed glass manufacturing facility according to an embodiment of the present invention, and FIG. 2 is a diagram showing a manufacturing process in the zeolitic foamed glass manufacturing facility shown in FIG.

  As shown in FIG. 1, a zeolitic foamed glass manufacturing facility 50 (hereinafter referred to as “manufacturing facility 50”) includes firing means A for heating and foaming a glass powder to which a foaming agent is added to form foamed glass. , Crushing means B1 for granulating the foamed glass formed by the firing means A, solution infiltration means B2 for impregnating the granular foamed glass formed by the crushing means B1 with the zeolitic solution, and granular foaming for impregnating the zeolitic solution Heating means C and microwave irradiation means D for zeoliticizing the glass.

  In the baking means A, the pre-tropical zone 52, the baking furnace 53, and the cooling zone 54 are arrange | positioned along the conveyance direction of the roller conveyor 51 which conveys a foamed glass raw material. Downstream of the pre-tropical zone 52 and the cooling zone 54, intake devices 55 and 56 for heat recovery are arranged. The intake devices 55 and 56 are heat supply means that suck in the high temperature air above the roller conveyor 51 by the fan F and supply it to other places.

  In the crushing means B1, crushing 57 and classification 58 of the foamed glass formed in the baking means A are performed. In the solution infiltration means B2, after the zeolitic solution immersion 59 of the foamed glass 57 crushed 57 and classified 58 by the crushing means B1, the excess zeolitic solution adhering to the foamed glass is removed. 60 is performed.

  The heating means C is provided with a roller conveyor 61 and a heating furnace 62, and a heater 63 that generates heat by high-temperature air supplied from the intake devices 55 and 56 of the baking means A below the roller conveyor 61 in the heating furnace 62. Is arranged.

  The microwave irradiation means D is provided with a roller conveyor 64 and a heating furnace 66 for irradiating the microwave generated by the microwave oscillator 65. Below the roller conveyor 64 in the heating furnace 66, heat is transmitted. A heater 67 that generates heat by high-temperature air supplied from the intake devices 55 and 56 as means is disposed.

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

  As shown in FIG. 2, pretreatment 1 is performed on the waste glass as a raw material. In the pretreatment 1, the metal such as a cap and the label mixed in the waste glass are removed. In this embodiment, waste glass is used as a raw material. However, the present invention is not limited to this, and a general glass material can be used as a raw material.

  The waste glass that has undergone the pretreatment step 1 is pulverized to a particle size of about 2 to 5 mm in the primary pulverization step 2, and then pulverized to a glass powder having a particle size of about 30 to 100 μm in the secondary pulverization step 3 Stock in glass powder raw material stock 4. Then, the foaming agent mixture 5 is performed on the glass powder supplied from the glass powder raw material stock 4. In this embodiment, about 0.5 to 15% by mass of calcium carbonate as a foaming agent is added to the glass powder, but the present invention is not limited to this.

  The glass powder that has passed through the foaming agent mixture 5 is fired 6 while passing through the pre-tropical zone 52, the firing furnace 53, and the cooling zone 54 on the roller conveyor 51 of the firing means A shown in FIG. In this embodiment, the firing temperature is 800 to 900 ° C. and the firing time is 30 to 120 minutes, but this is not limitative. The foamed glass formed through the firing 6 steps is crushed in the foamed glass rough breaking 7 step to form a lump having a particle size of about 100 mm, and then stocked in the primary stock 8.

  The lump foam glass supplied from the primary stock 8 is pulverized through 9 steps of foam glass pulverization in the crushing means B1 shown in FIG. 1 to form granules of 50 mm or less, and then classified in 10 steps of foam glass classification and bagging. And bagging. At this time, the classified granular foamed glass having a particle diameter of 2 mm or less is mixed into the glass powder before the five foaming agent mixing steps.

  In the solution infiltration means B2 shown in FIG. 1, the zeolitic solution immersion 59 and the zeolitic solution draining 60 are applied to the granular foam glass having a particle diameter of 2 to 50 mm classified in the foam glass classification / packing 10 steps. The In this embodiment, a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolitic solution, but the present invention is not limited to this.

  The granular foamed glass impregnated with the zeolitic solution through the solution infiltration means B2 passes through at least one of the heating means C and the microwave irradiation means D shown in FIG. Glass is formed. And the said zeolitic foamed glass is wash | cleaned 12 at the following process, and after dehydration and drying 13, it is shipped 14 products.

  As shown in FIG. 1, in the production facility 50, a part of heat necessary for the zeolitization reaction of the granular foamed glass impregnated with the zeolitic solution is used as residual heat generated in the foamed glass production process (firing means A). Since it collects and supplements, the energy consumption required for a zeolitic reaction decreases, and the energy required for manufacture of a zeolitic foamed glass can be reduced.

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

  Next, based on FIGS. 3 to 9, the structures and functions of various apparatuses constituting the manufacturing facility 50 will be described. 3 is a schematic view showing the vicinity of a stock silo constituting the manufacturing facility 50 shown in FIG. 1, FIG. 4 is a perspective view showing a part of a roller conveyor constituting the manufacturing facility 50, and FIG. FIG. 6 is a schematic view showing a glass roughing machine, FIG. 6 is a schematic view showing a solution infiltration device constituting the production facility 50, and FIG. 7 is a side view showing a zeolitic solution draining device constituting the production facility 50. FIG. 8 is a front view of the zeolitic solution draining apparatus shown in FIG. 7, and FIG. 9 is a perspective view showing a reaction vessel when the granular foamed glass impregnated with the zeolitic solution is zeolitized.

  The stock silo 20 shown in FIG. 3 is disposed in the glass powder raw material stock 4 shown in FIG. 2 in order to store the glass powder GP. The stock silo 20 includes a cylindrical portion 20a having the same inner diameter and a funnel portion 20b continuously provided therebelow, and the funnel portion 20b has a shape that is gradually reduced in diameter toward the lower end opening 21 thereof. The vibration device MB is disposed on the outer surface of the funnel portion 20b, and the lower end opening 21 of the funnel portion 20b is erected in a posture facing the screw conveyor 22. The glass powder GP stored in the stock silo 20 is sent out from the lower end opening 21 to the screw conveyor 22. By operating the vibration device MB and applying vibration to the stock silo 20, the glass powder GP can be sent out without delay. it can.

  As shown in FIG. 4, the mixture GPM of the glass powder and the foaming agent conveyed by the roller conveyor 51 (see FIG. 1) is spread on the mesh belt of the baking furnace 53, and the mixture GPM at that time And a plurality of rows of combs 26 are placed in the mixture GPM along the conveying direction by the tooth spreader 25. This spreads heat during firing into the mixture GPM, so that uniform foamed glass can be formed.

  The foamed glass roughing machine 27 shown in FIG. 5 is used in the foamed glass roughing process 7 (see FIG. 2). The foamed glass BG formed in the baking furnace 53 is plate-shaped, and cracks are generated when it is rapidly cooled by touching the outside air. However, since it is too large to be transferred by the belt conveyor 28, it is roughly divided by the roughing machine 27. Is done. The rough divider 27 crushes the cracked plate-like foamed glass BG conveyed by the roller conveyor 51 having the mesh belt 51a rotating in the direction of the arrow with a crushing tool 29 that moves up and down by the motor M. Thereby, the foam glass BG becomes a lump LG having a particle size of about 100 mm, and is transferred to the next process by the belt conveyor 28.

  In the zeolitic solution immersion step 59 shown in FIGS. 1 and 2, the solution infiltration device 30 shown in FIG. 6 is used. The solution permeation device 30 includes an airtight container 31 that contains a zeolitic solution ZL in which granular foamed glass CG is immersed, a vacuum pump P that sucks and discharges air in the airtight container 31, a storage tank 32 for the zeolitic solution ZL, It has. An opening / closing valve 34 is provided in the ventilation path 33 that communicates the hermetic container 31 and the vacuum pump P, and an opening / closing valve 36 is provided in the liquid passage 35 that communicates the hermetic container 31 and the storage tank 32. The airtight container 31 is provided with a drainage passage 37 having an opening / closing valve 38.

  When the air in the airtight container 31 containing the granular foamed glass CG is sucked and discharged by the vacuum pump P with the open / close valves 36 and 38 closed, the inside of the airtight container 31 is depressurized and a large number of the granular foamed glass CG has. The air present in the pores is exhausted. Next, when the on-off valve 34 is closed and the on-off valve 36 is opened, the zeolitic solution ZL flows into the airtight container 31 through the liquid passage 35, and the pores of the accommodated granular foamed glass CG, particularly micron. The zeolitic solution ZL also penetrates into microscopic pores. Thereby, the zeolitization rate of the granular foam glass CG in the zeolitic heating process 11 (refer FIG. 2) which is a post process can be raised.

  The granular foamed glass CG infiltrated with the zeolitic solution ZL in the solution permeation apparatus 30 is taken out from the zeolitic solution ZL in the airtight container 31, and then in the liquid draining apparatus 40 shown in FIGS. Excess zeolitic solution ZL adhering to glass CG is removed. The liquid draining device 40 includes two rotating shafts 43 parallel to the support frame 44, a plurality of rollers 42 attached to the rotating shaft 43, a motor M that rotationally drives the rotating shaft 43, and two rotations. And a cylindrical net cage 41 that is detachably mounted on the roller 42 between the shafts 43.

  After placing the mesh basket 41 loaded with the granular foamed glass CG taken out from the airtight container 31 on the roller 42 between the two rotating shafts 43, when the motor M is operated, as shown in FIG. The rotating shaft 43 and the roller 42 rotate, and the mesh basket 41 in contact with the roller 42 also rotates. Thereby, the excess zeolitic solution ZL adhering to the granular foamed glass CG can be quickly removed.

  The granular foamed glass CG, which has been drained in the liquid draining device 40, is placed in a ceramic reaction vessel 45 shown in FIG. 9 and covered with a ceramic lid 46, and the heating means C shown in FIG. Sequentially sent to the microwave irradiation means D. The granular foamed glass CG in the reaction vessel 45 is heated in the heating means C to cause a zeolitic reaction, and the zeolitic reaction is promoted by microwave heating in the next microwave irradiation means D. Since the reaction vessel 45 is covered with the lid 46, it is possible to prevent the water necessary for the zeolitic 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. However, the present invention is not limited to this. In this embodiment, since the granular foamed glass CG placed in the reaction vessel 45 is heated by the heating means C and the microwave irradiation means D, the irradiation time in the microwave irradiation means D is shortened and energy consumption is reduced. However, the zeolitic heating can be carried out with only one of them.

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

It is a figure which shows schematic structure of the zeolitic foam glass manufacturing equipment which is embodiment of this invention. It is a figure which shows the manufacturing process in the zeolitic foam glass manufacturing equipment shown in FIG. It is a schematic diagram which shows the stock silo vicinity which comprises the zeolitic foam glass manufacturing equipment shown in FIG. It is a perspective view which shows a part of roller conveyor which comprises the zeolitic foam glass manufacturing equipment shown in FIG. It is a schematic diagram which shows the foam glass roughing machine which comprises the zeolitic foam glass manufacturing equipment shown in FIG. It is a schematic diagram which shows the solution infiltration apparatus which comprises the zeolitic foam glass manufacturing equipment shown in FIG. It is a side view which shows the zeolitic solution liquid draining apparatus which comprises the zeolitic foam glass manufacturing equipment shown in FIG. It is a front view of the zeolitic solution liquid draining apparatus shown in FIG. It is a perspective view which shows the reaction container at the time of making zeoliticization the granular foam glass impregnated with the zeolitic solution.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pretreatment 2 Primary grinding 3 Secondary grinding 4 Glass powder raw material stock 5 Foaming agent mixing 6 Firing 7 Foamed glass roughing 8 Primary stock 9 Foamed glass grinding 10 Foamed glass classification and bagging 11 Zeolite heating 12 Washing 13 Product shipment 20 Stock silo 20a Tubular part 20b Funnel part 21 Lower end opening part 22 Screw conveyor 25 Tooth-type spreader 26 Comb 27 Foam glass roughing machine 28 Belt conveyor 29 Crushing tool 30 Solution penetration device 31 Airtight container 32 Storage tank 33 Ventilation path 35 Liquid-flowing path 34, 36, 38 Open / close valve 37 Drainage path 40 Liquid draining device 41 Net cage 42 Roller 43 Rotating shaft 44 Support frame 45 Reaction vessel 46 Lid 50 Zeolized foamed glass manufacturing equipment 51, 61, 64 Roller conveyor 52 Pre-tropical 53 Firing furnace 5 4 Cooling zone 55, 56 Intake device 57 Crushing 58 Classification 59 Zeolite solution immersion 60 Zeolite solution draining 62 Heating furnace 63 Heater 65 Microwave oscillator 66 Heating furnace 67 Heater A Baking means B1 Crushing means B2 Solution infiltration means C Heating means D Microwave irradiation means F Fan BG Foamed glass GP Glass powder GPM mixture LG Foamed glass mass M Motor MB Vibrator P Vacuum pump ZL Zeolite solution CG Granular foamed glass

Claims (7)

A baking process for heating and foaming glass powder to which a foaming agent is added to form foamed glass, a crushing process for granulating the foamed glass formed in the baking process, and a granular foamed glass formed in the crushing process A solution infiltration step for impregnating with the zeolitic solution, and the granular foamed glass impregnated with the zeolitic solution is placed in a ceramic reaction vessel and heated by microwave irradiation with a ceramic lid covered, and the granular foam is obtained. glass and the higher luma microwave irradiation Engineering is zeolitization comprises,
Oite to as prior Symbol microwave irradiation Engineering, zeolitization foam glass production method characterized by using the residual heat generated in the firing step.   The method for producing a zeolitic foamed glass according to claim 1, wherein a sodium aluminate aqueous solution is used as the zeolitic solution.   The method for producing zeolitic foamed glass according to claim 1, wherein a mixed aqueous solution of sodium hydroxide and aluminum hydroxide is used as the zeolitic solution.   The method for producing a zeolitic foamed glass according to claim 1, wherein a mixed aqueous solution of glass powder and sodium aluminate is used as the zeolitic solution.   The method for producing a zeolitic foam glass according to claim 1, wherein a mixed aqueous solution of water glass and sodium aluminate is used as the zeolitic solution. A baking means for heating and foaming glass powder to which a foaming agent is added to form foamed glass, a crushing means for granulating the foamed glass formed by the baking means, and a granular foamed glass formed by the crushing means A solution infiltration means for impregnating the zeolitic solution and the granular foam glass impregnated with the zeolitic solution are placed in a ceramic reaction vessel, and covered with a ceramic lid and heated by microwave irradiation to form the granular foam. glass and a luma microwave irradiation hand stage is zeolitization,
The zeolite of foam glass production equipment, characterized by providing the Okunetsu means for supplying the residual heat generated by the firing means to the front Symbol microwave irradiation hand stage.   The zeolitic foamed glass manufacturing equipment according to claim 6, wherein as the solution permeating means, an airtight container for storing the zeolitic solution in which the granular foamed glass is immersed, and a pressure reducing means for reducing the air pressure in the airtight container are provided. .

Images