JP4435083B2 - Manufacturing method of foam glass material - Google Patents

Description

The present invention relates to various types of glass waste, such as waste plate glass and waste glass bottles to the production how the foam glass material as a raw material.

  BACKGROUND ART Foamed glass materials having a porous structure containing a large number of voids are conventionally used as civil engineering materials or building aggregates. As a technique for manufacturing such a foamed glass material from a glass cullet using a waste glass bottle as a main raw material, for example, a foamed glass manufacturing method described in Patent Document 1 is known.

  In the method for producing foamed glass described in Patent Document 1, glass cullet is finely pulverized, and calcium carbonate, silicon carbide, borax or the like is added as a foaming agent in an amount of 0.1 to 5.0%. Continuously spread on a belt in a roller hearth kiln with a built-in belt conveyor to a thickness of 5 to 50 mm, heated to 700 to 1,000 ° C. in the roller hearth kiln, melted, foamed and fired, and stayed in the kiln. The plate-like foamed glass produced for 5 to 60 minutes is exposed to room temperature or cooled air, or rapidly cooled by watering, and then spontaneously collapsed by the strain generated at this time, thereby causing foaming of an indefinite lump. Get glass.

  In addition to the above, as a foaming agent used for obtaining foamed glass, for example, as described in Patent Documents 2 and 3, magnesium carbonate, sodium hydrogen carbonate, barium carbonate, fine carbon, limestone, dolomite, talc, etc. Is mentioned.

  By the way, as one of wastewater treatment techniques, a MAP (magnesium ammonium phosphate) method for removing and recovering phosphate ions in wastewater as crystals as described in Non-Patent Documents 1 and 2 is known. In the MAP method, wastewater treatment is performed by adding magnesium to wastewater to form MAP granules and taking out phosphorus out of the system.

Japanese Patent Laid-Open No. 10-203838 JP 2004-34596 A (paragraph 0006) JP 2000-317316 A (paragraph 0012) "About advanced processing", line 8-11, MAP method, [online], Fukuoka City Sewerage Bureau, [searched on September 30, 2005], Internet <URL: http://gesui.city.fukuoka.jp /sewage/koudosyori.htm> "Laboratory Introduction", page 15, right column, lines 5-29, wastewater treatment technology using MAP crystallization method, Waseda Society of Applied Chemistry, [searched September 30, 2005], Internet <URL: http : //www.waseda-oukakai.gr.jp/bulletin/bulletin-68/68_06.pdf>

  In the conventional MAP method, magnesium itself is added to the wastewater. However, phosphorus in the wastewater is adsorbed only on the surface of the added magnesium, so that phosphate ions in the wastewater can be sufficiently removed. A lot of magnesium is needed. Therefore, it is a wastewater treatment technology that is expensive to use in wastewater treatment and is difficult to use in practice.

  Accordingly, an object of the present invention is to provide a magnesium-based foam glass material that can be used for wastewater treatment.

  The manufacturing method of the foamed glass material of the present invention is a mixture obtained by mixing glass powder having a particle size of 5 μm to 100 μm, powder containing a magnesium component, and a foaming agent at 600 ° C. to 1000 ° C. It is characterized by including a baking step of heating, melting, foaming, and baking, and a rapid cooling step of rapidly cooling the fired product formed in the baking step.

  In the method for producing a foamed glass material of the present invention, a mixture obtained by mixing glass powder having a particle size of 5 μm to 100 μm, a powder containing a magnesium component, and a foaming agent is set to 600 ° C. to 1000 ° C. By heating, melting, foaming, and firing, a plate-like foamed glass material containing a magnesium component and having voids as a fired product is obtained. Then, the fired product is rapidly cooled to be naturally crushed by the strain generated during the rapid cooling, and a granular foamed glass material having an average particle size of about 5.0 to 40.0 mm (maximum particle size of about 50 mm) is obtained.

  The quenching step can be performed by exposing to normal temperature blown air or by spraying with normal temperature water, but spraying a cooling liquid at room temperature or lower in the form of a mist or spraying a cooling gas at room temperature or lower. It is also possible to do this. The temperature of the cooling liquid is preferably about 5 ° C to 10 ° C, and the temperature of the cooling gas is preferably about 5 ° C to 10 ° C. Moreover, water is suitable as the cooling liquid, and air is suitable as the cooling gas. Moreover, what crushed various waste glass materials, such as a used glass bottle, can be used as a glass granular material.

  Here, the content of the granular material containing the magnesium component in the mixture is preferably 1 to 20% by mass, more preferably 10 to 20% by mass. If it is 1-20 mass%, the baking state of a foamed glass material will be the best, and the granular material containing a magnesium component will be integrated with a foamed glass material, and will become difficult to isolate | separate. Moreover, in order to fully exhibit the phosphorus adsorption effect by the magnesium component, the content is desirably 10% by mass or more. On the other hand, if it exceeds 20% by mass, the fired state of the foam glass material is deteriorated, and the granular material containing the magnesium component is easily separated.

  Moreover, it is desirable to use magnesite as the granular material containing a magnesium component. High-purity magnesite with high magnesium purity has a low content of metal elements and a low MgO content compared to basic magnesium carbonate. Moreover, the specific surface area is small, it is heavy and excellent in the fluidity of the powder. Furthermore, it is a cubic crystal with a uniform particle size, has a sharp particle size distribution, and does not have water of crystallization. Therefore, when mixed with glass powder having a particle size of 100 μm or less, it is well meshed and has a strong bonding force. There is an advantage.

  As the foaming agent, conventionally known ones such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate, barium carbonate, silicon carbide, borax, fine carbon, limestone, dolomite, and talc can be used alone or in combination. However, the content of the foaming agent is preferably 0.1 to 5.0% by mass. If the total content of calcium carbonate or the like is less than 0.1% by weight, foaming will be insufficient, the bubbles will also become smaller and the specific gravity will increase, and if it exceeds 5.0% by weight, the bubbles will become larger and so-called nests will increase. Therefore, since the value as a material is lost, the range is an appropriate range. In addition, the specific gravity of a foamed glass material can freely obtain the thing of the range of 0.3-1.5 by adjusting the content rate of this foaming agent.

  In addition, if the total content of calcium carbonate or the like is 0.1 wt% to 2.0 wt%, there is a general tendency that an independent gap structure is formed, and 0.1 wt% to 5.0 wt%. This tends to form a continuous gap structure. In addition, if the heating temperature is 600 ° C. to 900 ° C. and the baking time is 10 minutes to 20 minutes, an independent gap structure is formed, and a non-water-absorbing material tends to be fired. If the baking time is 15 minutes to 30 minutes at 1000 ° C., a continuous gap structure is formed, and the water-absorbing material tends to be fired. If the heating temperature is lower than 600 ° C., it becomes difficult to form an independent gap structure inside the material and it will not be foamed. If it is higher than 1000 ° C., it becomes difficult to form a continuous gap structure inside the material, and the bubbles are also very weak. It becomes a state.

  In addition, the foamed glass material obtained as described above has exposed powder particles containing a magnesium component on the surface and the inner wall surface of the space. Therefore, if this foamed glass material is added to the water to be treated, phosphorus contained in the water to be treated can be adsorbed on the foamed glass material to perform water treatment. Further, the bottom quality can be improved by spraying the foamed glass material on or in the bottom mud of the water to be treated and adsorbing phosphorus eluted from the bottom mud to the foamed glass material. Moreover, the foamed glass material which adsorb | sucked this phosphorus can be used as soil improvement materials, such as a fertilizer.

(1) A mixture obtained by mixing glass powder having a particle size of 5 μm to 100 μm, a powder containing a magnesium component, and a foaming agent is heated to 600 ° C. to 1000 ° C. to be melted, foamed, and fired. And a quenching step of quenching the fired product formed in the firing step, thereby having an average particle size of about 5.0 to 40.0 mm (maximum particle size of about 50 mm), and in the surface and voids It is possible to efficiently produce a foamed glass material in which a granular material containing a magnesium component is exposed on the wall surface.

(2) By making the content rate of the granular material containing the magnesium component in the mixture 1 to 20% by mass, the glass granular material can be well mixed, and the foamed glass material is efficient without being separated even during firing. Can be manufactured well.

(3) By using magnesite as a granular material containing a magnesium component, it is possible to produce a foam glass material having high bonding strength and good quality.

(4) By setting the content of the foaming agent to 0.1 to 5.0% by mass, it is possible to obtain granular foamed glass having an independent gap structure or a continuous gap structure in which bubbles of an appropriate size are incorporated. Further, by adjusting the content of the foaming agent, it is possible to obtain a granular foamed glass material having a bulk specific gravity suitable for the intended purpose and application while having buoyancy or submergence.

(5) A foamed glass material in which voids are formed by foaming glass powder particles, and compared with the same amount of magnesium by the foamed glass material in which powder particles containing a magnesium component are exposed on the surface and the inner wall surface of the voids. Thus, a foamed glass material exhibiting a strong adsorption action of phosphoric acid is obtained, so that a large amount of phosphorus can be adsorbed with a small amount of magnesium.

(6) Direct purification of closed water areas such as dams and inflows into closed water areas by a water treatment method in which the foam glass material is added to the treated water and phosphorus contained in the treated water is adsorbed to the foamed glass material. Direct purification of rivers and waterways, advanced treatment such as sewage treatment water and livestock wastewater becomes possible.

(7) The above foam glass material is sprayed in or on the bottom mud of the water to be treated, and phosphorus is dissolved out from the bottom mud and adsorbed to the foam glass material. It is possible to improve the sediment quality of water and sea areas, and improve the sediment quality of dams and lakesides.

(8) By adsorbing phosphorus to the foamed glass material, it can be reused as a soil improving material such as fertilizer, so that it does not eventually become waste. Therefore, it becomes a foamed glass material that matches the needs of society and can contribute to a recycling-oriented society.

  FIG. 1 is a process diagram showing a method for producing a foam glass material according to a first embodiment of the present invention.

  As shown in FIG. 1, the collected waste glass 1 such as used waste glass bottles and waste plate glass is separated and removed by a separation device 3 and is roughly pulverized by a coarse pulverization device 4 into a cullet shape. After being finely pulverized by the fine pulverization apparatus 5 to form glass powder particles having a particle diameter of 5 μm to 100 μm, they are put into the mixing apparatus 6. Further, the mixing device 6 is supplied with an additive 2 containing a foaming agent such as calcium carbonate, dolomite, silicon carbide, borax and magnesite powder supplied via another route. The glass powder and additive 2 are sufficiently mixed to form a mixture 7. In this case, the content of the foaming agent in the mixture 7 is 0.1 to 5.0 mass%, and the content of the magnesite powder is 1 to 20 mass%.

  The magnesite powder having a particle size of about 10 μm to 30 μm is used. Moreover, it is desirable for the glass powder to contain 80% particles having a particle size of 40 to 60 μm. When 80% of glass particles having an average particle diameter of 40 μm to 60 μm are contained, the glass powder can be best mixed with the foaming agent. Therefore, the foamed state is improved, and a foamed glass material having an internal structure close to a continuous gap structure and having a water absorption rate of 40 to 120% is obtained.

  The mixture 7 formed by mixing the glass particles and the additive 2 in the mixing device 6 is spread in a layer of a certain thickness on the start end of the belt conveyor 8 having a length of about 30 m. Is rotated into the firing furnace 9 and heated to 600 ° C. to 1000 ° C. while moving through the furnace. As a result, the glass component in the mixture 7 is melted, foamed, and fired in the firing furnace 9, and when it comes out from the end of the firing furnace 9, a plate-like fired product 10 having a temperature of about 400 ° C. to 800 ° C. is formed. Is done.

  The fired product 10 formed by passing through the inside of the firing furnace 9 moves horizontally as it exits from the end of the firing furnace 9 by the rotation of the belt conveyor 8. From the jet fountain device 12 disposed above, jet water 13 cooled to about 5 ° C. to 10 ° C. is sprayed in the form of a mist toward the fired product 10, and the fired product 10 is rapidly cooled. A water pump 15 supplies high-pressure water to the jet fountain device 12.

  The fired product 10 bathed in the cold mist-like jet water 13 while moving horizontally together with the belt conveyor 8 is rapidly cooled from a high temperature of about 400 ° C. to 800 ° C. to room temperature. The granular foamed glass material 14 having a particle size of about 5.0 mm to 30.0 mm can be obtained at the end of the belt conveyor 8 by crushing finely. In the case of this embodiment, jet water 13 is sprayed and cooled on the fired product 10 so that the granular foamed glass material 14 gets wet, but glass fine powder generated by crushing during rapid cooling is in the air. It is possible to prevent scattering and floating. Moreover, since the granular foamed glass material 14 will be wash | cleaned with water by jetting the jet water 13 in the shape of a mist, even if the granular foamed glass material only baked shows alkalinity of about pH 8-9. On the other hand, the granular foamed glass material 14 is neutral at about pH 7.

  Thus, by passing through the process shown in FIG. 1, the granular foamed glass material 14 having a particle size of about 5.0 mm to 30.0 mm is efficiently produced from the glass particles using the waste glass 1 as a raw material. Can be manufactured automatically. In addition, the fired product is rapidly cooled even if it is exposed to normal temperature blown air or is sprayed with normal temperature water, and the fired product 10 is finely crushed by the strain generated during this cooling, so the average particle size is 5.0 to 40.0 mm. A granular foamed glass material of the order (maximum particle size of about 50 mm) is obtained. Therefore, in such a method for producing a foamed glass material, the step of re-crushing the fired product to make it finer is unnecessary, so that the production process is simplified and the cost can be reduced.

  The bulk specific gravity of the granular foamed glass material 14 is adjusted by the amount of additive 2 added, the particle size of the glass particles, the thickness of the mixture 7 spread on the belt conveyor 8, the heating temperature or the heating time, etc. Can do. Moreover, the raw material of a glass granular material is not limited to the waste glass 1 such as a waste glass bottle or waste plate glass, and various types of waste glass materials can be used.

  Next, with reference to FIG. 2, the foamed glass material manufacturing method which is 2nd embodiment of this invention is demonstrated. In FIG. 2, portions that exhibit the same functions and effects as those in the method of manufacturing a foam glass material shown in FIG. 1 are denoted by the same reference numerals as those in FIG.

  In the manufacturing method of the foam glass material of the present embodiment shown in FIG. 2, after the same process as in FIG. 1 is performed, the fired product 10 of about 400 ° C. to 800 ° C. is formed, and then the firing that moves horizontally with the belt conveyor 8. A high-pressure air 22 of about 5 ° C. to 10 ° C. that is forcibly blown from the blower fan 20 and ejected from the air injection device 21 is blown against the object 10. The fired product 10 bathed in such cold high-pressure air 22 is rapidly cooled from a high temperature of about 400 ° C. to 800 ° C. to room temperature. Then, a granular foamed glass material 24 having a particle size of about 5.0 mm to 30.0 mm is obtained.

  In the case of the present embodiment, since it is a so-called air cooling system that cools the fired product 10 using the high-pressure air 22, a cooling water supply pipe or drainage equipment is unnecessary, and the granular foamed glass material 24 gets wet. Since there is nothing, the granular foamed glass material 24 in a dry state can be obtained. About the function of another part, an effect, etc., it is the same as that of the foam glass material manufacturing method shown in FIG.

  Moreover, as for the foamed glass material obtained by the manufacturing method of the foamed glass material in the said embodiment, the granular material containing a magnesium component is exposed to the surface and the space | gap inner wall surface. Therefore, since this foamed glass material has many magnesium components exposed compared to the same amount of magnesium, it exhibits a strong adsorption action of phosphoric acid, and if added to the treated water, it is contained in the treated water. Phosphorus can be adsorbed on the foamed glass material and treated with water. Examples of the scope of application of the foam glass material include direct purification of closed water areas such as dams, direct purification of rivers and waterways flowing into the closed water areas, and advanced treatment such as sewage treated water and livestock wastewater.

  Moreover, this foamed glass material can be applied to the bottom mud in the water to be treated, and the bottom quality can be improved by adsorbing phosphorus eluted from the bottom mud to the foamed glass material. Moreover, since this can make bottom mud high pH, the activity of a sulfate reducing bacterium can be lowered | hung and generation | occurrence | production of hydrogen sulfide can be prevented. For example, it is possible to improve sediment quality in tidal flats, coastal areas and sea areas, and improve sediment quality in dams and lakesides.

  Moreover, the foamed glass material which adsorb | sucked this phosphorus can also be used as soil improvement materials, such as a fertilizer.

An experiment was conducted to confirm the phosphorus adsorptivity of the foamed glass obtained in the above embodiment. FIG. 3 is a diagram showing the relationship between the orthophosphoric acid phosphorus (PO ₄ -P) concentration of the water to be treated and the elapsed time. As shown in FIG. 3, the PO ₄ -P concentration in the water to be treated is 1/3 at 6 hours when magnesium is 7% and 14% when magnesium is 7%, compared to the foamed glass material not containing magnesium. Including, it decreased to 1/6.

  The foamed glass material of the present invention is useful for water treatment, bottom sediment improvement, and soil improvement material.

It is process drawing which shows the manufacturing method of the foam glass material which is 1st embodiment of this invention. It is process drawing which shows the manufacturing method of the foam glass material which is 2nd embodiment of this invention. It is a figure which shows the relationship between PO4-P density | concentration of to-be-processed water, and elapsed time.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Waste glass 2 Additive 3 Separation apparatus 4 Coarse crushing apparatus 5 Fine crushing apparatus 6 Mixing apparatus 7 Mixture 8 Belt conveyor 9 Firing furnace 10 Firing product 12 Jet fountain apparatus 13 Jet water 14, 24, 34 Granular foam glass material 15 Water feed pump 20 Blower Fan 21 Air Injector 22 High Pressure Air

Claims (2)

A mixture in which the content of the magnesite powder obtained by mixing a glass powder having a particle size of 5 μm to 100 μm, a magnesite powder, and a foaming agent is 10 to 20% by mass. A firing step of heating to 600 ° C. to 1000 ° C. to melt, foam, and fire;
A method for producing a foam glass material, comprising: a quenching step of quenching a fired product formed in the firing step. Method for producing foam glass material according to claim 1, wherein 0.1 to 5.0 mass% content of the blowing agent.

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