JP2005022903A - Ceramic porous body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic porous body which is suitable for cleaning and aerating water, especially as a water cleaning material for a fish-farming pond. <P>SOLUTION: The ceramic porous body is a porous molded body prepared by subjecting a basis material comprising refractory aggregate and a foaming material to extrusion molding, drying, and firing. The refractory aggregate mainly comprises silica stone, and the foaming material is a crushed polystyrene foam being particles prepared by crushing waste polystyrene foam blocks. By enhancing the adsorption performance of the ceramic porous body by causing it to carry carbon, the water cleaning performance of the ceramic porous body is enhanced. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００２７】
【表２】

【００２８】
実施例２
実施例１で得られた押出ベースを用いて製品の種類を増すために、ミンチクリ機の孔径を１０〜４０ｍｍφ、押出物の切断長を３〜２００ｍｍに変更して押出成形をし、種々の製品を作成した。製品の種類について、製品番号１〜７として表３に示す。いずれも充填密度０．３〜０．４付近のものが得られた。製品３は実施例１で作られたものである。平均的な充填嵩密度は０．２６〜０．３７の範囲であった。
【００２９】
これらの製品は用途に応じて適宜の比率で混合使用することができる。例えば、鯉の養魚池の浄化に対しては、孔径４０ｍｍ、長さ２００ｍｍ程度が好ましく、家庭用水槽に対しては、孔径１０ｍｍ、長さ３０ｍｍ程度が利用できる。
【００３０】
【表３】

【００３１】
実施例３
耐火材料として、硅石、カオリン、ムライトの混合物を用いた以外は実施例１と同様に処理した。プレス成形用基材を調整した。このプレス成形用基材を３００トン大型プレス成形機により３００×３００×１００ｍｍの板状ブロックに成形し、実施例１と同様に自然乾燥、強制乾燥後、１３００℃で焼成し、多孔ブロックの製品８とした。得られた多孔ブロックの嵩比重は０．４であった。
【００３２】
実施例４
表３に示す製品番号１と３の１：１混合物１００ｋｇ及び製品番号４と５の１：１混合物１００ｋｇをそれぞれ濃度約１５％のカーボンブラックと約２％のポリビニルアルコール混合水溶液２００ｋｇ中に浸漬、液切りして１５０℃で熱風乾燥してカーボン約１７￣１９ｋｇを担持させた製品９，１０とした。これらの物理的性状を表４に示す。
【００３３】
【表４】

【００３４】
上記製品番号９の炭素担持のセラミック多孔体１につき、遠赤外線の放射強度を試料表面温度４０．５℃の測定条件で調べた。波長と強度の関係は図１のとおりである。対象に麦飯石２を用いたが、麦飯石よりも遙かに優れる遠赤外線放射能を示した。
【００３５】
比較例
多孔質成形体に本発明のポリスチロール発泡体破砕物と対比するため、粒子径０．６￣１．０ｍｍ未発泡の熱発泡性ポリスチロールビーズ及び平均粒子径３ｍｍ以下の木チップを用いて実施例１と同様の耐火材組成と方法によってセラミック多孔体を作成した。これらの発泡材を耐火材料の容積の５倍と所定量の澱粉質バインダー及び水と共に混合し、押出成形に適した塑性限界に近い粘性を有するスラリー状の押出ベースとした。この押出ベースを大型のミンチくり機の直径４０ｍｍφの多数の孔径から押出成形しながら長さほぼ１０ｃｍに切断して、円形棒状の基材とした。
【００３６】
この成形体を実施例１と同様に乾燥後焼成して表５に示す焼結体を得た。この焼結体は、本発明のポリスチロール発泡体破砕物のように８００℃以下での速やかな収縮、ガス化が起こり難く、より高温で急激な大量のガス化によって焼結体の型くずれや木チップの場合はその一部が炭化したまま内部に気孔を形成しないことになって、気孔率は低く、充填嵩密度は高くなっている。
【００３７】
【表５】

【００３８】
使用例
本発明のセラミック多孔体を鯉の養魚場の水質浄化に応用した実施例につき述べる。養魚場の大きさは約５００ｍ^２、水量約１５００トンであり、これに大型鯉が４０匹収容されている。これに対して、容積０．６×２．０×０．３のパンチングメタル底の容器に２０００ｋｇの製品番号９のセラミック多孔体を収容した浄化器を５段重ねにしたユニットを３ユニット配置して、養魚池からの水を流下循環した。
セラミック多孔体は、硅石を主体とした基材であることに加えて、混合した発泡スチロール粒子の焼却粒が微細かつ多孔な形状の連続気孔があって有益なバクテリアの固着が良好であるうえ曝気効果も抜群で極めて優れた高い水の浄化作用が得られた。
【００３９】
【発明の効果】
本発明のセラミック多孔体は、硅石を主体とした基材であることに加えて、混合した発泡スチロール粒子の焼却粒が微細かつ多孔な形状の連続気孔があって有益なバクテリアの固着が良好で極めて優れた高い水の浄化作用が得られる。
【００４０】
得られた製品は純白高焼成品で、無菌無害製品で、有富溶出成分も皆無に近く、人体・動植物に無害であり、変質することもなく、雨焼成により活性化して繰返し使用できる。
【００４１】
また、この焼成品にカーボンを付着させると、基材の多孔質の効果によって、カーボン粒子単独よりも目詰まりがなく、基材の遮光外線放射作用と、バクテリアによる有機物分解作用と相俟って水の浄化作用が一段と増大する。
【００４２】
したがって、前述の飲料水の浄化から土壌廃水の浄化に至る広範囲な水の浄化のほか、酒、醤油の製造工程におけるバイオリアクターとしての利用、触媒の担体や水耕栽培用植物担体等広範囲な用途において有効に活用できる。
【図面の簡単な説明】
【図１】遠赤外線放射強度を示す、波長と放射強度の関係グラフである。
【符号の説明】
１ 炭素担持のセラミック多孔体
２ 麦飯石[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a porous ceramic body that can be suitably used for water purification and aeration, and is particularly useful for use as a water purification material for fish ponds.
[0002]
[Prior art]
As prior arts in the technical field of the present invention, Patent Document 1 “Process for producing sponge-like ceramic body”, Patent Document 2 “Microorganism immobilization support for wastewater treatment”, Patent Document 3 “Porous sintered body having continuous air holes” Manufacturing method ”, and Patent Document 4“ Manufacturing method of ceramic porous body ”. As a prior art mainly for purifying the water inhabiting the fish in relation to each of the above prior arts, Patent Document 5 “Water purification body for purifying water in a raw fish container and a water quality purifier using the same” and Patent Reference 6 “Water Aeration Device” is available.
[0003]
[Patent Document 1]
Japanese Patent Laid-Open No. 50-075608 (page 3, upper left column and upper right column)
[Patent Document 2]
JP-A-63-077756 (Claim 1, page 2, upper right column)
[Patent Document 3]
JP 63-265880 A (Claim 1, page 2, lower left column)
[Patent Document 4]
JP-A-06-227873 ([0008], [0010])
[Patent Document 5]
Japanese Patent Laid-Open No. 05-111338 (Claim 1, [0006], [0007], FIG. 1)
[Patent Document 6]
JP 2002-346590 A (2nd page, FIG. 2)
[0004]
Patent Document 1 is a sponge-like ceramic body in which a ceramic material is filled in a hollow space of a spherical skeleton obtained by bonding polystyrene spheres to each other, and the remaining ceramic skeleton is removed at 1000 to 1500 ° C. by removing the polystyrene sphere. . Specifically, foamable polystyrene is mentioned as the polystyrene sphere, and aluminum oxide is mentioned as the ceramic material.
[0005]
Patent Document 2 is a microorganism-immobilized carrier obtained by blending clay and pore forming material into blast furnace water granulation, molding and firing. This uses blast furnace water granulation which has the effect of increasing the affinity with microorganisms.
[0006]
Patent Document 3 describes a method for producing a porous sintered body by filling a void of a resin particle molded body formed by binding resin particles with a slurry of an inorganic powder, and in particular, curing in a slurry of an inorganic powder. A technique containing a mold resin is disclosed. Here, there is a case where a polystyrene foam is used as the resin constituting the resin particle molded body.
[0007]
In Patent Document 4, (A) a step of filling a mold containing a ceramic raw material and water pre-filled with a synthetic resin foam, (B) compressing and fixing the mold, and a gap between the synthetic resin foam Ceramics comprising a step of sufficiently filling the slurry with a slurry, (C) a step of curing the slurry-like ceramic, (D) a step of removing the synthetic resin foam, and (E) a step of firing the cured molded body. A method for producing a porous body is disclosed. Here, “polystyrene foam” is exemplified as the synthetic resin foam used, and it is described that the synthetic resin foam is removed by heating to a temperature equal to or higher than the thermal decomposition point of the synthetic resin.
[0008]
Patent Document 5 describes a water purification unit for purifying water in a raw fish container and a water purification unit using the water purification unit. Specifically, a purification unit for purifying water in a raw fish container is made of silica and clay. It is formed by firing the substrate. This purifier has a large number of pores, and after mixing these pores with a base material containing silica and clay and a pore-forming material burned out at a temperature lower than the firing temperature of the silica and clay, In some cases, the substrate containing the pore forming material is fired to burn out the pore forming material. Here, foamable beads (polystyrene) are exemplified as the pore forming material.
[0009]
Also, in the purification device described in “Water Aeration Device” of Patent Document 6, a large one is an aeration device in which a filter medium is placed on a perforated plate of an aeration unit.
[0010]
[Problems to be solved by the invention]
As described above, in these conventional techniques, there are descriptions of a very wide variety of ceramic raw materials and resin materials. In particular, the use of silica used in the present invention, and thermoplastic resin particles as pore forming materials. There is also a description of using expandable beads, in particular polystyrene beads. However, in these conventional methods, the foaming method is complicated, the foaming rate cannot be increased, and there are many problems such as cracks in the molded product at the time of foaming. There was a difficulty in getting.
[0011]
Moreover, the ceramic porous body for fish pond water quality purification seen in these prior arts is not large-scale, but is used for water quality purification of a small aquarium for indoor appreciation, or is insufficient in performance. Furthermore, extremely nervous water quality management is required. In particular, it is insufficient as a high-porosity ceramic body with performance that can be provided for fish ponds such as ultra-high-grade Nishikigoi and Japanese flounder, that is, organic bacteria resolution, air entrainment or aeration Met.
[0012]
[Means for Solving the Problems]
The present invention is a novel ceramic porous body that solves such problems, and is a porous molded body formed by extruding or press-molding a base obtained by adding a pore-forming material to a refractory aggregate, drying and firing. The fireproof aggregate is mainly composed of silica stone, and the porous molded body is a crushed material of a polystyrene foam.
[0013]
Here, various types of crushed polystyrene foam can be used. For example, foamed plastic used as a fresh fish transportation toro box, such as packaging materials and containers that are often used as heat insulation and cushioning materials. The crushed particles of the styrene block waste are also preferable from the viewpoint of waste reuse.
[0014]
Polystyrene foams having a wide range of particle diameters can be used depending on applications, but usually the particle diameter is pulverized to 10 mm or less, preferably 5 to 3 mm or less. The particle size need not be particularly uniform, and even fine particles generated during crushing may be included. Thus, it is the feature to use the crushing thing particle | grains of what is foamed.
[0015]
The refractory aggregate can be freely selected from powders of ordinary general-purpose refractories such as silica-based, alumina-based, silica-alumina-based, magnesia-based, etc., but silica-based silica powder is preferred as a germ bed for bacteria. is there. In actual use, in addition to silica-alumina feldspar powder, kaolin clay, halloysite clay, mullite clay, mica clay and the like are appropriately mixed and used. The blending ratio is selected, for example, in the range of 40 to 85 parts by weight of quartzite, 5 to 20 parts of feldspar powder, and 10 to 40 parts of clay, depending on the shape of the molded product.
[0016]
The amount of the polystyrene foam added to the refractory aggregate is 100 to 800%, preferably 300 to 700%, more preferably 400 to 550% in volume. If it is 100 volume% or less, the porosity is too low, and if it is 800 volume% or more, it becomes brittle in strength. The porosity can be adjusted in the range of 15 to 80%.
[0017]
For molding, in addition to refractory aggregate and polystyrene foam, add a suitable amount of water and a water-soluble polymer binder such as methylcellulose, hydroxymethylcellulose, and polyvinyl alcohol for press molding and extrusion molding. A suitable viscosity is prepared and formed into a desired shape, for example, a plate shape, a columnar shape, a prismatic shape, or the like. The obtained molded body is moisture-dried by natural drying and forced drying, and then fired at a high temperature of about 1300 degrees to incinerate and remove the polystyrene foam to obtain a porous fired body.
[0018]
The obtained fired body uses a polystyrene foam as a pore-forming material, so that the polystyrene foam rapidly contracts during the heating process during firing, and the combustion gas of the polystyrene foam is formed through the formed communication holes. Quickly diffuses to the outside. As a result, even if the porous body has a high porosity, the shape does not easily collapse, and a relatively strong ceramic porous body can be obtained. If a large amount of unfoamed resin, sawdust, carbon, etc., which is another organic substance instead of polystyrene foam, is used as the pore forming material, the organic substance will not shrink and the molded body will expand due to the generated gas. As a result, cracks will occur and the mold will be deformed. In particular, when 2 to 4 times as much organic material as the refractory aggregate is added, it collapses remarkably. For this reason, conventionally, firing has to be performed for a long time in which the temperature is gradually raised, and the working efficiency is poor. This problem is solved by using a polystyrene foam granular material.
[0019]
When the porous molded body is a synthetic organic compound other than a polystyrene foam or a hard granular material such as a wood chip, extrusion molding may be difficult particularly when the porous molded body is 3 mm or more. In addition, rapid shrinkage and gasification at 800 ° C. or less are unlikely to occur like polystyrene foam, so that no pores are formed inside the molded body while it is deformed or carbonized due to a large amount of gasification at a higher temperature. Thus, the object of the present invention cannot be achieved. Polystyrene foam can be used for recycled waste such as used trays and trolley boxes, and the particle size can be easily prepared in the pulverization process, so it is extremely low cost as a raw material. As described above, since the use of the polystyrene foam facilitates molding and baking, for example, a large block of 300 × 300 × 100 mm or the like can be manufactured.
[0020]
The use of the polystyrene foam not only improves work efficiency and economy, but also causes a large gap of 3 mm or more to be uniformly and neatly generated due to the rapid shrinkage of the polystyrene foam. For this reason, a large amount of water is taken into the fired body, and the taken-in water is easy to move, so that there is no water in the interior and the water purifying effect is improved. In addition, since it is a ceramic high-temperature fired product, it emits abundant far-infrared rays, so that the water cluster becomes smaller and the uptake of dissolved oxygen increases.
[0021]
Carbon can be supported on the ceramic porous body made of the porous molded body of the present invention produced as described above, and further water purification performance can be enhanced. The carbon used here can be various types of carbon such as carbon black, ketjen black, graphite carbon, charcoal and bamboo charcoal powder, activated carbon powder, etc., but using a micron-order ultrafine particle solution such as a carbon colloid solution. It is better to impregnate.
[0022]
As for the loading conditions, the porosity of the porous molded body is 10 to 80%, and in this way, the carbon loading range was 1 to 50% by weight, preferably 10 to 20% by weight. It will be a thing. As described above, even when a large amount of carbon is supported, the porosity is hardly lowered, and a product having a large adsorption surface area can be obtained by uniformly supporting the inside of the pores. This is an effect of using a crushed polystyrene foam as the pore forming material, and cannot be obtained with a pore forming material made of a normal organic material.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the ceramic porous body of the present invention will be described based on specific examples, but the ceramic porous body of the present invention is not limited to these examples.
[0024]
Example 1
What was washed and dried from the waste product of the Styrofoam made of styrene foam for transporting fish was put into a pulverizer to obtain powder particles having a particle size of 3 mm or less. On the other hand, as a refractory material, 70 parts by weight of meteorite having an average particle diameter of 1 mm, 10 parts by weight of feldspar with an average particle diameter of 0.5 mm, 10 parts by weight of kaolin grain soil (180 mesh pass), and 10 mica type grain soil (180 mesh path). Using a mixture of parts by weight, the above expanded polystyrene granules of 5 times the volume of the refractory material are mixed with a predetermined amount of starchy binder and water, and a slurry-like viscosity having a viscosity close to the plastic limit suitable for extrusion molding is used. An extrusion base was used. This extrusion base was cut into a length of approximately 10 cm while being extruded from a large number of holes having a diameter of 40 mmφ of a large mincing machine to obtain a circular rod-like base material.
[0025]
After air-drying this molded body, it is forcedly dried in a hot air dryer at 100 ° C., and then fired at about 1300 ° C., and the styrene foam granules are incinerated and removed. The porosity is about 60% and the water absorption is about 150%. A sintered body was obtained. This sintered body has a high water absorption rate and is connected not only to the porous surface but also to the middle part, and independent pores exist in a state of water communication, and is a product with high water purification efficiency described later. Table 1 shows the general physical properties of the obtained product, and Table 2 shows the chemical components and the like.
[0026]
[Table 1]

[0027]
[Table 2]

[0028]
Example 2
In order to increase the types of products using the extrusion base obtained in Example 1, extrusion molding was performed by changing the hole diameter of the mincing machine to 10 to 40 mmφ and the cut length of the extrudate to 3 to 200 mm. It was created. The product types are shown in Table 3 as product numbers 1-7. In each case, a packing density of about 0.3 to 0.4 was obtained. Product 3 was made in Example 1. The average filling bulk density was in the range of 0.26 to 0.37.
[0029]
These products can be mixed and used at an appropriate ratio depending on the application. For example, a hole diameter of about 40 mm and a length of about 200 mm are preferable for purifying a salmon fish pond, and a hole diameter of about 10 mm and a length of about 30 mm can be used for a domestic water tank.
[0030]
[Table 3]

[0031]
Example 3
The same treatment as in Example 1 was conducted except that a mixture of meteorite, kaolin and mullite was used as the refractory material. A base material for press molding was prepared. This press-molding substrate was formed into a 300 × 300 × 100 mm plate-like block by a 300-ton large-size press molding machine, naturally dried and forced-dried in the same manner as in Example 1, and then fired at 1300 ° C. It was set to 8. The bulk specific gravity of the obtained porous block was 0.4.
[0032]
Example 4
100 kg of a 1: 1 mixture of product numbers 1 and 3 and 100 kg of a 1: 1 mixture of product numbers 4 and 5 shown in Table 3 were immersed in 200 kg of a mixed solution of about 15% carbon black and about 2% polyvinyl alcohol, respectively. The product was drained and dried with hot air at 150 ° C. to obtain products 9 and 10 carrying about 17 to 19 kg of carbon. These physical properties are shown in Table 4.
[0033]
[Table 4]

[0034]
With respect to the carbon-supported ceramic porous body 1 having the product number 9, the far-infrared radiation intensity was examined under the measurement condition of the sample surface temperature of 40.5 ° C. The relationship between wavelength and intensity is as shown in FIG. Although barley stone 2 was used for the object, it showed far-infrared radioactivity far superior to barley stone.
[0035]
In order to contrast with the crushed polystyrene foam of the present invention in the comparative example porous molded body, the particle diameter of 0.6 to 1.0 mm unfoamed thermally foamable polystyrene beads and wood chips with an average particle diameter of 3 mm or less were used. A ceramic porous body was prepared by the same refractory material composition and method as in Example 1. These foamed materials were mixed with 5 times the volume of the refractory material and a predetermined amount of starchy binder and water to obtain a slurry-like extrusion base having a viscosity close to the plastic limit suitable for extrusion molding. This extrusion base was cut into a length of approximately 10 cm while being extruded from a large number of holes having a diameter of 40 mmφ of a large mincing machine to obtain a circular rod-like base material.
[0036]
This molded body was dried and fired in the same manner as in Example 1 to obtain sintered bodies shown in Table 5. This sintered body is unlikely to rapidly shrink and gasify at a temperature of 800 ° C. or lower like the crushed polystyrene foam of the present invention. In the case of the chip, pores are not formed inside while a part thereof is carbonized, so that the porosity is low and the filling bulk density is high.
[0037]
[Table 5]

[0038]
Example of Use An example in which the ceramic porous body of the present invention is applied to the purification of water in a salmon fish farm will be described. The size of the fish farm is about 500 m ² and the amount of water is about 1500 tons, which contains 40 large sharks. On the other hand, three units of a purifier containing a ceramic porous body of 2000 kg of product number 9 in a container of punched metal bottom with a volume of 0.6 × 2.0 × 0.3 are arranged in three units. The water from the fish pond was circulated down.
In addition to the base material mainly composed of meteorite, the ceramic porous body has fine pores and continuous pores with a fine and porous shape, and has good adhesion of beneficial bacteria and aeration effect The water purification action was excellent and excellent.
[0039]
【The invention's effect】
The ceramic porous body of the present invention is not only a base material mainly composed of meteorite, but also the incinerated grains of the mixed expanded polystyrene particles have continuous pores with a fine and porous shape, and the adhesion of beneficial bacteria is extremely good. Excellent high water purification effect is obtained.
[0040]
The obtained product is a pure white high-baked product, is a sterile and harmless product, has almost no elution-rich components, is harmless to humans, animals and plants, and does not deteriorate, and can be activated by rain firing and used repeatedly.
[0041]
In addition, when carbon is attached to this fired product, due to the porous effect of the base material, there is less clogging than the carbon particles alone, combined with the light shielding external radiation action of the base material and the organic matter decomposition action by bacteria. Water purification action is further increased.
[0042]
Therefore, in addition to the purification of a wide range of water from the purification of drinking water to the purification of soil wastewater as described above, it can be used as a bioreactor in the production process of liquor and soy sauce, and in a wide range of applications such as catalyst carriers and plant carriers for hydroponics Can be used effectively.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between wavelength and radiation intensity, showing far-infrared radiation intensity.
[Explanation of symbols]
1 Carbon-supporting ceramic porous body 2 Barleystone

Claims (8)

A porous molded body formed by extruding or press-molding a base obtained by adding a pore-forming material to a refractory aggregate, drying and firing, wherein the refractory aggregate is mainly composed of silica stone, and the pores A ceramic porous body, wherein the forming material is a crushed material of a polystyrene foam. The porous ceramic body according to claim 1, wherein the crushed polystyrene foam is crushed particles of foamed polystyrene block waste. 3. The ceramic porous body according to claim 1, wherein the pulverized material of the foamed polystyrene block waste has a particle size of 10 mm or less and is a mixture containing fine powder generated upon crushing. The ceramic porous body according to claim 1, wherein the amount of the polystyrene foam added to the refractory aggregate is 100 to 800% in volume and the porosity is in the range of 15 to 80%. The refractory aggregate is a ceramic raw material composed of 40 to 85 parts by weight of quartzite, 5 to 20 parts of feldspar powder, and 10 to 40 parts of clay content, and 100 polystyrene foam powder is added to 100 parts by volume of the refractory aggregate. The ceramic porous body according to claim 1, which is a ceramic filter obtained by mixing ~ 800 parts by volume, forming and drying, and firing at around 1300 ° C. The ceramic porous body according to claim 1, wherein carbon fine particles are supported on the porous molded body. The porous ceramic body according to claim 6, wherein the amount of carbon fine particles supported on the porous molded body is 1 to 50 wt%. The ceramic porous body according to claim 1, which is used for water purification in a salmon farm.

Images