JP2003221285A - Inorganic foam composition and inorganic foam, and method for manufacturing inorganic foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic foam composition, by which wastes can be recycled as resources, an inorganic foam having a required specific-gravity value can be stably obtained, and an inorganic foam having excellent performance for improving water quality can be formed, to provide an inorganic foam, in which layers having various specific-gravity values are integrally laminated and which has excellent immovability, and furthermore to provide a manufacturing method for an inorganic foam, which is excellent in energy saving property and besides makes smaller the load to equipment such as a heating furnace and where foaming surely occurs to form air bubbles and the inorganic foam excellent in stability of product quality can be obtained. <P>SOLUTION: The inorganic foam composition contains inorganic powder, which is obtained by pulverizing inorganic waste materials, and a shell powder, which is obtained by pulverizing shells. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic foam composition, an inorganic foam, and a method for producing an inorganic foam using an inorganic waste material such as glassy waste material, incinerated ash and brick waste material. Is.

[0002]

2. Description of the Related Art Conventionally, in order to recycle glassy waste materials and coal ash, which are one type of inorganic waste materials, the glassy waste materials and coal ash have been used to uniformly disperse them in a matrix of glassy material. Glassy foams, lightweight artificial aggregates, etc., which form independent or continuous bubbles and are excellent in heat insulation and soundproofing, have been developed. For example, in (Patent Document 1), “a granulated raw material in which limestone powder is mixed with crushed bottle glass etc.
The manufacturing method of the foam glass heated at -960 degreeC is disclosed.

[Patent Document 2] "Artificial lightweight in which coal ash is mixed with waste glass, a binder, and a foaming agent such as iron oxide, silicon carbide, or carbon material, which is crushed and then molded and fired. A method of manufacturing an aggregate "is disclosed.

[Patent Document 3] describes that "waste glass is crushed to form powder particles, and at least one of metal carbonates such as sodium carbonate, metal carbides such as silicon carbide, and metal nitrides such as silicon nitride. A method of making a glass foam by adding seeds and heating "is disclosed.

(Patent Document 4) discloses "a method for producing a glassy foam by mixing coarsely pulverized glass powder and finely pulverized glass powder, adding silicon carbide to the mixture, and heating".

[0006]

[Patent Document 1] JP-A-58-60634

[Patent Document 2] Japanese Patent Laid-Open No. 11-335146

[Patent Document 3] JP-A-11-343128

[Patent Document 4] Japanese Patent Laid-Open No. 11-236232

[0007]

However, the above conventional techniques have the following problems. In the technology disclosed in (1) (Patent Document 3), the particle size of the powdered waste glass or the foaming agent is not specified, so even if the conditions for heating the raw material are constant, There is a problem in that the molten state and the foamed state are different, the specific gravity and the size of the bubbles are not stable, and the quality is not stable. (2) Although the techniques disclosed in (Patent Document 1) to (Patent Document 4) use glass scraps or the like as the raw material glass,
Since a natural resource such as limestone or a chemical agent such as silicon carbide is mainly used as the foaming agent, there is a problem that the resource saving property is lacking.

The present invention solves the above-mentioned problems of the prior art. It is possible to recycle waste, obtain an inorganic foam having a desired specific gravity in a stable manner, and have an excellent water quality improving action. It is an object to provide an inorganic foam composition capable of forming an inorganic foam.
Further, the present invention has an object to provide an inorganic foam excellent in landing property, in which layers having different specific gravities are laminated and integrated, and when they are dropped into water such as lakes and marshes, they settle down with the high specific gravity layer facing down and land. To do. Another object of the present invention is to provide a method for producing an inorganic foam which is excellent in energy saving and has a small equipment load such as a heating furnace, and is further surely foamed to form bubbles and having a high product yield. . Further, there is provided a method for producing an inorganic foam capable of easily producing an inorganic foam in which an inorganic base layer having a specific gravity of 1 or more and a low specific gravity foam layer having a specific gravity of less than 1 are integrated. The purpose is to provide.

[0009]

In order to solve the above-mentioned conventional problems, an inorganic foam composition, an inorganic foam and a method for producing an inorganic foam of the present invention have the following constitutions. .

The inorganic foam composition according to claim 1 of the present invention comprises an inorganic powder obtained by pulverizing an inorganic waste material,
And a shell powder obtained by crushing shells. With this configuration, the following effects can be obtained. (1) Since wastes such as inorganic waste materials and shells are used, the wastes can be recycled and excellent in resource saving. (2) Since the shell has a low hardness and is easily crushed, shell powder can be easily obtained, and the load of the crushing equipment and the number of steps can be reduced. (3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide gas, and the molten inorganic powder is foamed to form bubbles, and the humic acid contained in the shell burns and burns out. Thus, an inorganic foam having fine pores and a large surface area can be stably obtained. (4) Depending on the type of shell, it has a fibrous material such as red shell and the like, and the fibrous material is positioned around the bubbles formed by melting and foaming at a predetermined melting temperature to function as a reinforcing agent. Prevent bursting. (5) The shell has not only calcium ions but also magnesium ions, and these reduce the viscosity of the melt in which the inorganic powder is melted and reduce the residual strain generated during cooling, which makes it difficult to break during cooling. It is easy to form a long inorganic foam such as a plate and has excellent moldability. (6) Since calcium oxide produced by decomposing shell powder by heating absorbs water and carbon dioxide, it is possible to produce an inorganic foam having excellent hygroscopicity. (7) Since calcium hydroxide, which is generated by absorbing water by calcium oxide, is easily eluted, an inorganic foam that can be used as a soil modifier can be produced. (8) The main component of the shell powder is calcium carbonate, but since other components are also included and all do not undergo thermal decomposition, shell residues are dispersed in the substrate. For this reason,
When the inorganic foam formed by heating is immersed in water as a water purification treatment material or the like, calcium, magnesium, etc. are eluted from the fractured surface of the inorganic foam, shell residue, etc. in water.
As a result, the phosphoric acid dissolved in water reacts with the eluted calcium or is adsorbed by the calcium component in the inorganic foam to become calcium phosphate (insoluble), which can improve the water quality. In addition, the eluted magnesium can promote the growth of shellfish and algae.

Here, as the inorganic waste material, glassy waste material, incinerated ash, brick waste material, bones of livestock and fish, etc. are used.
These 1 type or multiple types can be mixed and used. Glassy waste materials are generated from chemical bottles, cosmetic bottles, food seasoning bottles, glass bottles such as beverage bottles, plate glass, window glass, wastes such as glass panels of TVs and displays, and glass product factories. Scrap or the like is used. As the incineration ash, coal ash of a combustion device which mainly uses solid fuel such as coal power generation, garbage power generation, or municipal waste incinerator is used. Brick materials include red brick, refractory brick, lightweight brick, pavement brick, glaze brick, slag brick, silica ash brick, cement brick, etc.
Scrap generated from a brick product factory is used.
As the bones of livestock and fish, bones obtained when processing livestock and fish such as cows, pigs, horses and chickens are used.

The shells include oysters, scallops, red clams, clams, clams, abalone, turban shells, clams, mussels,
Bivalves and snail shells such as bluffs are used. The shell is washed with water to remove sand, etc., dried, and then ground. When the wet pulverization is performed, it may be pulverized and then dried. In addition, the red shell has an inorganic fibrous material, and the fibrous material is located around the bubbles formed by melt-foaming and functions as a reinforcing agent, preventing the bubbles from bursting, stabilizing the bubbles and making them uniform. Since it can be realized, it is preferably used.

The crushing of the inorganic waste materials and shells can be carried out by using a crusher such as a hammer crusher, an edge runner, a screen mill, a roller mill, an elofol mill, a ball mill and a jet mill.

The invention according to claim 2 of the present invention is the inorganic foam composition according to claim 1, wherein 1 to 25 parts by weight of the shell powder is added to 100 parts by weight of the inorganic powder. It preferably has a structure containing 8 to 20 parts by weight, more preferably 10 to 15 parts by weight. With this configuration, claim 1
In addition to the effect obtained in step 1, the following effect is obtained. (1) Since the shell powder is blended in a predetermined amount, when the inorganic powder is heated and melted, an optimum amount of carbon dioxide gas is generated to form bubbles, and an inorganic foam having a large expansion ratio is obtained. (2) Since the shell powder has a low density, it has a large capacity and can be uniformly mixed with the inorganic powder.

The content of the shell powder is 1 to 25 parts by weight, preferably 8 to 20 parts by weight, more preferably 10 to 15 parts by weight, based on 100 parts by weight of the inorganic powder. Is. When the shell powder is 10 to 15 parts by weight with respect to 100 parts by weight of the inorganic powder, the amount of carbon dioxide gas generated by the decomposition of the shell powder is optimal, and the amount of foaming is large and the mechanical strength of the inorganic foam is also high. Is obtained. When the amount is 8 to 10 parts by weight, depending on the type of shell powder, the amount of carbon dioxide gas generated by decomposition is small and it tends to be difficult to foam, but a relatively large expansion ratio is obtained. When the amount is 15 to 20 parts by weight, the amount of carbon dioxide gas generated by decomposition of the shell powder is large and fine cracks are generated on the surface of the inorganic foam, and gas tends to escape, which makes it difficult to increase the bulk. A relatively high mechanical strength is obtained. When the amount is 1 to 8 parts by weight, the amount of carbon dioxide gas generated by decomposition of the shell powder is small and it is difficult to increase the bulk, and it tends to be difficult to form open cells.
If the amount is 5 parts by weight, the surface of the inorganic foam will have large cracks and the mechanical strength will tend to decrease. Especially 1
If the amount is less than 25 parts by weight or more than 25 parts by weight, these tendencies are remarkable, which is not preferable.

The invention according to claim 3 of the present invention is the inorganic foam composition according to claim 1 or 2, wherein the particle size of the inorganic powder is 0.01 to 3000 μm, preferably 0.1 to 1000 μm, more preferably 0.5 to 500 μm
It has a configuration that is m. With this configuration, claim 1
Alternatively, the following action is obtained in addition to the action obtained in 2. (1) Since the particle size of the inorganic powder is adjusted within a predetermined range, the melting temperature of the inorganic powder is stable, the size of the bubbles is stable, the particle size distribution of the bubbles is small, and the mechanical strength is improved. It can be increased and the stability of the quality of the inorganic foam is excellent.

Here, the particle size of the inorganic powder is 0.
0 to 3000 μm, preferably 0.1 to 1000 μm, more preferably 0.5 to 500 μm. When the particle size is 0.5 to 500 μm, it is possible to obtain an inorganic foam which is excellent in mechanical strength and is hard to crack even after cooling after heating and melting. As the particle size becomes smaller than 0.5 μm, the pulverization efficiency of the inorganic waste material decreases, the pulverization equipment load and the man-hour increase, and it tends to be melted during firing, making it difficult to control the melting temperature. This tendency becomes larger as the particle size becomes smaller than 0.1 μm, and the amount collected by the dust collector such as a bag filter at the time of crushing increases, and the load of crushing equipment tends to increase. Further, as it becomes larger than 500 μm, since the gap between the inorganic powders is large, it is difficult to melt and bond at the time of firing, the mechanical strength is lowered, and the inorganic foam tends to be easily cracked at the time of cooling after heating and melting. 1000μ
This tendency becomes larger as it becomes larger than m, and the specific gravity of the inorganic foam increases depending on the type of the inorganic powder, making it difficult to control the specific gravity of the product of the inorganic foam. Since the thermal conductivity is low, it is difficult to transfer heat to the inside of the inorganic powder during firing, and a portion where the firing is insufficient is formed, and the mechanical strength of the inorganic foam tends to decrease. In particular, when the particle size is smaller than 0.01 μm or larger than 3000 μm, these tendencies are remarkable, and thus both are not preferable. It is also possible to granulate an inorganic powder having a particle size within this range and use it as a granulated powder having a predetermined particle size.

Inorganic powders are classified by gravity classifier, inertia classifier,
If a dry classifier such as a centrifugal classifier or a sieving machine or a gravity type wet classifier such as a Spitzkasten or a spiral classifier or a centrifugal force type wet classifier such as a hydrocyclone classifies to a predetermined particle size, it will surely adjust within a predetermined range It is preferable because it is possible. When a wet classifier is used, the temperature is raised after drying or after completely evaporating water or the like at about 200 ° C. when heating in a heating furnace. This is to prevent the water content in the molded body molded from the inorganic powder from expanding in the heating furnace and the molded body from collapsing.

The particle size distribution of the inorganic powder is 10
100% by weight of integrated sieve of inorganic powder of 00 μm
In that case, it is preferable that the content thereof is 50 to 70% by weight in terms of cumulative sieving with a particle size of 250 μm and 70 to 90% by weight in terms of cumulative sieving with a particle size of 500 μm. The inorganic powder having this particle size distribution has excellent mechanical strength because the sintering progresses sufficiently during heating and melting, and it is possible to form an inorganic foam having excellent homogeneity by uniformly dispersing cells. . The inorganic powder having a particle size of 1000 to 3000 μm can be added and mixed at a ratio of 0 to 30 parts by weight with respect to 100 parts by weight of the inorganic powder having a particle size of 0.1 to 1000 μm. This makes it possible to increase the specific gravity of the formed inorganic foam, depending on the amount added.
The specific gravity of the product of the inorganic foam can be easily controlled. By setting the specific gravity to 1 or more, it easily settles in water under its own weight, which is particularly convenient when performing filtration or activation of water, and by setting the specific gravity to less than 1, weight reduction can be achieved. it can. In addition, 0.1-100
1000 to 3000 for inorganic powder having a particle size of 0 μm
When the inorganic powder having a particle diameter of μm is not added (when the addition amount is 0 part by weight), the cells are uniformly dispersed and an inorganic foam having excellent homogeneity can be formed. Particle size is 10
As the addition amount of the inorganic powder having a particle size of 0 to 3000 μm is more than 30 parts by weight, it is difficult for heat to be transferred to the inside of the inorganic powder during firing, and a large number of insufficient firing sites are formed. It is not preferable because the mechanical strength tends to decrease. When the inorganic powder having a particle size of 1000 to 3000 μm is not added and mixed, the powder can be pulverized again using a crusher such as a hammer crusher to be used as an inorganic powder having a particle diameter of 1000 μm or less.

The invention according to claim 4 of the present invention is the inorganic foam composition according to any one of claims 1 to 3, wherein the shell powder has a particle size of 0.1. ~ 3000 μm
Has a configuration that is With this configuration, the following action is obtained in addition to the action obtained in any one of claims 1 to 3. (1) Since the particle size of shell powder is 0.1 to 3000 μm,
It is difficult to aggregate and can be dispersed so as to be scattered in the inorganic powder, and bubbles can be uniformly distributed so as to be scattered by heating and melting and foaming. (2) As a result, it is possible to form independent bubbles having a relatively large diameter, and it is possible to form an inorganic foam having a specific gravity of more than 1.

The particle size of the shell powder is JIS
The particle size measured by a sieving method using a standard sieve, a microscopic method, or the like. Particle size of shell powder is 0.1 μm
As the load of crushing equipment and man-hour increase as it gets smaller, the shell powder tends to agglomerate easily and it becomes difficult to disperse it uniformly in the inorganic powder, and as it exceeds 3000 μm, one shell powder is heated. A large amount of gas is generated when is decomposed, and coarse bubbles are easily formed, and the inorganic foam is easily cracked from there, and the number of shell powder relative to the inorganic powder is reduced. Therefore, the number of cells is reduced and the expansion ratio of the inorganic foam tends to be small, which is not preferable. In addition,
The shell powder can be classified in the same manner as the inorganic powder described in claim 3. As a result, the particle size is 0.1 to 30
It can be reliably adjusted to the range of 00 μm.

A fifth aspect of the present invention is the inorganic foam composition according to any one of the first to third aspects, wherein the shell powder has a particle size of 0.1. ~ 1000 μm
Has a configuration that is With this configuration, the following action is obtained in addition to the action obtained in any one of claims 1 to 3. (1) Since the particle diameter of the shell powder is 0.1 to 1000 μm, which is almost the same as the particle diameter of the inorganic powder, it can be uniformly dispersed in the inorganic powder, and bubbles can be formed by heating and melting and foaming. Can be evenly distributed. (2) As a result, since the particles of the shell powder are small and uniformly dispersed, it is possible to form a large number of independent bubbles and continuous bubbles formed by connecting them, and an inorganic foam having a specific gravity of less than 1. Can form a body. (3) Since the particle size of the bubbles can be made small,
When used as a water purification treatment material, it is possible to capture suspended substances in water and has excellent water purification performance.

Here, as the particle size of the shell powder becomes smaller than 0.1 μm, the load of crushing equipment and the number of steps increase, and the shell powder tends to agglomerate and tends to be difficult to be uniformly dispersed in the inorganic powder. As a result, a large amount of gas is generated when one shell powder is decomposed by being heated as it becomes larger than 1000 μm and coarse bubbles are formed, and the number of shell powder relative to the inorganic powder is small. Since it tends to be difficult to form open cells, both are not preferable. The particle size of the shell powder used is that measured by a sieving method or the like as described in claim 4.

The invention according to claim 6 of the present invention is the inorganic foam composition according to any one of claims 1 to 3, wherein the shell powder has a particle size of 0.01. ˜50 μm, preferably 0.1 to 10 μm. With this configuration, the following action is obtained in addition to the action obtained in any one of claims 1 to 3. (1) Since the density of the shell powder is small and the particle size is small, the number of particles is large, so that the surface of the inorganic powder is sprinkled with the shell powder, and fine air bubbles are uniformly dispersed and formed. be able to. (2) As a result, it is possible to form continuous cells in which a large number of fine cells are connected, and it is possible to form an inorganic foam having a large surface area and a specific gravity of more than 1.

Here, as the particle size of the shell powder becomes smaller than 0.1 μm, the load and man-hours of the crushing equipment and the like increase, and the shell powder easily aggregates and becomes difficult to be uniformly dispersed in the inorganic powder. There is a tendency, and as the particle size becomes larger than 10 μm, the number of shell powder relative to the inorganic powder required to form the open cells is insufficient, and the open cells tend to be less likely to be formed. In particular, when the particle size is smaller than 0.01 μm or larger than 50 μm, these tendencies are remarkable, and neither is preferable. Further, as the shell powder, shell powder collected by a filter dust collector such as a bag filter or an air filter used when crushing the shell powder or a dust collector such as an electric dust collector is preferably used. Used. In the bag filter, shell powder having a particle size of 0.1 to 10 μm is 0.01 in the air filter and the electrostatic precipitator.
Capable of collecting shell powder having a fine particle size of about μm,
This is because it is efficient. As the particle size of the shell powder, the particle size measured by a microscope method or the like is used as in the case described in claim 4.

The invention according to claim 7 of the present invention is the inorganic foam composition according to any one of claims 1 to 6, wherein the inorganic waste material contains a glassy waste material. Have a configuration. With this configuration, the following action is obtained in addition to the action obtained in any one of claims 1 to 6. (1) Since many glassy waste materials are softened at a low temperature of 1000 ° C. or less, the load of equipment such as a heating furnace is small, and the viscosity of the melt is high, so that bubbles are easily formed and the specific gravity is easily controlled. And has high mechanical strength and excellent durability. Further, it is easy to form a long inorganic foam such as a plate and has excellent moldability. (2) After the glassy waste material is melted and solidified, cadmium,
Since it does not elute harmful substances such as cyanide, it is possible to obtain an optimal inorganic foam as a water treatment material for rivers and lakes.

Here, the glassy waste material can be mixed with other inorganic waste material at a predetermined ratio and used. Thereby, the melting point can be lowered and the viscosity at the time of melting can be increased.

The inorganic foam according to claim 8 of the present invention is obtained by pulverizing an inorganic base material layer obtained by pulverizing an inorganic waste material by heating and melting the inorganic base material layer and the inorganic waste material. And a low specific gravity foam layer formed by heating a homogeneous mixture of the inorganic powder and the shell powder obtained as described above to be integrated with the inorganic base layer and having a specific gravity smaller than that of the inorganic base layer. It has a different configuration. With this configuration, the following effects can be obtained. (1) Since it has the inorganic base layer integrated with the low specific gravity foam layer, it can reinforce the low specific gravity foam layer having relatively low mechanical strength and enhance the mechanical strength. Excellent durability. (2) Since the specific gravity of the inorganic base layer is higher than that of the low specific gravity foam layer, the inorganic base layer is formed to have a specific gravity of 1 or more so that the inorganic foam is submerged in water such as a lake, a swamp, or the sea. In that case, the inorganic base layer can be placed on the lake bottom or the like with the low specific gravity foam layer facing upward. Therefore, it becomes easy for the water flow to hit the low specific gravity foam layer having a large surface area, and algae easily adhere to the low specific gravity foam layer or microbial groups are easily fixed,
The low specific gravity foam layer can efficiently decompose organic substances and purify water. (3) When it is dropped into water such as lakes and marshes, it is settled and settled with the inorganic base layer having a high specific gravity facing down, and it has excellent emplacement properties in water, and it is stably fixed at the bottom of lakes and marshes and purified. You can

Here, the inorganic base layer is obtained by cutting inorganic powder obtained by crushing an inorganic waste material, shell powder, calcium carbonate, dolomite, limestone, marble, etc. A material formed by melting an inorganic powder to which waste powder or the like is added is used. In addition, claim 4
It is also possible to use a product obtained by melt-foaming the inorganic foam composition described in 1. This is because the specific gravity can be set to 1 or more and the specific gravity of the inorganic powder or less. As the low specific gravity foam layer, a layer in which shell powder is added to inorganic powder and heated to be integrated with the inorganic base layer so that the specific gravity is smaller than that of the inorganic base layer is used. Moreover, the thing which melt-foamed the inorganic type foam composition of Claim 5 can also be used. This is because the specific gravity can be less than 1.

The thickness of the inorganic base layer and the low specific gravity foam layer (volume ratio of the inorganic base layer and the low specific gravity foam layer) depends on the type of the inorganic powder and the like. Overall specific gravity is 1
Various selections can be made within the above range. This is because when the specific gravity of the whole is less than 1, it does not settle when dropped in water such as lakes and marshes and cannot be stably fixed to the bottom of lakes and marshes.

The method for producing an inorganic foam according to claim 9 of the present invention comprises a mixing step of mixing the inorganic foam composition according to any one of claims 1 to 7, and the mixing. The mixed powder obtained in the step is heated to 750 to 1100 ° C., preferably 900 to 1000 ° C. to melt and foam, and a heating and foaming step is provided. With this configuration, the following effects can be obtained. (1) Since the mixed inorganic foam composition is heated in a predetermined temperature range to melt and foam, the inorganic powder is sufficiently softened to completely wrap the shell powder, and the shell powder is decomposed. The generated carbon dioxide gas can surely cause foaming and has excellent stability. (2) Since the shell powder is uniformly mixed, it acts as a melting aid to lower the melting temperature of the whole and prevent the generation of melting spots that are likely to be the starting point of breakage and stabilize the mechanical strength. (3) The heating temperature is 750 to 1100 ° C., preferably 900
Since the temperature is relatively low at up to 1000 ° C., the load on equipment such as a heating furnace is small, and energy saving is excellent.

Here, in the heating and foaming step, the mixed powder obtained in the mixing step is filled in a mold made of stainless steel or deposited on a mesh belt or caterpillar made of stainless steel. , Or a molded body formed by molding with a mold, etc., is heated in a box furnace, a shuttle kiln, a roller hearth kiln, a tunnel furnace, etc. in an intermittent or continuous manner, and an inorganic powder (molded body) What melts is used. In the heating and foaming process, the carbon dioxide gas generated by the decomposition of the shell powder causes an inorganic powder (molded body).
Bubbles are formed in the melted material that is melted and softened. In addition, after the mixing step, a granulating step of granulating the mixed powder to form a granulated powder can be added. As a result, it is possible to prevent the fine inorganic powder or the like from agglomerating, etc., and improve the moldability of the molded product in the heat-foaming step, which is excellent in workability and the product yield.

The heating temperature in the heating and foaming step is
Although depending on the type of the inorganic powder, 750 to 1100 ° C, preferably 900 to 1000 ° C is preferably used. As the heating temperature becomes lower than 900 ° C, the softening of the inorganic powder is insufficient and it tends to be difficult to foam even if the shell powder is decomposed.
As the temperature rises above 1000 ° C, the air bubbles generated by the decomposition of the shell powder expand and become coarse, making it difficult to obtain fine air bubbles, and the foamed substances tend to remelt and become a smooth glassy material. To be In particular, when the temperature is lower than 750 ° C. or higher than 1100 ° C., these tendencies become remarkable, and thus both are not preferable.

In the heating and foaming step, at a heating temperature of 750 to 1100 ° C., depending on the thickness and size of the molded body,
Hold for 20 minutes. When the holding time is less than 5 minutes, foaming unevenness occurs and the sizes of the bubbles tend to be significantly uneven, and when the holding time is more than 20 minutes, the bubbles tend to expand and become coarse. Absent. In addition, heat transfer unevenness occurs depending on the thickness and size of the molded body, and an inhomogeneous inorganic foam is formed.Therefore, in order to prevent this, the molded body has a predetermined size depending on the size of the heating furnace. It is formed in thickness and size.

Particularly preferably, the temperature is set to (1) 600 to 750 ° C. and (2) 850 to 9 in a long tunnel type heating furnace.
50 ° C, (3) 950 to 1000 ° C, (4) 900 to 9
What is divided into a plurality of zones previously held at a temperature of 50 ° C., and the mixed powder is conveyed and heated and melted so as to pass through each zone in order for 5 to 20 minutes is used. Since the mixed powder is conveyed through the area that is held at a predetermined temperature in advance,
Excellent productivity with continuous production. Also, 600 to 75
Since it is preheated at 0 ° C and then heated to 850 ° C or higher,
The melting of the inorganic powder and the decomposition / foaming of the shell powder can be reliably performed, and the product yield can be increased. Further, after that, since the product is heated to 900 to 950 ° C., it is possible to prevent the product from being cracked, obtain the mechanical strength as designed, and improve the product yield.

The molten foam obtained in the heat-foaming step is cooled in a heating furnace, naturally cooled in air, or rapidly cooled with air, water or the like to obtain a long or lumpy inorganic foam. Are formed and, if desired, crushed or cut or cracked. The inorganic foam is, for example, as a civil engineering material used for embankment, backfilling, backfilling, etc., as a lightweight aggregate such as concrete and asphalt, a heat insulating material, a soundproofing material, etc. It can be mixed with soil and used as a soil modifier. In particular, when it is used as a heat insulating material for the underfloor of a house, an attic, a wall, etc., it is possible to reduce the weight of a house and the like, and since it has a large surface area, heat insulating property, dehumidifying property and the like are imparted. Further, since it contains calcium, magnesium, etc., and is porous and has a large surface area, it is suitable for use as a water purification treatment material because it exhibits excellent water quality improving performance. In addition, since it is porous, algae and grasses easily grow in water, which is suitable as a fishing reef. Moreover, since calcium, magnesium and the like are eluted from shell residue and the like to promote the growth of plants by utilizing their water retention and lightweight properties, they can also be used as lightweight soil materials for rooftop gardens and potted plants. In addition, the specific gravity of the inorganic foam can be easily controlled by the particle size of the shell powder, so that the specific gravity is set to less than 1 or almost 1 to float on the water surface or in water like floating islands and rafts. It can be used as a material. Further, it can be used as a water purification material that is formed to have a specific gravity of 1 or more and is stably landed on the bottom of lakes and marshes, the bottom of water tanks and vases, the shore of rivers, etc. to purify water. Incidentally, since the inorganic foam, since it is possible to mold a long inorganic foam that is hard to crack upon cooling after heating,
It can be used as a lightweight material to be embedded in a reinforced concrete floor slab, and as a result, it has excellent environmental protection and safety without causing problems such as waste treatment. At present, lightweight materials made of Styrofoam are mainly used, so when dismantled, it scatters, pollutes the surrounding environment and causes problems in waste disposal, etc., and also becomes a source of toxic gas in case of fire. Because.

The method for producing an inorganic foam according to claim 10 of the present invention comprises: a. Including 0 to 10 parts by weight of stone powder to 100 parts by weight of inorganic powder obtained by pulverizing an inorganic waste material, or b. A lamination step of laminating a high specific gravity powder layer containing the inorganic foam composition according to claim 4 and a low specific gravity powder layer containing the inorganic foam composition according to claim 5. The laminated product obtained in the laminating step is 750 to 110.
The high specific gravity powder layer and the low specific gravity powder layer are melted by heating to 0 ° C., preferably 900 to 1000 ° C. to form an inorganic base layer and a low specific gravity foam layer, respectively, and the inorganic base layer and the And a heating step of integrating the low specific gravity foam layer with each other. With this configuration, the following effects can be obtained. (1) Since the low specific gravity powder layer and the high specific gravity powder layer having different compositions are laminated in the laminating step and then melted and integrated in the heating step, the inorganic base layer having a specific gravity of 1 or more and the specific gravity of less than 1 An inorganic foam in which a low-density foam layer is integrated can be easily formed, and the productivity is excellent.

Here, as the laminating step, a. Including 0 to 10 parts by weight of stone powder to 100 parts by weight of inorganic powder obtained by pulverizing inorganic waste materials such as glassy waste materials, incinerated ash, brick waste materials, or b. A high specific gravity powder layer containing the inorganic foam composition according to claim 4 is spread in a mold made of stainless steel or is deposited on a mesh belt or a caterpillar made of stainless steel, and then, What laminated | stacks the low specific gravity powder layer containing the inorganic type foam composition of Claim 5 on a high specific gravity powder layer is used. As a result, in the heating step, the low specific gravity foam layer is pressure-bonded to the inorganic base layer by the weight of the low specific gravity powder layer to be integrated. A high specific gravity powder layer may be laminated on the low specific gravity powder layer. This is because, in the heating step, the high specific gravity powder layer is similarly pressed and integrated by its own weight.

As the stone powder added to the inorganic powder, a waste powder or the like obtained by crushing, cutting or cutting limestone or marble is used. In addition, shell powder can also be used. All of them can effectively utilize what has been conventionally discarded, can be recycled, and are excellent in resource saving. The stone powder is added in an amount of 0 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the inorganic powder in the high specific gravity powder layer. Inorganic powder 10
By adding 0.5 to 8 parts by weight of stone powder to 0 parts by weight, the waste powder obtained from limestone, marble, etc. is thermally decomposed to generate carbon dioxide gas and slightly foam the inorganic base layer. Thus, air bubbles can be formed and the surface area of the inorganic base layer can be increased to facilitate the attachment of algae and the fixing of microorganisms when immersed in water such as lakes and ponds. When the amount of stone powder added was less than 0.5 parts by weight, the inorganic base layer tended to be less likely to foam, and when it was more than 8 parts by weight, the inorganic powder was less likely to be melt-integrated and fragile. The strength tends to decrease. In particular,
If the addition amount is more than 10 parts by weight, this tendency is remarkable, which is not preferable.

In the heating step, the laminate obtained by laminating the high specific gravity powder layer and the low specific gravity powder layer is heated intermittently or continuously in a heating furnace such as a box furnace, a shuttle kiln, a roller hearth kiln, or a tunnel type. Then, the low-specific-gravity powder layer and the high-specific-gravity powder layer are melted to form the inorganic base layer and the low-specific gravity foam layer, and they are integrated at the boundary surface. The heating temperature in the heating step is the same as that described in the heating and foaming step of claim 7, and thus the description thereof is omitted. Further, as the inorganic waste material, the one described in claim 1 is used, and as the particle diameter of the inorganic powder obtained by crushing the inorganic waste material, the one described in claim 3 can be used, and therefore the description is omitted. To do.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below.
A description will be given with reference to the drawings. (Embodiment 1) FIG. 1 is a perspective view of an inorganic foam according to Embodiment 1 of the present invention. In FIG. 1, 1 is an inorganic foam according to the first embodiment, 1a is a substrate of an inorganic foam 1 formed by melting an inorganic powder obtained by pulverizing an inorganic waste such as a glass waste, and 1b. Is a shell residue, which is a residue formed by crushing shells such as oyster shells and decomposed by the shell powder added to the inorganic powder, and 1c is formed on the substrate 1a by foaming calcium carbonate in the shell powder. The bubbles are composed of open cells and closed cells. The main component of the shell powder is calcium carbonate, but since it does not thermally decompose because it also contains other compositions, the shell residue 1b is dispersed in the substrate 1a especially when the particle size of the shell powder is large. And then exist.

A method of manufacturing the inorganic foamed material according to the first embodiment having the above-described structure will be described below. First, an inorganic waste material such as a glassy waste material is crushed to form an inorganic powder having a particle size of 0.01 to 3000 μm. Separately from this, oyster shells and other shells are crushed to a particle size of 0.1.
Form shell powder formed to ~ 3000 μm. 1 to 25 parts by weight of shell powder is added and mixed with 100 parts by weight of the inorganic powder to prepare an inorganic foam composition. Next, in a mixing step, this inorganic foam composition is uniformly mixed to prepare a mixed powder. Next, in the heat-foaming step, the mixed powder thus prepared is filled in a mold made of stainless steel or the like, or is deposited on a mesh belt or a caterpillar made of stainless steel, or molded by a mold or the like. The formed body is heated to 750 to 1 in a tunnel type heating furnace.
It is heated intermittently or continuously at a temperature of 100 ° C. More preferably, the inside of the heating furnace is (1) 600 to 750 ° C.,
(2) 850 to 950 ° C, (3) 950 to 1000 ° C,
(4) The mixed powder is divided into a plurality of zones preliminarily held at a temperature of 900 to 950 ° C., and the mixed powder is conveyed so as to pass through each zone in order for 5 to 20 minutes to be continuously heated and melted. In the heating and foaming step, carbon dioxide gas generated by decomposition of the shell powder forms bubbles in the melted and softened inorganic powder.

As described above, since the inorganic foamed material according to the first embodiment is constructed, the following effects can be obtained. (1) Since wastes such as inorganic waste materials and shells are used, the wastes can be recycled and excellent in resource saving. (2) Since the shell has a low hardness and is easily crushed, shell powder can be easily obtained, and the load of the crushing equipment and the number of steps can be reduced. (3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide gas, and the molten inorganic powder is foamed to form bubbles, and the humic acid contained in the shell burns and burns out. Thus, an inorganic foam having fine pores and a large surface area can be stably obtained. (4) The shell has not only calcium ions but also magnesium ions, and these reduce the viscosity of the melt in which the inorganic powder is melted and reduce the residual strain generated during cooling, making it difficult to break during cooling. It is easy to form a long inorganic foam such as a plate and has excellent moldability. (5) Calcium oxide produced by decomposition of shell powder by heating absorbs water and carbon dioxide, so that an inorganic foam having excellent hygroscopicity can be produced. (6) Since calcium hydroxide produced by absorbing water with calcium oxide is easily eluted, an inorganic foam that can be used as a soil modifier can be produced. (7) When the inorganic foam formed by heating is immersed in water, calcium, magnesium and the like are eluted in water from the fractured surface of the inorganic foam and the shell residue. As a result, the phosphoric acid dissolved in water becomes calcium phosphate (insoluble) due to the eluted calcium, and the water quality can be improved, which is optimal as a water purification treatment material. Further, in addition to having a large surface area, the eluted magnesium can promote the growth of shellfish, algae, etc., and is optimal as a fishing reef. (8) Since the particle size of the inorganic powder is adjusted within a predetermined range, the melting temperature of the inorganic powder is stable and the size of the bubbles is also stable, so that the mechanical strength can be increased and the inorganic powder can be improved. Excellent stability of foam quality. (9) Since the particle size of shell powder is 0.1 to 3000 μm,
It is difficult to aggregate and can be dispersed so as to be scattered in the inorganic powder, and bubbles can be evenly distributed in the substrate so as to be scattered. As a result, it is possible to form independent cells having a relatively large diameter, and an inorganic foam having a specific gravity of more than 1 can be obtained. As a result, it can be used as a water purification material that purifies water quality by stably landing on the bottom of lakes and marshes, the bottom of tanks and vases, and the shores of rivers.

Here, in the present embodiment, the case where the shell powder has a particle size of 0.1 to 3000 μm has been described, but it can also be formed in the range of 0.1 to 1000 μm. As a result, the following effects are obtained. (1) The shell powder does not easily agglomerate and can be uniformly dispersed in the inorganic powder, and the bubbles can be uniformly distributed in the substrate by heating and melting and foaming. (2) As a result, it is possible to form a large number of independent cells and continuous cells in which they are connected, and it is possible to form an inorganic foam having a specific gravity of less than 1. As a result, it is possible to form floating islands and rafts that also float on the surface of water such as lakes and marshes, and also as water purification treatment materials.

The particle size of the shell powder is 0.01 to 50 μm.
m, preferably 0.1 to 10 μm. As a result, the following effects are obtained. (1) Since the density of the shell powder is small and the particle size is small, the number of particles is large, so the surface of the inorganic powder is sprinkled with the shell powder, and fine bubbles are evenly distributed in the substrate. It can be dispersed and formed. (2) As a result, it is possible to form continuous cells in which a large number of fine cells are connected, and it is possible to form an inorganic foam having a large surface area and a specific gravity of more than 1. This allows
It can be used as a water purification material that purifies water quality by steadily landing on the bottom of lakes, tanks, vases, etc., or on the shore of a river.

Further, according to the method for manufacturing an inorganic foamed body of the first embodiment configured as described above, the following effects can be obtained. (1) Since the mixed inorganic foam composition is heated in a predetermined temperature range to melt and foam, the inorganic powder is sufficiently softened to completely wrap the shell powder, and the shell powder is decomposed. The generated carbon dioxide gas can surely cause foaming and has excellent stability. (2) Since the shell powder is uniformly mixed, it acts as a melting aid to lower the melting temperature of the whole and prevent the generation of melting spots that are likely to be the starting point of breakage and stabilize the mechanical strength. Further, the specific gravity of the inorganic foam can be freely adjusted by simply changing the particle size of the shell powder, which is excellent in flexibility. (3) The heating temperature is 750 to 1100 ° C., preferably 900
Since the temperature is relatively low at up to 1000 ° C., the load on equipment such as a heating furnace is small, and energy saving is excellent. (4) The heating furnace is divided into a plurality of zones, and the mixed powder is conveyed so as to sequentially pass through each zone and continuously heated and melted, which enables continuous production and is excellent in productivity and inorganic It is possible to reliably perform melting of the powder of the system and decomposition / foaming of the powder of the shell, and it is possible to improve the product yield.

(Second Embodiment) FIG. 2 is a perspective view of an inorganic foam according to the second embodiment, and FIG. 3 is a second embodiment.
FIG. 3 is a schematic view of a main part of an apparatus for manufacturing an inorganic foam in FIG.
In FIG. 2, 1'indicates the inorganic foam according to the second embodiment, and 2 indicates the inorganic powder having a particle diameter of 0.01 to 3000 μm obtained by crushing the inorganic waste material such as glassy waste material by heating and melting. The inorganic base layer 3 is a particle size obtained by crushing an inorganic powder having a particle size of 0.01 to 3000 μm obtained by crushing an inorganic waste material such as a glassy waste material and a shell such as an oyster shell. 0.
Low specific gravity foam layer in which shell powder of 1 to 1000 μm is mixed, heated and melted to be integrated with the inorganic base layer 2, 3
a is a boundary surface between the inorganic base layer 2 and the low specific gravity foam layer 3. In FIG. 3, 4 is a long heating furnace such as a tunnel type, 5 is a mesh belt made of stainless steel or the like that moves in the heating furnace 4, 6 is a first hopper arranged on the mesh belt 5, and 6a is The high specific gravity powder layer is supplied from the first hopper 6 onto the mesh belt 5 with a predetermined thickness and deposited. The high specific gravity powder layer 6a is 0 to 10 parts by weight of stone powder such as cutting powder such as marble, preferably 0.5 to 100 parts by weight of inorganic powder obtained by crushing inorganic waste material such as glassy waste material. It contains 8 parts by weight. 7 is a second hopper disposed on the mesh belt 5 between the first hopper 6 and the heating furnace 4,
Reference character a is a low specific gravity powder layer which is deposited and laminated from the second hopper 7 on the high specific gravity powder layer 6a to a predetermined thickness. The low specific gravity powder layer 7a contains an inorganic foam composition in which the shell powder having a particle diameter of 0.1 to 1000 μm is added to the inorganic powder having a particle diameter of 0.01 to 3000 μm. It is a thing.

A method of manufacturing the inorganic foamed material according to the second embodiment having the above-described structure will be described below. First, an inorganic waste material such as a glassy waste material is crushed to form an inorganic powder having a particle size of 0.01 to 3000 μm. Stone powder 0-10 for 100 parts by weight of this inorganic powder
One part by weight, preferably 0.5 to 8 parts by weight is added and mixed and stored in the first hopper 6. Further, an inorganic waste material such as a glassy waste material is crushed to form an inorganic powder having a particle diameter of 0.01 to 3000 μm. Further, a shell such as an oyster shell is crushed to form a shell powder having a particle size of 0.1 to 1000 μm. A mixture of 1 to 25 parts by weight of shell powder to 100 parts by weight of this inorganic powder is stored in the second hopper 7. In the laminating step, inorganic powder or the like is deposited on the mesh belt 5 from the first hopper 6 to form the high specific gravity powder layer 6a. Then, an inorganic powder or the like is deposited from the second hopper 7 on the high specific gravity powder layer 6a to form the low specific gravity powder layer 7a.
a is laminated. Next, in the heating step, the laminate obtained by laminating the high specific gravity powder layer 6a and the low specific gravity powder layer 7a is heated in the heating furnace 4 at 750 to 1100 ° C, preferably 900 to 1000 ° C.
Heat to. As a result, the high specific gravity powder layer 6a is melted to form the inorganic base layer 2, the low specific gravity powder layer 7a is melted to form the low specific gravity foam layer 3, and the low specific gravity foam layer 3 is self-weighted. Then, the low specific gravity foam layer 3 and the inorganic base layer 2 are integrated by pressure bonding to the inorganic base layer 2.

As described above, since the inorganic foamed material according to the second embodiment is constituted, the following effects can be obtained. (1) Since it has the inorganic base layer integrated with the low specific gravity foam layer, it can reinforce the low specific gravity foam layer having relatively low mechanical strength and enhance the mechanical strength. Excellent durability. (2) Since the specific gravity of the inorganic base layer is higher than that of the low specific gravity foam layer, the inorganic base layer is formed to have a specific gravity of 1 or more so that the inorganic foam is submerged in water such as a lake, a swamp, or the sea. In that case, the inorganic base layer can be placed on the lake bottom or the like with the low specific gravity foam layer facing upward. For this reason, the water flow is likely to hit the low specific gravity foam layer with a large surface area, and algae and microbial groups are easily attached to the low specific gravity foam layer, and decomposition of organic substances and water in the low specific gravity foam layer are performed. Purification can be efficiently performed. (3) When it is dropped into water such as lakes and marshes, it is settled and settled with the inorganic base layer having a high specific gravity facing down, and it has excellent emplacement properties in water, and it is stably fixed at the bottom of lakes and marshes and purified. You can

Further, according to the method for manufacturing an inorganic foam in the second embodiment, the following effects can be obtained. (1) Since the low specific gravity powder layer and the high specific gravity powder layer having different compositions are laminated in the laminating step and then melted and integrated in the heating step, the inorganic base layer having a specific gravity of 1 or more and the specific gravity of less than 1 An inorganic foam in which a low-density foam layer is integrated can be easily formed, and the productivity is excellent. (2) By controlling the thicknesses of the high specific gravity powder layer and the low specific gravity powder layer, the volume ratio of the inorganic base layer and the low specific gravity foam layer can be easily adjusted. As a result, the inorganic foam can be produced so that the overall specific gravity becomes 1 or more, and when the inorganic foam is dropped into water such as lakes and marshes, the inorganic substrate layer faces downward and settles to the bottom of lakes and marshes. It is possible to produce an inorganic foam that is stably fixed.

In this embodiment, the case of using the high specific gravity powder layer in which the inorganic powder and the stone powder are mixed has been described, but the inorganic powder formed to have a particle diameter of 0.01 to 3000 μm is used. It is also possible to use a high specific gravity powder layer containing an inorganic foam composition to which is added a shell powder having a particle size of 0.1 to 3000 μm. As a result, the specific gravity is 1
It is possible to obtain an inorganic base layer containing a larger amount of shell residue. Since this inorganic base layer dissolves calcium and magnesium when immersed in water, it is optimal as a water purification treatment material and a fishing reef.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. (Example 1) A glassy waste material such as a glass bottle and a window glass as an inorganic waste material was roughly crushed to an average particle diameter of 2 to 3 mm by using a crusher such as an edge runner. Then, it was finely pulverized using a pulverizer such as an Elofol mill. Next, the particles were classified by a classifier using a 20-mesh standard sieve (opening 850 μm) to obtain an inorganic powder having a particle size of 850 μm or less. Next, shells such as oysters, scallops and red shells were washed with water and dried, and then coarsely crushed to an average particle size of 2 to 3 mm using a crusher such as an edge runner. Then, it was finely pulverized using a pulverizer such as an Elofol mill. Next, classification was performed by a classifier using a 16-mesh standard sieve (opening 1000 μm) to obtain a shell powder having a particle size of 1000 μm or less. In the mixing step, 100 parts by weight of the inorganic powder and the shell powder 12 were added to the pulverized and classified inorganic foam composition.
Part by weight was sufficiently mixed with a mixer such as a stirrer to obtain a mixed powder. In the heating and foaming step, a tunnel type heating furnace in which a mesh belt made of stainless steel or the like and having a width of 1.5 m is stretched over a length of 25 m was used. The obtained mixed powder is approximately 14 mm thick and 1.0 m wide on the mesh belt, and 1.2 m along the longitudinal direction of the mesh belt.
Deposited to length. The mesh belt is in the first zone 60
0 to 750 ° C, second zone 850 ° C, third zone 940
The mixed powder that has been set to pass through each zone within 5 to 10 minutes in the heating furnace maintained at ℃, 4th zone 960 ° C, and 5th and 6th zone 940 ° C. The body is melt-foamed over 30 to 60 minutes and the thickness is about 45 m.
m, a width of about 1.0 m, and a length of about 1.2 m were obtained as a plate-shaped inorganic foam of Example 1. When the specific gravity of the inorganic foam of Example 1 was measured, it was 0.6. It was confirmed that this inorganic foam floats on water. Observing the fracture surface,
It was confirmed that bubbles having an inner diameter of 0.3 to 2 mm were uniformly distributed.

(Example 2) In order to produce the inorganic foam of Example 1, shells such as oysters, scallops and red shells were finely pulverized using a pulverizer such as an elofol mill. A shell powder having a particle size of 0.01 to 50 μm collected by a filter dust collector such as a filter or an air filter was prepared. Inorganic foaming of Example 2 was performed in the same manner as in Example 1 except that 11 parts by weight of this shell powder was added and mixed with 100 parts by weight of the inorganic powder obtained in the same manner as in Example 1. Got the body When the specific gravity of the inorganic foam of Example 2 was measured, it was 1.1. It was confirmed that this would sink when immersed in water. When the fracture surface was observed, the inner diameter was 0.
It was confirmed that bubbles of 2 to 1 mm were uniformly distributed.

(Comparative Example 1) Silicon carbide (average particle size 3.9 μm, product name C-4000F, manufactured by Yakushima Electric Works) was added to 4 parts by weight of 100 parts by weight of the inorganic powder obtained in the same manner as in Example 1. In the same manner as in Example 1 except that parts by weight were added and mixed,
The inorganic foam of Comparative Example 1 was obtained. When the specific gravity of the inorganic foam of Comparative Example 1 was measured, it was 0.4.

(Dissolution Test) The results of evaluating the amount of harmful substances eluted when the inorganic foams of Examples 1 and 2 were immersed in water are shown in (Table 1).

[Table 1] In the measurement method shown in (Table 1), the one labeled "JK0102" is an abbreviation for "JIS K 0102", and the one labeled "S49 Notification" is "Showa 4".
It is an abbreviation for "Environment Agency Notification of 9 years", and what is displayed as "S46 Announcement" is an abbreviation of "Notice of Environment Agency 1969".
As a result, it was revealed that no harmful substance was eluted in the inorganic foam of this example.

(Evaluation as Water Purification Material) Examples 1 and 2
Also, the inorganic foam of Comparative Example 1 was used for evaluation as a water purification treatment material. FIG. 4 is a schematic diagram of an evaluation test device for a water purification treatment material. In FIG. 4, 10 is a water purification treatment material evaluation test device, 11 is a column having a capacity of 100 ml, 12 is a cube having a side of about 1 cm, which is cut or crushed and packed in the column 11 of Examples 1 and 2 and the like. The sample is an inorganic foam, 13 is a beaker with a capacity of about 1 L, 14 is 0.4 m
About 1 L of an aqueous solution containing g / L of ammonia nitrogen and 0.2 mg / L of phosphoric acid phosphate injected into the beaker 13, 15 is connected to the downstream side of the column 11 and the beaker 13 and passes through the column 11. The liquid circulation path for supplying the prepared aqueous solution 14 to the beaker 13, 16 is a liquid circulation path connected to the upstream side of the beaker 13 and the column 11 for supplying the aqueous solution 14 in the beaker 13 to the column 11, and 17 is the liquid circulation path 16. A pump such as a roller tube pump that is provided and circulates the aqueous solution 14. In this evaluation test, the inorganic foam 12 having a substantially same volume filled in the column 11 having a capacity of 100 ml is used.
The water purification performance was evaluated. The inorganic foam 12 was cut or crushed into a substantially cubic shape with one side of about 1 cm, and then naturally dried in a room at room temperature for 10 days, and the inorganic foam 12 was filled in the column 11. The filling amount of the inorganic foam of Example 1 was 25.5 g, the inorganic foam of Example 2 was 50.2 g, and the inorganic foam of Comparative Example 1 was 20.1 g.
Met. Further, the pump 17 was adjusted so that the flow rate of the aqueous solution 14 passing through the column 11 was 200 ml / h. In addition, the reason why the amount of ammonia nitrogen is 0.4 mg / L and the amount of phosphate phosphorus is 0.2 mg / L is because a river having a considerably large pollution load is assumed. In addition, in the case of the inorganic foam of Comparative Example 1, when packed in a column, the parts rubbed against each other were relatively easily broken, and many powdered substances were generated. On the other hand, no such phenomenon was observed in the inorganic foams of Examples 1 and 2. This indicates that the inorganic foams of Examples 1 and 2 are excellent in mechanical strength.

Evaluation test apparatus 10 configured as described above
After starting the experiment by driving the pump 17 using
The aqueous solution 14 after 1, 3, 5, 12, 24, and 48 hours was collected from the beaker 13, and ammonia nitrogen and phosphoric acid phosphorus were measured for the collected aqueous solution. The results are shown in FIGS. 5 and 6. FIG. 5 is a diagram showing the relationship between the elapsed time from the start of the experiment and the specific concentration of ammoniacal nitrogen, and FIG. 6 is a diagram showing the relationship between the elapsed time from the start of the experiment and the specific concentration of phosphate phosphorus. . Here, the specific concentration indicates the ratio with respect to the concentration of ammonia nitrogen etc. at each elapsed time when the concentration of ammonia nitrogen etc. before the start of the experiment (elapsed time 0) is set to 1.

As shown in FIG. 5, the inorganic foams of Example 1 and Example 2 using the shell powder were about 4 from the start of the test.
The specific concentration of ammoniacal nitrogen could be reduced to a low concentration of 0.2 or less in 8 hours. From this, with respect to ammonia nitrogen, the inorganic foams of Examples 1 and 2 using the shell powder have substantially the same water quality improving effect as the inorganic foam of Comparative Example 1 using silicon carbide. It became clear to show.

Next, as for phosphoric acid phosphate, as shown in FIG. 6, the inorganic foam of Example 1 was used from the start of the experiment to 48%.
The specific concentration could be reduced to 0.4 or less in time. on the other hand,
In the inorganic foam of Comparative Example 1, the specific concentration was about 0.7 within 48 hours from the start of the experiment. Therefore, the inorganic foam of Example 1 was remarkably excellent in the effect of removing phosphate phosphorus. It became clear that there is. This means that phosphate-phosphorus becomes calcium phosphate (insoluble) by elution of calcium and magnesium contained in the shell from the fracture surface of the inorganic foam, or the calcium-containing shell contains phosphate in water. It is presumed that calcium phosphate is formed by the adsorption of activated phosphorus to improve the water quality. The ability of the inorganic foam of Example 1 to remove phosphate phosphorus is higher than that of the inorganic foam of Example 2 because the particle size of the shell powder used in the inorganic foam of Example 1 is This is because the shell residue (calcium content) is dispersed and present in a large amount in the substrate because it is as large as 0.1 to 1000 μm, and phosphate phosphate in water is removed by converting it to calcium phosphate. I'm guessing. As described above, according to the present embodiment, the purification effect is excellent in the effect of removing ammoniacal nitrogen and phosphorous phosphate, and no elution of harmful substances is observed, and the mechanical strength is high and the water is less likely to be collapsed by external force such as water flow. It was clarified that the optimum inorganic foam as a material can be obtained.

(Evaluation as a water purification treatment material using a breeding water tank) Next, an organism was actually bred in the breeding water tank and evaluated as a water purification treatment material. FIG. 7 is a schematic diagram showing a test device using a breeding aquarium. In the figure, 20 is a test device using a breeding aquarium, 21 is 90 cm in length, 40 cm in width, and 60 in height.
cm is a rectangular parallelepiped breeding water tank, 22 is an inorganic foam (water purification treatment material) in which the inorganic foam of Example 1 is crushed to an average particle size of 40 mm and laid at the bottom of the breeding water tank 21 to a thickness of about 10 cm. Water treatment material layer consisting of, 23 is water treatment material layer 2
2 is a wire mesh, 24 is a partition plate having water permeability such as a wire mesh or a mesh that is erected on the wire mesh 23, and 25 is a partition body 24 made of glass particles having an average particle diameter of 2 mm. A glass particle layer laid with a thickness of about 7 cm on a partitioned wire net 23, and 26 is a glass particle layer 2 partitioned by a partition body 24.
Adjacent to No. 5, on the wire net 23 on the red ball clay (average particle size 3 mm)
And Kanuma soil (average particle size 3 mm) and the above inorganic foam (crushed to an average particle size 3 mm) in a volume ratio of 4:
A soil particle portion mixed with 4: 2 and deposited to a thickness higher than the laying thickness of the glass particle layer 25, 27 is an underwater pump arranged in the water purification treatment material layer 22, 28 is a wire mesh connected to the underwater pump 27.
3, a water injection pipe that penetrates through the soil particle portion 26 and injects the water sucked up from the submersible pump 27 from above the glass particle layer 25, 29 is tap water that has been pumped all day and night to remove chlorine, and then a breeding aquarium It is about 50 L of water stored in 21.
The submersible pump 27 circulates the water 29 stored in the breeding aquarium 21 at a flow rate of 10 L / min.
L / min of air is supplied into the water purification treatment material layer 22 and the glass particle layer 25.

The fireflies were bred with the test apparatus using the breeding aquarium constructed as described above. In the beginning of September, about 50 L of the pumped water was stored in the breeding aquarium, and the submersible pump was driven to circulate the water for about 5 days. Then, 30 larvae of fireflies and 60 kawarinas were fed in the glass grain layer. And the apple skin was placed on the surface of the glass grain layer as bait for the kawana.
The larvae of fireflies grew while eating Kawana in the glass grain layer and repeatedly molt, landed in the soil grain part in March of the following year, pupated, and emerged in June to become adults. During this period, water was simply replenished and the apple skin, which was the food for the kawana, was replaced, and maintenance such as water replacement and cleaning of the breeding aquarium was completely unnecessary. This is because generation of phytoplankton, water-bloom, etc., and floating substances such as food slag were not observed on the inner surface of the breeding aquarium or in the water, and the breeding aquarium and water were not contaminated at all. This is because since the inorganic foam is a porous body, it is possible to supplement and remove suspended solids such as food slags, and it is easy for microbial groups to easily settle on the surface of the inorganic foam, which may be harmful to the microbial groups that have settled. It is speculated that this is because the nitrification of ammonia into nitrate and the anti-nitrification of nitrate into nitrogen gas were performed, and the concentrations of ammonia and nitrate in water could be kept low. In addition, since the inorganic foam is foamed using shell powder and has a calcium component, etc., it can be removed from water by adsorbing water-soluble nitrogen, phosphorus, etc. It is presumed that it was possible to prevent the growth of phytoplankton and water-bloom, etc., which feed on sorghum, and to prevent the deterioration of water quality. In addition, since the inorganic foam is foamed using shell powder and has calcium and magnesium components, etc., these useful minerals are dissolved in water and promote the growth of shellfish such as kawaina. I guess it was made. As described above, according to the present example, even when the organism is actually bred, suspended solids in water, water-soluble nitrogen and phosphorus, etc. can be removed, and a water purification material having excellent water purification performance can be obtained. It became clear.

Example 3 To 100 parts by weight of an inorganic powder having a particle size of 850 μm or less formed in the same manner as in Example 1, 11 parts by weight of a shell powder having a particle size of 3000 μm or less was added and mixed. A mixed powder was prepared and deposited on a mesh belt in a thickness of about 14 mm. Then, it was heated and melt-foamed in a heating furnace set in the same manner as in Example 1 to obtain an inorganic foam of Example 3. When the specific gravity of the inorganic foam of Example 3 was measured, it was 1.1. It was confirmed that this would sink when immersed in water. Observation of the fracture surface confirmed that air bubbles having an inner diameter of 0.2 to 3 mm were distributed.

(Example 4) 100 parts by weight of an inorganic powder having a particle size of 850 μm or less formed in the same manner as in Example 1 such as a cutting powder of marble or the like having a particle size of 0.1 to 20 μm 4 parts by weight of stone powder was added and mixed, and the mixture was deposited on a mesh belt to form a high specific gravity powder layer having a thickness of about 7 mm. Next, a mixed powder was prepared in the same manner as in Example 1, and a low specific gravity powder layer having a thickness of about 7 mm was laminated on the high specific gravity powder layer deposited on the mesh belt. (Lamination Step) Next, in the heating step, the high specific gravity powder layer and the low specific gravity powder layer are melted by using the heating furnace set up in the same manner as the heating and foaming step described in Example 1 to melt the inorganic base layer. The low specific gravity foam layer integrated with the above is formed, and the thickness of the inorganic base layer is about 10 m.
m, low specific gravity foam layer thickness of about 30 mm, width of about 1.0 m,
A plate-like inorganic foam of Example 4 having a length of about 1.2 m was obtained. The obtained inorganic foam was crushed so that the length and width became about 10 cm, and it was dropped into a water tank having a depth of about 2 m. Then, it was allowed to settle in the water, and the low specific gravity foam layer faced upward, and the inorganic base layer landed on the bottom of the water tank. As described above, according to this example, since the inorganic base layer can be stably landed on the bottom of the lake with the low-specific-gravity foam layer facing upward, the low-specific-gravity foam layer having a large surface area is easily exposed to the water flow. As a result, algae adhere to the low-density foam layer and microbial groups easily settle in it, and the low-density foam layer can efficiently decompose organic substances and purify water. It has been revealed that an optimum inorganic foam can be obtained.

The same evaluation was performed by changing the contents and particle sizes of the inorganic powder and the shell powder within a predetermined range. It was confirmed that the water can be formed in the same manner and is excellent in water purification.

[0065]

As described above, according to the inorganic foam composition, the inorganic foam and the method for producing the inorganic foam of the present invention, the following advantageous effects can be obtained. Claim 1
According to the invention described in (1), since wastes such as inorganic waste materials and shells are used, it is possible to recycle the wastes and provide an inorganic foam composition excellent in resource saving. can do. (2) Since the shell has a low hardness and is easy to be crushed, a shell powder can be easily obtained, and an inorganic foam composition can be provided which can reduce the load on the crushing equipment and the number of steps. (3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide gas, and the molten inorganic powder is foamed to form bubbles, and the humic acid contained in the shell burns and burns out. Thus, it is possible to provide an inorganic foam composition in which fine pores are formed and an inorganic foam having a large surface area can be stably obtained. (4) Depending on the type of shell, it has a fibrous material such as red shell and the like, and the fibrous material is positioned around the bubbles formed by melting and foaming at a predetermined melting temperature to function as a reinforcing agent. An inorganic foam composition that prevents bursting can be provided. (5) The shell has not only calcium ions but also magnesium ions, and these reduce the viscosity of the melt in which the inorganic powder is melted and reduce the residual strain generated during cooling, which makes it difficult to break during cooling. It is possible to provide an inorganic foam composition that is easy to form a long inorganic foam such as a plate and has excellent moldability. (6) An inorganic foam composition capable of producing an inorganic foam excellent in hygroscopicity and the like because calcium oxide produced by decomposition of shell powder by heating absorbs water and carbon dioxide. Can be provided. (7) Provided is an inorganic foam composition capable of producing an inorganic foam that can be used as a soil modifier, since calcium hydroxide produced by absorbing water by calcium oxide is easily eluted. can do. (8) When the inorganic foam formed by heating is immersed in water as a water purification treatment material or the like, calcium, magnesium, etc. are eluted into water from the fractured surface of the inorganic foam and the shell residue. As a result, the phosphoric acid dissolved in water reacts with the eluted calcium or is adsorbed by the calcium component in the inorganic foam to become calcium phosphate (insoluble), which can improve the water quality. Further, it is possible to provide an inorganic foam composition in which eluted magnesium can promote the growth of shellfish, algae and the like.

According to the invention described in claim 2, claim 1
In addition to the effects of (1), a certain amount of shell powder is blended, so when heated to melt the inorganic powder, an optimum amount of carbon dioxide gas is generated to form bubbles, and the inorganic foam has a large expansion ratio. It is possible to provide an inorganic foam composition from which a body is obtained. (2) Since the density of the shell powder is small, the capacity is large, and it is possible to provide an inorganic foam composition that can be uniformly mixed with the inorganic powder.

According to the invention of claim 3, claim 1
In addition to the effect of (2), (1) Since the particle size of the inorganic powder is adjusted within a predetermined range, the melting temperature of the inorganic powder is stable, the size of the bubbles is also stable, and the particle size distribution of the bubbles is stable. It is possible to provide an inorganic foam composition which is small in size, has high mechanical strength, and is excellent in stability of quality of the inorganic foam.

According to the invention of claim 4, claim 1
In addition to the effect of any one of 3 to 3, (1) since the particle size of the shell powder is 0.1 to 3000 μm,
Provided is an inorganic foam composition which is hard to aggregate and can be dispersed so as to be scattered in an inorganic powder, and can be uniformly distributed so as to be scattered by being heated and melt-foamed. be able to. (2) As a result, it is possible to form independent bubbles having a relatively large diameter, and it is possible to form an inorganic foam having a specific gravity of more than 1. Thereby, it is possible to provide an inorganic foam composition capable of producing an inorganic foam that can be used as a water purification treatment material that purifies water quality by stably landing on the bottom of a lake or the like or the bottom of an aquarium or a vase. You can

According to the invention of claim 5, claim 1
In addition to the effect of any one of 1 to 3, (1) the particle size of the shell powder is 0.1 to 1000 μm, which is almost the same as the particle size of the inorganic powder, so that it should be dispersed uniformly in the inorganic powder. It is possible to provide an inorganic foam composition capable of uniformly distributing cells by heating and melting and foaming. (2) As a result, since the particles of the shell powder are small and uniformly dispersed, it is possible to form a large number of independent bubbles and continuous bubbles formed by connecting them, and an inorganic foam having a specific gravity of less than 1. Can form a body. This allows
It is possible to provide an inorganic foam composition capable of producing an inorganic foam that can be used as a floating island having water purification performance that floats on the surface of water such as lakes and marshes, or as a water purification treatment material. (3) Since the particle size of the bubbles can be made small,
When used as a water purification treatment material, it is possible to provide an inorganic foam composition capable of capturing floating substances in water and producing an inorganic foam excellent in water purification performance.

According to the invention of claim 6, claim 1
In addition to any one of effects 1 to 3, (1) the density of the shell powder is small and the particle size is small, so that the number of particles is large and the surface of the inorganic powder is sprinkled with the shell powder. In addition, it is possible to provide an inorganic foam composition capable of uniformly forming fine bubbles. (2) As a result, it is possible to form continuous cells in which a large number of fine cells are connected, and it is possible to form an inorganic foam having a large surface area and a specific gravity of more than 1. This allows
Provide an inorganic foam composition capable of producing an inorganic foam that can be used as a water purification treatment material that purifies water quality by stably landing on the bottom of lakes, tanks, vases, etc. can do.

According to the invention of claim 7, claim 1
In addition to the effect of any one of 1 to 6, (1) since many glassy waste materials are softened at a low temperature of 1000 ° C. or less, the load of equipment such as a heating furnace is small, and the viscosity of the melt is high, so Is easily formed, the specific gravity can be easily controlled, and the mechanical strength is high and the durability is excellent. Further, it is possible to provide an inorganic foam composition which is easy to form a long inorganic foam such as a plate and has excellent moldability. (2) After the glassy waste material is melted and solidified, cadmium,
Since no harmful substances such as cyanide are eluted, it is possible to provide an inorganic foam composition capable of obtaining an optimum inorganic foam as a water purification treatment material for rivers and lakes.

According to the eighth aspect of the present invention, (1) the low specific gravity foam layer has relatively low mechanical strength because it has the inorganic base layer integrated with the low specific gravity foam layer. It is possible to provide an inorganic foam that can be reinforced with high mechanical strength and excellent durability. (2) Since the specific gravity of the inorganic base layer is higher than that of the low specific gravity foam layer, the inorganic base layer is formed to have a specific gravity of 1 or more so that the inorganic foam is submerged in water such as a lake, a swamp, or the sea. In that case, the inorganic base layer can be placed on the lake bottom or the like with the low specific gravity foam layer facing upward. Therefore, it becomes easy for the water flow to hit the low specific gravity foam layer having a large surface area, and algae easily adhere to the low specific gravity foam layer or microbial groups are easily fixed,
It is possible to provide an inorganic foam capable of efficiently decomposing organic substances and purifying water in a low specific gravity foam layer. (3) When it is dropped into water such as lakes and marshes, it is settled and settled with the inorganic base layer having a high specific gravity facing down, and it has excellent emplacement properties in water, and it is stably fixed at the bottom of lakes and marshes and purified. It is possible to provide an inorganic foam capable of

According to the invention of claim 9, (1) the mixed inorganic foam composition is heated in a predetermined temperature range to melt and foam, so that the inorganic powder is sufficiently softened. It is possible to provide a method for producing an inorganic foam which is capable of completely enclosing the shell powder and surely foaming it with carbon dioxide gas generated by the decomposition of the shell powder and having excellent stability. (2) Since the shell powder is uniformly mixed, it acts as a melting aid to lower the melting temperature of the whole, and to prevent the occurrence of melting spots, which easily become the starting point of fracture, and to stabilize the mechanical strength of the inorganic foam. A manufacturing method can be provided. (3) The heating temperature is 750 to 1100 ° C., preferably 900
Since the temperature is relatively low at ˜1000 ° C., it is possible to provide a method for producing an inorganic foam that has a small facility load such as a heating furnace and is excellent in energy saving.

According to the invention described in claim 10, (1) since the low specific gravity powder layer and the high specific gravity powder layer having different compositions are laminated in the laminating step and then melted and integrated in the heating step, Provided is a method for producing an inorganic foam having excellent productivity, which can easily form an inorganic foam in which an inorganic base layer having a specific gravity of 1 or more and a low specific gravity foam layer having a specific gravity of less than 1 are integrated. can do.

[0075]

[Brief description of drawings]

FIG. 1 is a perspective view of an inorganic foam according to the first embodiment.

FIG. 2 is a perspective view of an inorganic foam according to the second embodiment.

FIG. 3 is a schematic diagram of a main part of an apparatus for manufacturing an inorganic foam according to a second embodiment.

FIG. 4 is a schematic diagram of an evaluation test apparatus for water purification treatment materials.

FIG. 5 is a diagram showing the relationship between the elapsed time from the start of the experiment and the specific concentration of ammoniacal nitrogen.

FIG. 6 is a diagram showing the relationship between the elapsed time from the start of the experiment and the specific concentration of phosphate phosphorus.

FIG. 7 is a schematic diagram showing a test device using a breeding aquarium.

[Explanation of symbols]

1,1 'Inorganic foam 1a base 1b Shell residue 1c bubbles 2 Inorganic base layer 3 Low specific gravity foam layer 3a boundary surface 4 heating furnace 5 mesh belt 6 First hopper 6a High specific gravity powder layer 7 Second hopper 7a Low specific gravity powder layer 10 Evaluation equipment for water purification treatment 11 columns 12 Inorganic foam 13 beakers 14 Aqueous solution 15, 16 Liquid circulation path 17 pumps 20 test equipment 21 Breeding aquarium 22 Water treatment layer 23 wire mesh 24 partition boards 25 glass grain layer 26 soil particles 27 Submersible Pump 28 Water injection pipe 29 water

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiki Yamane             200-2 Miyaya, Gunya-cho, Yazu-gun, Tottori Prefecture             Construction Co., Ltd. (72) Inventor Shiro Hisatomi             1-3-1-21 Tokiwadai, Ube City, Yamaguchi Prefecture (72) Inventor Hiroaki Watanabe             Equity prefecture Niihama city Kubotacho 3-9-20 shares             Within the company Eco City (72) Inventor Naoki Mori             25, Engyoji Temple, Kochi City, Kochi Prefecture             Within F-term (reference) 4D004 AA04 AA16 AA18 AA36 BA02                       BA10 CA04 CA08 CA14 CA15                       CA29 CB01 CB13 DA03 DA06                 4D038 AA02 AB29 AB31 AB45 AB48

Claims (10)

[Claims] 1. An inorganic foam composition comprising an inorganic powder obtained by crushing an inorganic waste material and a shell powder obtained by crushing a shell. 2. The shell powder is contained in an amount of 1 to 25 parts by weight, preferably 8 to 20 parts by weight, more preferably 10 to 15 parts by weight, based on 100 parts by weight of the inorganic powder. Item 2. The inorganic foam composition according to item 1. 3. The particle size of the inorganic powder is 0.01 to 3
The inorganic foam composition according to claim 1 or 2, which has a thickness of 000 µm, preferably 0.1 to 1000 µm, and more preferably 0.5 to 500 µm. 4. The particle size of the shell powder is 0.1 to 300.
It is 0 micrometer, The inorganic type foam composition of any one of Claim 1 thru | or 3 characterized by the above-mentioned. 5. The shell powder has a particle size of 0.1 to 100.
It is 0 micrometer, The inorganic type foam composition of any one of Claim 1 thru | or 3 characterized by the above-mentioned. 6. The particle size of the shell powder is 0.01 to 50.
The inorganic foam composition according to any one of claims 1 to 3, wherein the thickness is preferably 0.1 to 10 µm. 7. The inorganic foam composition according to claim 1, wherein the inorganic waste material contains a glassy waste material. 8. An inorganic substrate layer obtained by heating and melting an inorganic powder obtained by pulverizing an inorganic waste material, and the inorganic powder and shell powder obtained by pulverizing the inorganic waste material. And a low specific gravity foam layer having a specific gravity smaller than that of the inorganic base layer, which is integrated with the inorganic base layer by heating. 9. A mixing step of mixing the inorganic foam composition according to any one of claims 1 to 7, and a mixed powder obtained in the mixing step at 750 to 1100 ° C., preferably 900. And a heating and foaming step of melting and foaming by heating to 1000 ° C, the method for producing an inorganic foam. 10. A. Including 0 to 10 parts by weight of stone powder to 100 parts by weight of inorganic powder obtained by pulverizing an inorganic waste material, or b. A lamination step of laminating a high specific gravity powder layer containing the inorganic foam composition according to claim 4 and a low specific gravity powder layer containing the inorganic foam composition according to claim 5. The laminated product obtained in the laminating step is heated to 750 to 1100 ° C., preferably 900 to 1000 ° C. to melt the high specific gravity powder layer and the low specific gravity powder layer to form an inorganic base layer and a low specific gravity foam, respectively. A heating step of forming a body layer and integrating the inorganic base layer and the low specific gravity foam layer with each other;