JP3898116B2 - Inorganic foam and method for producing inorganic foam - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention is a glassy waste material.TheUsingInorganic foams andThe present invention relates to a method for producing an inorganic foam.
[0002]
[Prior art]
  Conventionally, in order to recycle glassy waste, coal ash, etc., which is a kind of inorganic waste, uniform, independent or continuous bubbles in glassy matrix using glassy waste, coal ash, etc. A vitreous foam having excellent heat insulation and soundproofing, a lightweight artificial bone, and the like have been developed.
  For example, (Patent Document 1) discloses “a method for producing foam glass in which a raw material obtained by mixing limestone powder into crushed bottle glass or the like is granulated and then heated at 810 to 960 ° C.”.
[0003]
  (Patent Document 2) states that “an artificial lightweight aggregate in which waste glass, a binder, and a foaming agent such as iron oxide, silicon carbide, and charcoal are mixed and pulverized and then fired. Manufacturing method "is disclosed.
[0004]
  (Patent Document 3) “Waste glass is crushed and formed into powder, and at least one metal carbonate such as sodium carbonate, metal carbide such as silicon carbide, and metal nitride such as silicon nitride is added thereto. And a method for producing a heated glass foam ".
[0005]
  (Patent Document 4) discloses “a method for producing a glassy foam in which coarsely pulverized glass powder and finely pulverized glass powder are mixed, and silicon carbide is added thereto and heated.”
[0006]
[Patent Document 1]
  JP 58-60634 A
[Patent Document 2]
  JP 11-335146 A
[Patent Document 3]
  JP-A-11-343128
[Patent Document 4]
  JP-A-11-236232
[0007]
[Problems to be solved by the invention]
  However, the above conventional techniques have the following problems.
(1) The technology disclosed in (Patent Document 3) does not specify the particle size of powdered waste glass or foaming agent, so depending on the particle size of waste glass or the like even if the conditions for heating the raw material are constant. The melted state, the foamed state, and the like are different, and the specific gravity, the size of bubbles, and the like are not stable, and the quality is not stable.
(2) The technologies disclosed in (Patent Document 1) to (Patent Document 4) use glass wastes as raw material glass, but as a foaming agent, natural resources such as limestone and chemicals such as silicon carbide Because of the use of, there was a problem of lack of resource saving.
[0008]
  SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and can recycle waste and can stably obtain an inorganic foam having a desired specific gravity, and is excellent in water quality improving action. The purpose is to provide a body.
  Another object of the present invention is to provide an inorganic foam having excellent landing properties, with layers having different specific gravities stacked and integrated, and when dropped in water such as lakes and marshes, settles down and lands with the high specific gravity layer down. To do.
  Another object of the present invention is to provide a method for producing an inorganic foam that is excellent in energy saving and has a small equipment load such as a heating furnace, and more reliably foams to form bubbles and has a high product yield. .
[0009]
[Means for Solving the Problems]
  In order to solve the above conventional problems, the present inventionInorganic foams andThe manufacturing method of the inorganic foam has the following configuration.
[0010]
  The inorganic foam according to claim 1 of the present invention includes 100 parts by weight of an inorganic powder obtained by pulverizing a glassy waste material, and shell powders 1 to 1 obtained by pulverizing a shell.15And an inorganic foam composition containing parts by weightThe calcium carbonate contained in the shell is decomposed to generate carbon dioxide.MeltingThe inorganic powderFoamLet bubbles formAnd cooledThe shell residue containing calcium and magnesium is dispersedIt has a structure made of a molten foam having a plate shape, a block shape, or a long shape.
  With this configuration, the following effects can be obtained.
(1) Since wastes such as glassy waste and shells are used, it is possible to recycle the waste and it is excellent in resource saving.
(2) Since the shell is low in hardness and easily pulverized, shell powder can be easily obtained, and the load on the pulverization equipment, the number of man-hours, etc. can be reduced.
(3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide and foam the molten inorganic powder to form bubbles, and the humic acid contained in the shell burns and burns out Thus, an inorganic foam having a large surface area by forming fine pores can be stably obtained.
(4) Depending on the type of shell, it has a fiber like red shell, etc., and the fiber is located around the bubble formed by melting and foaming at a predetermined melting temperature and functions as a reinforcing agent. Prevent rupture.
(5) The shell has not only calcium ions but also magnesium ions, which 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 crack 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 decomposition of shell powder by heating absorbs moisture and carbon dioxide, an inorganic foam excellent in hygroscopicity can be produced.
(7) Since calcium hydroxide produced by absorption of moisture by calcium oxide is easily eluted, an inorganic foam that can be used as a soil modifier can be produced.
(8) Although the main component of the shell powder is calcium carbonate, it contains other compositions and does not thermally decompose, so shell 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 material or the like, calcium, magnesium and the like are eluted into the water from the fracture surface of the inorganic foam and shell residue. As a result, phosphoric acid dissolved in water reacts with the eluted calcium and is adsorbed by the calcium content in the inorganic foam to become calcium phosphate (insoluble), thereby improving the water quality. Moreover, the eluted magnesium can promote the growth of shellfish, algae and the like.
(9) Since a predetermined amount of shell powder is blended, when an inorganic powder is melted by heating, an optimal amount of carbon dioxide gas is generated and bubbles are formed, and an inorganic foam having a large expansion ratio is obtained.
(10) Since the density of the shell powder is small, the capacity is large and the shell powder can be uniformly mixed with the inorganic powder.
(11) Many glassy waste materials soften at a low temperature of 1000 ° C. or less, so the equipment load of the 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. In addition, it has high mechanical strength and excellent durability. Moreover, it is easy to form a long inorganic foam such as a plate, and is excellent in moldability.
(12) After the vitreous waste material is melted and solidified, toxic substances such as cadmium and cyan are not eluted, so that an inorganic foam optimal as a water purification treatment material for rivers and lakes can be obtained.
[0011]
  Here, as inorganic waste materials, glassy waste materialsButUsedRu.
  Glass waste is generated from chemical bottles, cosmetics bottles, food seasoning bottles, glass bottles for beverages, etc., flat glass, window glass, TV and display glass panels, and glass product factories. Scrap etc. are used.
[0012]
  As the shell, bivalve shells and conch shells such as oysters, scallops, red shellfish, clams, clams, abalone, turban shell, swordfish, crow mussels and dolphin shells are used.
  The shell is washed with water to remove sand and the like, then dried and crushed. When pulverizing in a wet manner, it may be pulverized and then dried.
  In addition, red shellfish has inorganic fiber, and the fiber is located around the bubble formed by melting and foaming and functions as a reinforcing agent, preventing the bubble from bursting, stabilizing the bubble, and making it uniform Therefore, it is preferably used.
[0013]
  GlassyWaste materials and shells can be pulverized using a pulverizer such as a hammer crusher, edge runner, screen mill, roller mill, erotic fall mill, ball mill, or jet mill.
[0014]
  The content of the shell powder is suitably 1 to 25 parts by weight, preferably 8 to 20 parts by weight, more preferably 10 to 15 parts by weight with respect to 100 parts by weight of the inorganic powder. 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 generated by the decomposition of the shell powder is optimal, and the inorganic foam has a high foaming amount and high mechanical strength. Is obtained. When the amount is 8 to 10 parts by weight, depending on the type of shell powder, the amount of carbon dioxide generated by decomposition is small, and it tends to be difficult to foam, but a relatively large expansion ratio can be obtained. When the amount is 15 to 20 parts by weight, the amount of carbon dioxide generated by decomposition of the shell powder is large, and fine cracks are generated on the surface of the inorganic foam. A relatively high mechanical strength is obtained. When the amount is 1 to 8 parts by weight, the amount of carbon dioxide generated by decomposition of the shell powder is small and the bulk is difficult to increase, and it is difficult to form open cells. There is a tendency that cracks on the surface of the foam are increased and mechanical strength is lowered. In particular, if the amount is less than 1 part by weight or more than 25 parts by weight, these tendencies are remarkable, which is not preferable.
[0015]
  Invention of Claim 2 of this invention is the inorganic type foam of Claim 1, Comprising: The said molten foam has the structure cut | disconnected or crushed.
  With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
(1) As civil engineering materials used for embankment, backfilling, backfilling, etc., lightweight aggregates such as concrete and asphalt, construction materials such as heat insulating materials, soundproofing materials, etc. It can be used as a treatment material or a lightweight soil material.
[0016]
  The invention described in claim 3 of the present invention is described in claim 1 or 2.Inorganic foamAnd the particle size of the inorganic powder is0.01 to 3000 μmIt has the composition which is.
  With this configuration, in addition to the operation obtained in the first or second aspect, the following operation can be obtained.
(1) Since the particle size of the inorganic powder is adjusted within a predetermined range, the melting temperature of the inorganic powder is stabilized, the bubble size is also stabilized, the bubble particle size distribution is small, and the mechanical strength is reduced. It can be enhanced and the quality stability of the inorganic foam is excellent.
[0017]
  Here, 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. 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 hardly breaks even during cooling after heating and melting. As it becomes smaller than 0.5μmGlassyThere is a tendency that the pulverization efficiency of the waste material decreases, the load of the pulverization equipment and the number of man-hours increase, and it is easy to melt at the time of firing and the control of the melting temperature becomes difficult. As this becomes smaller than 0.1 μm, this tendency increases, and the amount collected by a dust collector such as a bag filter at the time of pulverization increases and the load on the pulverization equipment tends to increase. Moreover, as the gap is larger than 500 μm, the gap between the inorganic powders is large, so that 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 broken at the time of cooling after heating and melting. This tendency increases as the thickness becomes larger than 1000 μm, and depending on the type of inorganic powder, the specific gravity of the inorganic foam increases, making it difficult to control the specific gravity of the product of the inorganic foam. Since the thermal conductivity is small, there is a tendency that heat is not easily transferred 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 is lowered. In particular, when the particle diameter is smaller than 0.01 μm or larger than 3000 μm, these tendencies tend to be remarkable, and neither is preferable.
  An inorganic powder having a particle size in this range can be granulated and used as a granulated powder having a predetermined particle size.
[0018]
  Inorganic powders are collected by dry classifiers such as gravity classifiers, inertia classifiers, centrifugal classifiers, and sieving machines, and by gravity-type wet classifiers such as Spitzcasten and spiral classifiers, and hydrodynamic cyclones. Classification to a predetermined particle size is preferable because it can be reliably adjusted to a predetermined range. When a wet classifier is used, drying is performed after classification, or when heating in a heating furnace, the temperature is raised after completely evaporating moisture or the like at around 200 ° C. This is to prevent moisture in the molded body formed of the inorganic powder from expanding in the heating furnace and collapsing the molded body.
[0019]
  As the particle size distribution of the inorganic powder, when the cumulative sieve% of the inorganic powder having a particle diameter of 1000 μm is 100% by weight, the breakdown is 50 to 70% by weight with the cumulative sieve% of the particle diameter of 250 μm, It is preferable that the particle size is 70 to 90% by weight under an integrated sieve having a particle size of 500 μm. The inorganic powder having this particle size distribution is excellent in mechanical strength because sintering proceeds sufficiently at the time of heating and melting, and can form an inorganic foam excellent in homogeneity by uniformly dispersing bubbles. .
  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. Thereby, according to the addition amount, the specific gravity of the formed inorganic foam can be increased, and the specific gravity of the product of the inorganic foam can be easily controlled. Since the specific gravity easily settles in water by its own weight by setting it to 1 or more, it is particularly convenient when performing filtration or activation of water, and weight reduction can be achieved by making the specific gravity less than 1. it can. In addition, when the inorganic powder having a particle diameter of 1000 to 3000 μm is not added to the inorganic powder having a particle diameter of 0.1 to 1000 μm (when the addition amount is 0 part by weight), the bubbles are uniformly dispersed. An inorganic foam excellent in homogeneity can be formed. As the added amount of the inorganic powder having a particle size of 1000 to 3000 μm is more than 30 parts by weight, a lot of places where the heat is not easily transferred to the inside of the inorganic powder during firing and the firing is insufficient are formed, and the inorganic powder is formed. This is not preferable because the mechanical strength of the foam tends to decrease.
  When not adding and mixing 1000-3000 micrometers inorganic type powder, it can grind | pulverize again using grinders, such as a hammer crusher, and can use it as an inorganic type powder with a particle size of 1000 micrometers or less.
[0020]
  Invention of Claim 4 of this invention is described in any one of Claim 1 thru | or 3.Inorganic foamAnd the particle diameter of the said shell powder has the structure which is 0.1-3000 micrometers.
  According to this configuration, in addition to the action obtained in any one of claims 1 to 3, the following action is obtained.
(1) Since the particle diameter of the shell powder is 0.1 to 3000 μm, it is difficult to agglomerate and can be dispersed so as to be scattered in the inorganic powder, so that bubbles are scattered by heating and foaming. Can be uniformly distributed.
(2) As a result, independent bubbles having a relatively large diameter can be formed, and an inorganic foam having a specific gravity greater than 1 can be formed.
[0021]
  Here, the particle diameter of the shell powder refers to a particle diameter measured by a sieving method using a JIS standard sieve, a microscopic method, or the like.
  As the particle size of the shell powder becomes smaller than 0.1 μm, the load on the grinding equipment and the man-hour increase, and the shell powder tends to agglomerate and tends to be difficult to uniformly disperse in the inorganic powder, and becomes larger than 3000 μm. As a result, the amount of gas generated when one shell powder is decomposed by heating is increased, and it becomes easy to form coarse bubbles. From this point, the inorganic foam easily breaks, and the relative to the inorganic powder. Since the number of typical shell powders decreases, the number of bubbles decreases and the expansion ratio of the inorganic foam tends to decrease.
  The shell powder can be classified in the same manner as the inorganic powder described in claim 3. Thereby, a particle size can be reliably adjusted to the range of 0.1-3000 micrometers.
[0022]
  The invention according to claim 5 of the present invention is according to any one of claims 1 to 3.Inorganic foamAnd the particle size of the said shell powder is 0.1-1000 micrometers.
  According to this configuration, in addition to the action obtained in any one of claims 1 to 3, the following action is obtained.
(1) Since the particle size of the shell powder is about 0.1 to 1000 μm, which is substantially the same as the particle size of the inorganic powder, it can be uniformly dispersed in the inorganic powder, and can be heated and melted to foam. Can be uniformly distributed.
(2) As a result, since the shell powder particles are small and uniformly dispersed, it is possible to form a large number of independent bubbles and a continuous cell in which a large number of them are connected, and an inorganic foam having a specific gravity smaller than 1. The body can be formed.
(3) Since the bubble particle size can be formed small, when used as a water purification treatment material, suspended substances in water can be captured, and the water purification performance is excellent.
[0023]
  Here, as the particle size of the shell powder becomes smaller than 0.1 μm, the load on the grinding equipment and the man-hour increase, and the shell powder tends to aggregate and tends to be difficult to uniformly disperse in the inorganic powder. The larger the gas, the larger the amount of gas generated when one shell powder is decomposed by heating and the formation of coarse bubbles, and the number of shell powders relative to the inorganic powder is reduced, resulting in open cells. Neither is desirable because there is a tendency that is difficult to be formed.
  Note that the particle diameter of the shell powder is measured by a sieving method or the like as described in the fourth aspect.
[0024]
  Invention of Claim 6 of this invention is described in any one of Claim 1 thru | or 3.Inorganic foamAnd the particle diameter of the shell powder is0.01-50 μmIt has the composition which is.
  According to this configuration, in addition to the action obtained in any one of claims 1 to 3, the following action is obtained.
(1) Since the density of the shell powder is small and the particle size is small, the number of particles is large, the shell powder is coated on the surface of the inorganic powder, and fine bubbles are uniformly dispersed and formed. be able to.
(2) As a result, it is possible to form continuous bubbles in which many fine bubbles are connected, and to form an inorganic foam having a large surface area and a specific gravity greater than 1.
[0025]
  Here, as the particle diameter of the shell powder becomes smaller than 0.1 μm, the equipment load and man-hours of the pulverization equipment and the like increase, and the shell powder tends to agglomerate and tends not to be uniformly dispersed in the inorganic powder. As the thickness exceeds 10 μm, there is a tendency that the number of shell powders relative to the inorganic powder necessary to form open cells is insufficient and open cells are difficult to form. In particular, when the particle size is smaller than 0.01 μm or larger than 50 μm, these tendencies tend to be remarkable, which is not preferable.
  As the shell powder, shell powder collected by a dust collector such as a filter dust collector such as a bag filter or an air filter or an electric dust collector used when the shell powder is pulverized is preferably used. Used. It is efficient because shell powder having a particle size of 0.1 to 10 μm can be collected with a bag filter, and shell powder having a fine particle size of about 0.01 μm can be collected with an air filter or an electrostatic precipitator. It is.
  Note that the particle diameter of the shell powder is the same as that described in claim 4 and measured by a microscope or the like.
[0026]
  The inorganic foam according to claim 7 of the present invention comprises 100 parts by weight of inorganic powder obtained by pulverizing glassy waste material and 1 to 1 of shell powder.15The homogeneous mixture with parts by weight is heatedThe calcium carbonate contained in the shell is decomposed to generate carbon dioxide, and the molten inorganic powder is foamed to form bubbles, and cooled to disperse the shell residue containing calcium and magnesium.A low specific gravity foam layer integrated with the inorganic base layer and having a specific gravity smaller than that of the inorganic base layer.
  With this configuration, the following effects can be obtained.
(1) Since the inorganic base layer integrated with the low specific gravity foam layer is included, the low specific gravity foam layer having relatively poor mechanical strength can be reinforced and the mechanical strength can be increased. Excellent durability.
(2) Since the specific gravity of the inorganic base layer is greater than the specific gravity of the low specific gravity foam layer, the inorganic foam is submerged in water such as lakes, swamps, and seas by forming the specific gravity of the inorganic base layer to 1 or more. In this case, the inorganic base layer can be placed on the bottom of the lake with the low specific gravity foam layer facing upward. For this reason, it is easy for water flow to hit the low specific gravity foam layer having a large surface area, and algae adhere to the low specific gravity foam layer and microorganisms are easily settled. Can be performed efficiently.
(3) When dropped in water such as lakes, it settles down with an inorganic base layer having a high specific gravity down and landing, excels in placement in the water, settles stably on the bottom of lakes, etc., and purifies lakes, etc. Can do.
[0027]
  Here, as the inorganic base layer,GlassyInorganic powder obtained by crushing waste materials, and inorganic powder with added waste powders obtained by cutting shell powder, calcium carbonate, dolomite, limestone, marble, etc. Those formed by melting are used. Further, according to claim 4Inorganic foamCan also be used. This is because the specific gravity can be 1 or more and less than the specific gravity of the inorganic powder.
  As the low specific gravity foam layer, a shell powder added to an inorganic powder, heated and integrated with the inorganic base layer to have a specific gravity smaller than that of the inorganic base layer is used. Further, according to claim 5Inorganic foamCan also be used. This is because the specific gravity can be less than 1.
[0028]
  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 specific gravity of the entire inorganic foam. Various selections can be made within a range such that is 1 or more. When the total specific gravity is less than 1, it does not settle when dropped in water such as a lake and cannot be stably fixed to the bottom of the lake.
[0029]
  The method for producing an inorganic foam according to claim 8 of the present invention includes 100 parts by weight of an inorganic powder obtained by pulverizing a glassy waste material, and shell powder 1 to 1 obtained by pulverizing a shell.15A mixing step of mixing an inorganic foam composition containing parts by weight, and a molding obtained by filling or depositing or molding the mixed powder obtained in the mixing step in a mold Heat your body to 750-1100 ° CCarbon dioxide is generated by decomposing calcium carbonate contained in the shell.MeltingThe inorganic powderFoamBubbles were formedA heating foaming step for obtaining a molten foam, and cooling the molten foam.Dispersed shell residue containing calcium and magnesiumIt has a configuration for obtaining a plate-like, lump-like, or elongated inorganic foam.
  With this configuration, the following effects can be obtained.
(1) Since the mixed inorganic foam composition is heated and melted and foamed within a predetermined temperature range, the inorganic powder is sufficiently softened to completely wrap the shell powder, and the shell powder is decomposed. It can be reliably foamed with the generated carbon dioxide gas and has excellent stability.
(2) Since the shell powder is uniformly mixed, it acts as a melting aid, lowers the entire melting temperature, prevents the occurrence of melting spots that tend to be the starting point of destruction, and stabilizes the mechanical strength.
(3) The heating temperature is 750 to 1100 ° C., preferably 900 to 1000 ° C., so that the equipment load of the heating furnace is small, and the energy saving property is excellent.
[0030]
  Here, as 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 a caterpillar made of stainless steel, etc. The molded body formed by molding, etc. is heated intermittently or continuously in a furnace such as a box furnace, shuttle kiln, roller hearth kiln or tunnel type to melt inorganic powder (molded body). Things are used. In the heating and foaming step, bubbles are formed in the melted body in which the inorganic powder (molded body) is melted and softened by the carbon dioxide gas generated by decomposition of the shell powder.
  In addition, the granulation process which granulates mixed powder and forms granulated powder can also be added after a mixing process. Thereby, it can prevent that fine inorganic type powder etc. raise | generate aggregation etc., can improve the moldability of a molded object in a heating foaming process, and can improve a product yield while being excellent in workability | operativity.
[0031]
  The heating temperature in the heating and foaming step is preferably 750 to 1100 ° C, preferably 900 to 1000 ° C, although it depends on the type of inorganic powder. As the heating temperature became lower than 900 ° C., the softening of the inorganic powder was insufficient, and even when the shell powder decomposed, there was a tendency that it was difficult to foam, and as the heating temperature became higher than 1000 ° C., the shell powder was decomposed and generated. There is a tendency for the bubbles to expand and become coarse, making it difficult to obtain fine bubbles, or for the foamed material to be re-melted into a smooth glass. In particular, when the temperature is lower than 750 ° C. or higher than 1100 ° C., these tendencies become remarkable, so that neither is preferable.
[0032]
  In a heating foaming process, it is hold | maintained for 5 to 20 minutes at the heating temperature of 750-1100 degreeC according to the thickness and magnitude | size of a molded object. As the retention time is less than 5 minutes, uneven foaming tends to occur and the size of the bubbles tends to become extremely uneven, and as the retention time is longer than 20 minutes, the bubbles tend to expand and become coarse. Absent. In addition, depending on the thickness and size of the molded body, heat transfer spots are formed, and an inhomogeneous inorganic foam is formed. In order to prevent this, the molded body has a predetermined size according to the size of the heating furnace. Formed in thickness and size.
[0033]
  Particularly preferably, the inside of the long tunnel type heating furnace is set to a temperature of (1) 600 to 750 ° C, (2) 850 to 950 ° C, (3) 950 to 1000 ° C, and (4) 900 to 950 ° C. What is divided into a plurality of preliminarily held areas, and the mixed powder is conveyed and heated to melt so as to pass through each area in 5 to 20 minutes in order. Since the mixed powder is conveyed through an area that has been previously maintained at a predetermined temperature, continuous production is possible and the productivity is excellent. Moreover, since it heats to 850 degreeC or more after preheating at 600-750 degreeC, an inorganic type powder can be melt | dissolved and a shell powder can be decomposed | disassembled and foamed reliably, and a product yield can be raised. Moreover, since it heats to 900-950 degreeC after that, it can prevent that a crack etc. arise in a product, can obtain the mechanical strength as designed, and can raise a product yield.
[0034]
  The molten foam obtained in the heating and foaming process is cooled in a heating furnace, or naturally cooled in the air, or rapidly cooled with air or water to form a long or lump inorganic foam. , Crushed or cut or cracked as needed.
  Inorganic foam, for example, as a civil engineering material used for embankment, backfilling, backfilling, etc., after crushing as a construction material such as lightweight aggregate such as concrete or asphalt, heat insulating material, soundproofing material, etc. It can be used as a soil modifier by mixing with soil. In particular, if it is used as a heat insulating material used under a house floor, attic, wall, etc., it is possible to reduce the weight of the house and the like, and it is preferably used because it provides heat insulation, dehumidification and the like due to its large surface area.
  Moreover, since it contains calcium, magnesium, etc., and is porous and has a large surface area, if it is used as a water purification treatment material, it exhibits excellent water quality improvement performance and is suitable. Moreover, since it is porous, algae and grasses are easy to grow underwater, and it is suitable as a fishing reef. Moreover, since the water retention, light weight, etc. are utilized and calcium, magnesium, etc. elute from a shell residue etc. and it promotes the growth of a plant, it can also be used as lightweight soil materials, such as a rooftop garden or a pot plant.
  In addition, since the specific gravity of the inorganic foam can be easily controlled by the particle size of the shell powder, the specific gravity is less than 1 or almost 1, and the water purification process floats on the surface of the water like floating islands or coral. It can be used as a material. In addition, it can be used as a water purification treatment material that is formed to have a specific gravity of 1 or more and stably lands on the bottom of lakes and marshes, the bottom of water tanks and vases, the shore of rivers, and the like to purify water quality.
  Inorganic foams can be used as lightweight materials to be embedded in reinforced concrete floor slabs because they can be molded into long-sized inorganic foams that are difficult to crack when cooled after heating. It is excellent in environmental conservation and safety without causing problems such as waste disposal. At present, lightweight materials made of polystyrene foam are mainly used, so they disperse during dismantling and pollute the surrounding environment, causing problems in waste disposal, etc., and also a source of toxic gas in the event of a fire. Because.
[0035]
  In addition,The method for producing the inorganic foam comprises: a. Containing 0 to 10 parts by weight of stone powder with respect to 100 parts by weight of the inorganic powder obtained by pulverizing the vitreous waste material, or b. A powder layer containing 1 to 25 parts by weight of shell powder having a particle size of 0.1 to 3000 μm with respect to 100 parts by weight of the inorganic powder, and a particle size of 0.1 to 100 parts by weight of the inorganic powder. A laminating step of laminating 1 to 25 parts by weight of a 1000 μm shell powder, and a laminate obtained in the laminating step is heated to 750 to 1100 ° C. to melt the powder layer. Integrated heating processCan also be.
  With this configuration, the following effects can be obtained.
(1) Having different compositions in the lamination processPowder layerAre laminated in the heating process after being laminated, so that the specific gravity is 1 or morelayerAnd the specific gravity is less than 1layerInorganic foams integrated with can be easily formed and is excellent in productivity.
[0036]
  Here, as a lamination process, a.Glass wasteContaining 0 to 10 parts by weight of stone powder with respect to 100 parts by weight of the inorganic powder obtained by pulverizing or b.1 to 25 parts by weight of shell powder having a particle size of 0.1 to 3000 μm with respect to 100 parts by weight of inorganic powderContainsPowder layerLaid in a stainless steel mold, or deposited on a stainless steel mesh belt or caterpillar, etc.1 to 25 parts by weight of shell powder having a particle size of 0.1 to 1000 μm with respect to 100 parts by weight of inorganic powderContainsPowder layerThe, Previously deposited powder layerWhat is laminated on the top is used. Thereby, in a heating process,Powder layerDead weightsoCrimped and integrated.
  In addition,Reverse the order of depositing the powder layerYou may laminate. In the heating process,Powder layerIt is because it is crimped and integrated in the same manner by its own weight.
[0037]
  As the stone powder added to the inorganic powder, a waste powder obtained by crushing, cutting, cutting or the like of limestone or marble is used. Shell powder can also be used. In any case, what has been disposed of in the past can be used effectively, and can be recycled, resulting in excellent resource saving.
  Stone powderInorganic powderIt is added in the range of 0 to 10 parts by weight, preferably 0.5 to 8 parts by weight with respect to 100 parts by weight. By adding 0.5-8 parts by weight of stone powder to 100 parts by weight of inorganic powder, waste powder obtained from limestone, marble, etc. is thermally decomposed to generate carbon dioxide.layerCan be slightly foamed to form bubbleslayerWhen the surface area is increased and immersed in water such as a lake or pond, algae can be attached and microorganisms can be easily settled. In addition, as the amount of added stone powder is less than 0.5 parts by weightlayerTends to be difficult to foam, and as the amount exceeds 8 parts by weight, the inorganic powder tends to be difficult to melt and integrate, and tends to crack, and the mechanical strength tends to decrease. In particular, when the amount added exceeds 10 parts by weight, this tendency is remarkable, which is not preferable.
[0038]
  In the heating process,Powder layerIs heated in an intermittent or continuous manner in a furnace such as a box furnace, shuttle kiln, roller hearth kiln, tunnel type,Powder layerMeltFoamAt the same time, they are integrated at the interface.
  As the heating temperature of the heating process, claim8Since this is the same as that described in the heating and foaming step, description thereof is omitted.
  Also,GlassyAs the waste material, the one described in claim 1 is used.GlassySince the particle diameter of the inorganic powder obtained by pulverizing the waste material can be the same as that described in claim 3, the description thereof is omitted.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, an embodiment of the present invention will be described 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 the inorganic foam in Embodiment 1, 1a isGlassySubstrate of inorganic foam 1 formed by melting inorganic powder obtained by pulverizing waste material, 1b is formed by pulverizing shells such as oyster shells, and shell powder added to inorganic powder is decomposed Shell residue 1c, which is a residue obtained, is a bubble composed of open cells or closed cells formed in the substrate 1a by foaming calcium carbonate in the shell powder. The main component of the shell powder is calcium carbonate, but it contains other compositions and does not thermally decompose. Therefore, especially when the shell powder has a large particle size, the shell residue 1b is dispersed in the base 1a. Exist.
[0040]
  A manufacturing method of the inorganic foam according to Embodiment 1 configured as described above will be described below.
  At the beginning,Glass wasteIs pulverized to form an inorganic powder having a particle size of 0.01 to 3000 μm. Separately, shell powder such as oyster shell is pulverized to form shell powder having a particle size of 0.1 to 3000 μm. An inorganic foam composition is prepared by adding 1 to 25 parts by weight of shell powder to 100 parts by weight of the inorganic powder.
  Next, in the mixing step, the inorganic foam composition is uniformly mixed to prepare a mixed powder.
  Next, in the heating and foaming step, the prepared mixed powder is filled in a mold made of stainless steel or the like, or deposited on a mesh belt or a caterpillar made of stainless steel, or molded with a mold or the like. The formed body is heated in an intermittent or continuous manner at a temperature of 750 to 1100 ° C. in a tunnel-type heating furnace. More preferably, the inside of the heating furnace is divided into a plurality of sections previously maintained at temperatures of (1) 600 to 750 ° C, (2) 850 to 950 ° C, (3) 950 to 1000 ° C, and (4) 900 to 950 ° C. The mixed powder is conveyed so as to pass through each zone in 5 to 20 minutes in order and heated and melted in a continuous manner. In the heating and foaming process, bubbles are formed in the inorganic powder that has been melted and softened by the carbon dioxide gas generated by decomposition of the shell powder.
[0041]
  Since the inorganic foam in Embodiment 1 is configured as described above, the following action is obtained.
(1)GlassySince wastes such as waste materials and shells are used, it is possible to recycle the waste and it is excellent in resource saving.
(2) Since the shell is low in hardness and easily pulverized, shell powder can be easily obtained, and the load on the pulverization equipment, the number of man-hours, etc. can be reduced.
(3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide and foam the molten inorganic powder to form bubbles, and the humic acid contained in the shell burns and burns out Thus, an inorganic foam having a large surface area by forming fine pores can be stably obtained.
(4) The shell has not only calcium ions but also magnesium ions, which reduce the viscosity of the melt in which the inorganic powder is melted and reduce the residual strain that occurs during cooling, making it difficult to crack during cooling, It is easy to form a long inorganic foam such as a plate and has excellent moldability.
(5) Since calcium oxide produced by decomposition of shell powder by heating absorbs moisture and carbon dioxide, an inorganic foam excellent in hygroscopicity can be produced.
(6) Since calcium hydroxide produced by absorption of moisture by 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 from the fracture surface of the inorganic foam and the shell residue. As a result, phosphoric acid dissolved in water becomes calcium phosphate (insoluble) by the eluted calcium, and the water quality can be improved, which is optimal as a water purification treatment material. In addition to the large surface area, the eluted magnesium can promote the growth of shellfish, algae and the like, 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 stabilized and the size of the bubbles is stabilized, and the mechanical strength can be increased and the inorganic powder can be increased. Excellent foam quality stability.
(9) Since the particle diameter of the 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 the bubbles are uniformly distributed so as to be scattered in the substrate. be able to. As a result, independent bubbles having a relatively large diameter can be formed, and an inorganic foam having a specific gravity greater than 1 can be obtained. Thereby, it can be used as a water purification treatment material that purifies water quality by stably landing on the bottom of lakes and the like, the bottom of water tanks and vases, the shore of rivers, and the like.
[0042]
  Here, in this Embodiment, although the case where the particle size of shellfish powder was formed in 0.1-3000 micrometers was demonstrated, it can also form in the range of 0.1-1000 micrometers. Thereby, the following actions are obtained.
(1) The shell powder hardly aggregates 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 bubbles and continuous bubbles in which a large number of them are connected, and an inorganic foam having a specific gravity smaller than 1 can be formed. Thereby, it is possible to form floating islands, corals, etc. that also float on the surface of water such as lakes and the like and also serve as a water purification treatment material.
[0043]
  Further, the particle diameter of the shell powder can be 0.01 to 50 μm, preferably 0.1 to 10 μm. Thereby, the following actions are obtained.
(1) Since the density of the shell powder is small and the particle size is small, the number of particles increases, so that the shell powder is coated on the surface of the inorganic powder, and fine bubbles are uniformly distributed in the substrate. It can be formed in a dispersed manner.
(2) As a result, it is possible to form continuous bubbles in which many fine bubbles are connected, and to form an inorganic foam having a large surface area and a specific gravity greater than 1. Thereby, it can be used as a water purification treatment material that purifies water quality by stably landing on the bottom of lakes and the like, the bottom of water tanks and vases, the shore of rivers, and the like.
[0044]
  Moreover, according to the manufacturing method of the inorganic foam in Embodiment 1 comprised as mentioned above, the following effects are obtained.
(1) Since the mixed inorganic foam composition is heated and melted and foamed within a predetermined temperature range, the inorganic powder is sufficiently softened to completely wrap the shell powder, and the shell powder is decomposed. It can be reliably foamed with the generated carbon dioxide gas and has excellent stability.
(2) Since the shell powder is uniformly mixed, it acts as a melting aid, lowers the entire melting temperature, prevents the occurrence of melting spots that tend to be the starting point of destruction, and stabilizes the mechanical strength. In addition, 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) Since the heating temperature is 750 to 1100 ° C., preferably 900 to 1000 ° C., the equipment load such as a heating furnace is small, and the energy saving property is excellent.
(4) By dividing the inside of the heating furnace into a plurality of zones, and conveying the mixed powder so as to pass through each zone in order and heating and melting it continuously, it is possible to produce continuously and is excellent in productivity and inorganic The melting of the system powder and the decomposition and foaming of the shell powder can be reliably performed, and the product yield can be increased.
[0045]
  (Embodiment 2)
  FIG. 2 is a perspective view of the inorganic foam in the second embodiment, and FIG. 3 is a schematic diagram of a main part of the inorganic foam manufacturing apparatus in the second embodiment.
  In FIG. 2, 1 ′ is the inorganic foam in the second embodiment, 2 isGlass wasteAn inorganic base layer obtained by heating and melting an inorganic powder having a particle size of 0.01 to 3000 μm obtained by pulverizingGlass wasteInorganic powder with a particle size of 0.01 to 3000 μm obtained by crushing coconut shell and shell powder with a particle size of 0.1 to 1000 μm obtained by crushing shells such as oyster shells are mixed and heated to melt The low specific gravity foam layer 3 a integrated with the inorganic base layer 2 is a boundary surface between the inorganic base layer 2 and the low specific 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 disposed on the mesh belt 5, and 6a is This is a high specific gravity powder layer which is supplied from the first hopper 6 onto the mesh belt 5 with a predetermined thickness and deposited. High specific gravity powder layer 6a is a glassy waste materialTheIt contains 0 to 10 parts by weight, preferably 0.5 to 8 parts by weight of stone powder such as cutting powder such as marble, with respect to 100 parts by weight of the inorganic powder obtained by pulverization. Reference numeral 7 denotes a second hopper disposed on the mesh belt 5 between the first hopper 6 and the heating furnace 4, and 7a is deposited from the second hopper 7 on the high specific gravity powder layer 6a with a predetermined thickness and laminated. This is a low specific gravity powder layer. The low specific gravity powder layer 7a contains an inorganic foam composition in which a shell powder formed to a particle size of 0.1 to 1000 μm is added to an inorganic powder formed to a particle size of 0.01 to 3000 μm. Is.
[0046]
  About the inorganic type foam in Embodiment 2 comprised as mentioned above, the manufacturing method is demonstrated below.
  At the beginning,Glass wasteIs pulverized to form an inorganic powder having a particle size of 0.01 to 3000 μm. A mixture obtained by adding 0 to 10 parts by weight, preferably 0.5 to 8 parts by weight of stone powder to 100 parts by weight of the inorganic powder is stored in the first hopper 6.
  Also,Glass wasteIs pulverized to form an inorganic powder having a particle size of 0.01 to 3000 μm. Further, a shell powder such as oyster shell is pulverized to form a shell powder having a particle size of 0.1 to 1000 μm. A mixture obtained by adding 1 to 25 parts by weight of shell powder to 100 parts by weight of the 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. Next, inorganic powder or the like is deposited on the high specific gravity powder layer 6a from the second hopper 7, and the low specific gravity powder layer 7a is laminated.
  Next, in the heating step, the laminate in which the high specific gravity powder layer 6 a and the low specific gravity powder layer 7 a are laminated is heated to 750 to 1100 ° C., preferably 900 to 1000 ° C. in the heating furnace 4. 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. Thus, the low specific gravity foam layer 3 and the inorganic base layer 2 are integrated with each other by pressure bonding to the inorganic base layer 2.
[0047]
  As described above, since the inorganic foam in the second embodiment is configured, the following effects are obtained.
(1) Since the inorganic base layer integrated with the low specific gravity foam layer is included, the low specific gravity foam layer having relatively poor mechanical strength can be reinforced and the mechanical strength can be increased. Excellent durability.
(2) Since the specific gravity of the inorganic base layer is greater than the specific gravity of the low specific gravity foam layer, the inorganic foam is submerged in water such as lakes, swamps, and seas by forming the specific gravity of the inorganic base layer to 1 or more. In this case, the inorganic base layer can be placed on the bottom of the lake with the low specific gravity foam layer facing upward. For this reason, water flow easily hits the low specific gravity foam layer having a large surface area, and algae and microorganisms easily attach to the low specific gravity foam layer. Purification and the like can be performed efficiently.
(3) When dropped in water such as lakes, it settles down with an inorganic base layer having a high specific gravity down and landing, excels in placement in the water, settles stably on the bottom of lakes, etc., and purifies lakes, etc. Can do.
[0048]
  Moreover, according to the manufacturing method of the inorganic foam in Embodiment 2, the following effects are obtained.
(1) Since a low specific gravity powder layer and a high specific gravity powder layer having different compositions in the lamination step are laminated and then integrated in the heating step, the specific gravity is less than 1 and the inorganic base layer having a specific gravity of 1 or more An inorganic foam in which the low specific gravity 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 between the inorganic base layer and the low specific gravity foam layer can be easily adjusted. As a result, an inorganic foam can be produced so that the overall specific gravity is 1 or more, and when dropped into water such as a lake, the inorganic base layer is set downward and sinks to the bottom of the lake. An inorganic foam which can be stably fixed can be produced.
[0049]
  In the present embodiment, the case of using a high specific gravity powder layer in which inorganic powder and stone powder are mixed has been described. However, the particle size of the inorganic powder formed to a particle size of 0.01 to 3000 μm is described. It is also possible to use a high specific gravity powder layer containing an inorganic foam composition to which shellfish powder formed to 0.1 to 3000 μm is added. As a result, an inorganic base layer having a specific gravity greater than 1 and containing shell residue can be obtained. Since this inorganic base layer elutes calcium and magnesium when immersed in water, it is optimal as a water purification treatment material or fishing reef.
[0050]
【Example】
  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
  Example 1
  Glassy waste materials such as glass bottles and window glass were coarsely pulverized to an average particle size of 2 to 3 mm using a pulverizer such as an edge runner. Then, it was finely pulverized using a pulverizer such as an erotic fall mill. Next, it was classified by a classifier using a 20-mesh standard sieve (mesh 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 pulverized to an average particle size of 2 to 3 mm using a pulverizer such as an edge runner. Then, it was finely pulverized using a pulverizer such as an erotic fall mill. Next, classification was performed by a classifier using a 16-mesh standard sieve (aperture 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 12 parts by weight of the shell powder are sufficiently mixed with a pulverized and classified inorganic foam composition by a mixer such as a stirrer and mixed powder. Got.
  In the heating and foaming step, a tunnel-type heating furnace in which a mesh belt having a width of 1.5 m formed of stainless steel or the like was stretched over a length of 25 m was used. The obtained mixed powder was deposited on the mesh belt to a thickness of about 14 mm, a width of about 1.0 m, and a length of 1.2 m along the length of the mesh belt. The mesh belt is divided into five zones in a heating furnace maintained at a first zone 600 to 750 ° C., a second zone 850 ° C., a third zone 940 ° C., a fourth zone 960 ° C., and a fifth and sixth zones 940 ° C. The mixed powder that has passed through the heating furnace is melted and foamed over 30 to 60 minutes, has a thickness of about 45 mm, a width of about 1.0 m, and a length of about 1. A 2 m plate-like inorganic foam of Example 1 was obtained.
  The specific gravity of the inorganic foam of Example 1 was measured and found to be 0.6. It was confirmed that this inorganic foam floats on water. Observation of the fracture surface confirmed that bubbles with an inner diameter of 0.3 to 2 mm were uniformly distributed.
[0051]
  (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 Elofold mill. At this time, filtration collection such as bag filters and air filters was performed. A shell powder having a particle size of 0.01 to 50 μm collected by a dust device or the like 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 inorganic powder obtained in the same manner as in Example 1. Got the body.
  It was 1.1 when the specific gravity of the inorganic foam of Example 2 was measured. It was confirmed that this would sink when immersed in water. Observation of the fracture surface confirmed that bubbles with an inner diameter of 0.2 to 1 mm were uniformly distributed.
[0052]
  (Comparative Example 1)
  Except for adding 4 parts by weight of silicon carbide (average particle size 3.9 μm, product name C-4000F, manufactured by Yakushima Electric) to 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, an inorganic foam of Comparative Example 1 was obtained.
  The specific gravity of the inorganic foam of Comparative Example 1 was measured and found to be 0.4.
[0053]
  (Dissolution test)
  Table 1 shows the results of evaluating the amount of toxic substances eluted when the inorganic foams of Examples 1 and 2 were immersed in water.
[Table 1]
  In the measurement method shown in (Table 1), “JK0102” is an abbreviation for “JIS K0102”, and “S49 notification” is displayed in “Showa 49 Environment Agency Notification”. What is displayed as “S46 notification” is an abbreviation of “1971 Environment Agency Notification”.
  As a result, it became clear that no elution of harmful substances was observed with the inorganic foam of this example.
[0054]
  (Evaluation as water purification material)
  Using the inorganic foams of Examples 1 and 2 and Comparative Example 1, evaluation as a water purification treatment material was performed.
  FIG. 4 is a schematic diagram of a water purification treatment material evaluation test apparatus.
  In FIG. 4, 10 is a water purification treatment evaluation test apparatus, 11 is a column with a capacity of 100 ml, 12 is cut or crushed into a substantially cubic shape with a side of about 1 cm, and filled in the column 11 as in Examples 1 and 2, etc. Inorganic foam as a sample, 13 is a beaker with a capacity of about 1 L, 14 is about 1 L which contains 0.4 mg / L ammonia nitrogen and 0.2 mg / L phosphate phosphorus and is injected into the beaker 13. 15 is connected to the downstream side of the column 11 and the beaker 13 to supply the aqueous solution 14 that has passed through the column 11 to the beaker 13, and 16 is connected to the upstream side of the beaker 13 and the column 11. A liquid circulation path 17 for supplying the aqueous solution 14 to the column 11, 17 is a pump such as a roller tube pump provided in the liquid circulation path 16 for circulating the aqueous solution 14.
  In this evaluation test, the water purification performance of the inorganic foam 12 having substantially the same volume packed in the column 11 having a capacity of 100 ml was evaluated. The inorganic foam 12 was packed or packed into the column 11 using a material that was naturally dried for 10 days in a room temperature room after being cut or crushed into a substantially cubic shape with a side of about 1 cm. The filling amount was 25.5 g for the inorganic foam of Example 1, 50.2 g for the inorganic foam of Example 2, and 20.1 g for the inorganic foam of Comparative Example 1. 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. The reason why ammonia nitrogen was set to 0.4 mg / L and phosphate phosphorus was set to 0.2 mg / L is that a river with a considerably large pollution load was assumed.
  In addition, in the inorganic foam of Comparative Example 1, when the column was packed, many portions that were rubbed with each other collapsed relatively easily and became powdery. On the other hand, such a phenomenon was not 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.
[0055]
  After starting the experiment by driving the pump 17 using the evaluation test apparatus 10 configured as described above, the aqueous solution 14 after 0, 1, 3, 5, 12, 24, and 48 hours was collected from the beaker 13. The ammoniacal nitrogen and phosphate phosphorus were measured for the collected aqueous solution.
  The results are shown in FIGS.
  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 a ratio with the concentration of ammonia nitrogen and the like at each elapsed time when the concentration of ammonia nitrogen and the like before the start of the experiment (elapsed time 0) is 1.
[0056]
  As shown in FIG. 5, the inorganic foams of Example 1 and Example 2 using shell powder reduced the specific concentration of ammonia nitrogen to a low concentration of 0.2 or less in about 48 hours from the start of the test. I was able to. Therefore, for ammoniacal nitrogen, the inorganic foams of Example 1 and Example 2 using shell powder have almost the same water quality improving effect as the inorganic foam of Comparative Example 1 using silicon carbide. It became clear to show.
[0057]
  Next, as shown in FIG. 6, the phosphorous-state phosphorus was able to be reduced to a specific concentration of 0.4 or less in 48 hours from the start of the experiment with the inorganic foam of Example 1. On the other hand, in the inorganic foam of Comparative Example 1, since the specific concentration was about 0.7 after 48 hours from the start of the experiment, the inorganic foam of Example 1 has a remarkable phosphate phosphorus removal effect. It became clear that it was excellent.
  This is because calcium phosphate and magnesium contained in the shell are eluted from the fracture surface of the inorganic foam into water, so that phosphorous phosphate becomes calcium phosphate (insoluble), or the shell containing calcium contains phosphate in water. It is presumed that the water quality is improved by the formation of calcium phosphate by adsorption of the state phosphorus. The removal ability of phosphate phosphorus of the inorganic foam of Example 1 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 high. 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 the phosphate phosphorus in water is removed as calcium phosphate. I guess.
  As described above, according to the present embodiment, the water purification treatment is excellent in the removal effect of ammonia nitrogen and phosphate phosphorus and does not show elution of harmful substances, and has high mechanical strength and is not easily disintegrated by an external force such as a water flow. It became clear that the most suitable inorganic foam as a material was obtained.
[0058]
  (Evaluation as a water purification treatment material using a breeding aquarium)
  Next, the organism was actually raised in the breeding aquarium and evaluated as a water purification treatment material.
  FIG. 7 is a schematic view showing a test apparatus using a breeding water tank.
  In the figure, 20 is a test apparatus using a breeding aquarium, 21 is a rectangular parallelepiped breeding tank having a length of 90 cm, a width of 40 cm, and a height of 60 cm, and 22 is an inorganic foam of Example 1 crushed to an average particle size of 40 mm. A water purification treatment layer made of an inorganic foam (water purification treatment material) laid on the bottom of the breeding water tank 21 with a thickness of about 10 cm, 23 is a wire mesh disposed on the water purification treatment material layer 22, and 24 is a wire mesh 23. A partition plate 25 having water permeability such as a wire mesh or a mesh installed upright on the metal mesh 23 having a thickness of about 7 cm on a wire mesh 23 in which glass particles having an average particle diameter of 2 mm are partitioned by a partition body 24. Laminated glass grain layer 26 is adjacent to the glass grain layer 25 partitioned by the partition body 24 on the wire mesh 23 with red jade soil (average particle size 3 mm), kanuma soil (average particle size 3 mm) and the above inorganic Volume of foam (based on pulverization to an average particle size of 3 mm) 4 is a mixture of 4: 4: 2 and deposited more than the laying thickness of the glass particle layer 25, 27 is a submersible pump disposed in the water purification treatment material layer 22, and 28 is connected to the submersible pump 27. A water injection pipe 29 is provided through the wire mesh 23 and the soil grain portion 26 to inject water sucked from the submersible pump 27 from above the glass grain layer 25, and is bred after removing chlorine by pumping tap water all day and night. About 50 L of water stored in the water tank 21.
  The submersible pump 27 circulates water 29 stored in the breeding aquarium 21 at a flow rate of 10 L / min, and an air pump (not shown) supplies 6 L / min of air into the water purification treatment material layer 22 and the glass particle layer 25. ing.
[0059]
  Fireflies were bred using the test apparatus using the breeding aquarium constructed as described above.
  In the beginning of September, about 50 L of pumped water was stored in the breeding tank, and the submersible pump was driven to circulate the water for about 5 days. In addition, apple skin was placed on the surface of the glass grain layer as food for kawainina.
  The firefly larvae grew while eating kawainina in the glass grain layer and repeated molting. In March of the following year, they landed on the soil grain and hatched, and emerged in June and became adults. During this time, only the replenishment of the evaporated water and the replacement of the apple skin used as a food for the river bream, there was no need for maintenance such as water replacement and cleaning of the rearing tank. This is because there was no occurrence of phytoplankton, blue-tailed sea urchins, etc. in the inside or underwater of the breeding aquarium, no floating substances such as food eaters, and the breeding aquarium and water were not contaminated at all.
  This is because the inorganic foam is porous, so that it can capture and remove suspended solids such as food eaters, and microorganisms can easily settle on the surface of the inorganic foam. The reason is that nitrification using ammonia as nitrate and anti-nitrification using nitrate as nitrogen gas were performed, and the concentration of ammonia and nitrate in water could be kept low. Moreover, since the inorganic foam is foamed using shell powder and has a calcium component or the like, it can be removed from the water by adsorbing water-soluble nitrogen or phosphorus, etc. It is presumed that phytoplankton and blue-green algae, etc. that feed on water were prevented from growing and water quality was prevented from deteriorating. In addition, inorganic foams are foamed using shell powder and contain calcium and magnesium components, so these useful minerals are eluted in water and promote growth of shellfish such as kawaina. I guess that I let them.
  As described above, according to this example, even when an organism is actually bred, suspended substances in water, water-soluble nitrogen, phosphorus, and the like can be removed, and a water purification treatment material excellent in water purification performance can be obtained. It became clear.
[0060]
  (Example 3)
  A mixed powder was prepared by adding 11 parts by weight of a shell powder formed to a particle size of 3000 μm or less 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, and meshed. Deposited on the belt with a thickness of about 14 mm.
  Subsequently, it heated and melt-foamed with the heating furnace set similarly to Example 1, and the inorganic type foam of Example 3 was obtained.
  It was 1.1 when the specific gravity of the inorganic foam of Example 3 was measured. It was confirmed that this would sink when immersed in water. Observation of the fracture surface confirmed that bubbles with an inner diameter of 0.2 to 3 mm were distributed.
[0061]
  (Example 4)
  In the same manner as in Example 1, 4 parts by weight of stone powder such as cutting powder such as marble formed to a particle size of 0.1 to 20 μm was added to 100 parts by weight of inorganic powder having a particle size of 850 μm or less. A product was prepared and 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 process)
  Next, in the heating step, the high specific gravity powder layer and the low specific gravity powder layer are melted and integrated with the inorganic base layer using the heating furnace set in the same manner as the heating and foaming step described in Example 1. The low specific gravity foam layer is formed, and the inorganic base layer has a thickness of about 10 mm, the low specific gravity foam layer has a thickness of about 30 mm, a width of about 1.0 m, and a length of about 1.2 m. A foam was obtained.
  The obtained inorganic foam was crushed so that the length and width were about 10 cm, and dropped into a water tank having a depth of about 2 m. As a result, an inorganic base layer having a large specific gravity was placed on the lower side. As a result, the inorganic base layer landed on the bottom of the water tank with the low specific gravity foam layer facing upward.
  As described above, according to the present embodiment, the inorganic substrate layer can be stably landed on the bottom of the lake with the low specific gravity foam layer facing upward, so that the water flow easily hits the low specific gravity foam layer having a large surface area. At the same time, algae adhere to the low specific gravity foam layer and microorganisms are easily settled, and the low specific gravity foam layer can efficiently decompose organic substances and purify water. It became clear that an optimal inorganic foam was obtained.
[0062]
  Although the same evaluation was performed by changing the content and particle size of the inorganic powder and shell powder within a predetermined range, each of them was formed to have a predetermined specific gravity as in this example. CanInIt was confirmed that the water purification was excellent.
[0063]
【The invention's effect】
  As described above, the present inventionInorganic foams andAccording to the method for producing an inorganic foam, the following advantageous effects can be obtained.
  According to the invention of claim 1,
(1)GlassySince wastes and wastes such as shells are used, waste can be recycled and resource savingInorganic foamCan be provided.
(2) Since the shell is low in hardness and easily pulverized, shell powder can be easily obtained, and the load on the pulverization equipment and the number of man-hours can be reduced.Inorganic foamCan be provided.
(3) By heating, the calcium carbonate contained in the shell decomposes to generate carbon dioxide and foam the molten inorganic powder to form bubbles, and the humic acid contained in the shell burns and burns out Inorganic foam with large surface area that forms fine poresTheCan be provided.
(4) Depending on the type of shell, it has a fiber like red shell, etc., and the fiber is located around the bubble formed by melting and foaming at a predetermined melting temperature and functions as a reinforcing agent. Prevent ruptureInorganic foamCan be provided.
(5) The shell has not only calcium ions but also magnesium ions, which 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 crack during cooling. Easily form long inorganic foams such as plates, and has excellent moldabilityInorganic foamCan be provided.
(6) Calcium oxide produced by decomposition of shell powder by heating absorbs moisture and carbon dioxide, so that the inorganic foam has excellent hygroscopicity.TheCan be provided.
(7) Inorganic foam that can be used as a soil modifier because calcium hydroxide produced by absorption of moisture by calcium oxide is easily eluted.TheCan be provided.
(8) When the inorganic foam formed by heating is immersed in water as a water purification material or the like, calcium, magnesium and the like are eluted into the water from the fracture surface of the inorganic foam and the shell residue. As a result, phosphoric acid dissolved in water reacts with the eluted calcium and is adsorbed by the calcium content in the inorganic foam to become calcium phosphate (insoluble), thereby improving the water quality. In addition, the eluted magnesium can promote the growth of shellfish and algae.Inorganic foamCan be provided.
(9) Since a predetermined amount of shell powder is blended, when an inorganic powder is melted by heating, an optimal amount of carbon dioxide gas is generated, bubbles are formed, and an inorganic foam having a large expansion ratio is provided. Can do.
(10) Since the density of the shell powder is small, the capacity is large, and an inorganic foam composition that can be uniformly mixed with the inorganic powder can be provided.
(11) Many glassy waste materials soften at a low temperature of 1000 ° C. or less, so the equipment load of the 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. In addition, it has high mechanical strength and excellent durability. Also, it is possible to provide an inorganic foam that is easy to form a long inorganic foam such as a plate and has excellent moldability.
(12) After the vitreous waste material is melted and solidified, toxic substances such as cadmium and cyan are not eluted, and therefore, an inorganic foam optimal as a water purification treatment material for rivers and lakes can be provided.
[0064]
  According to invention of Claim 2, in addition to the effect of Claim 1,
(1) As civil engineering materials used for embankment, backfilling, backfilling, etc., lightweight aggregates such as concrete and asphalt, construction materials such as heat insulating materials, soundproofing materials, etc. An inorganic foam that can be used as a treatment material, a lightweight soil material, or the like can be provided.
[0065]
  According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) Since the particle size of the inorganic powder is adjusted within a predetermined range, the melting temperature of the inorganic powder is stabilized, the bubble size is also stabilized, the bubble particle size distribution is small, and the mechanical strength is reduced. Can be enhancedInorganic foam with excellent quality stabilityCan be provided.
[0066]
  According to the invention of claim 4, in addition to the effect of any one of claims 1 to 3,
(1) Since the particle diameter of the shell powder is 0.1 to 3000 μm, it is difficult to agglomerate and can be dispersed so as to be scattered in the inorganic powder, so that bubbles are scattered by heating and foaming. Can be evenly distributedInorganic foamCan be provided.
(2) As a result, independent bubbles having a relatively large diameter can be formed, and an inorganic foam having a specific gravity greater than 1 can be formed. This makes it possible to use an inorganic foam that can be used as a water purification treatment that purifies water quality by stably landing on the bottom of lakes and the like, and the bottom of water tanks and vases.TheCan be provided.
[0067]
  According to invention of Claim 5, in addition to the effect of any one of Claims 1 to 3,
(1) Since the particle size of the shell powder is about 0.1 to 1000 μm, which is substantially the same as the particle size of the inorganic powder, it can be uniformly dispersed in the inorganic powder, and can be heated and melted to foam. Can be evenly distributedInorganic foamCan be provided.
(2) As a result, since the shell powder particles are small and uniformly dispersed, it is possible to form a large number of independent bubbles and a continuous cell in which a large number of them are connected, and an inorganic foam having a specific gravity smaller than 1. The body can be formed. This makes it possible to use inorganic foams that can be used as floating islands or water purification treatment materials that have water purification performance that floats on the surface of water such as lakes and marshes.TheCan be provided.
(3) Since the bubble diameter can be made small, when used as a water purification treatment material, it is possible to capture suspended substances in water and the like, and an inorganic foam excellent in water purification performanceTheCan be provided.
[0068]
  According to invention of Claim 6, in addition to the effect of 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, the shell powder is coated on the surface of the inorganic powder, and fine bubbles are uniformly dispersed and formed. be able toInorganic foamCan be provided.
(2) As a result, it is possible to form continuous bubbles in which many fine bubbles are connected, and to form an inorganic foam having a large surface area and a specific gravity greater than 1. This makes it possible to use an inorganic foam that 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 water tanks and vases, river banks, etc.TheCan be provided.
[0069]
  Claim7According to the invention described in
(1) Since the inorganic base layer integrated with the low specific gravity foam layer is included, the low specific gravity foam layer having relatively poor mechanical strength can be reinforced and the mechanical strength can be increased. An inorganic foam having excellent durability can be provided.
(2) Since the specific gravity of the inorganic base layer is greater than the specific gravity of the low specific gravity foam layer, the inorganic foam is submerged in water such as lakes, swamps, and seas by forming the specific gravity of the inorganic base layer to 1 or more. In this case, the inorganic base layer can be placed on the bottom of the lake with the low specific gravity foam layer facing upward. For this reason, it is easy for water flow to hit the low specific gravity foam layer with a large surface area, and algae adhere to the low specific gravity foam layer and microorganisms are easily settled. It is possible to provide an inorganic foam that can be efficiently performed.
(3) When dropped in water such as lakes, it settles down with an inorganic base layer having a high specific gravity down and landing, excels in placement in water, settles stably on the bottom of lakes, etc., and purifies lakes, etc. It is possible to provide an inorganic foam that can be used.
[0070]
  Claim8According to the invention described in
(1) Since the mixed inorganic foam composition is heated and melted and foamed within a predetermined temperature range, the inorganic powder is sufficiently softened to completely wrap the shell powder, and the shell powder is decomposed. It is possible to provide a method for producing an inorganic foam that can be reliably foamed with the generated carbon dioxide gas and has excellent stability.
(2) Since the shell powder is uniformly mixed, the inorganic foam that acts as a melting aid and lowers the overall melting temperature, prevents the occurrence of melting spots that are likely to be the starting point of destruction, and stabilizes the mechanical strength. A manufacturing method can be provided.
(3) Since the heating temperature is 750 to 1100 ° C., preferably 900 to 1000 ° C., it is possible to provide a method for producing an inorganic foam having a small equipment load such as a heating furnace and excellent energy saving. .
[0072]
[Brief description of the drawings]
FIG. 1 is a perspective view of an inorganic foam in Embodiment 1. FIG.
FIG. 2 is a perspective view of an inorganic foam in Embodiment 2.
FIG. 3 is a schematic diagram of a main part of an inorganic foam manufacturing apparatus according to a second embodiment.
[Fig. 4] Schematic diagram of water purification treatment evaluation test equipment
FIG. 5 is a graph showing the relationship between the elapsed time from the start of the experiment and the specific concentration of ammoniacal nitrogen.
FIG. 6 is a graph 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 apparatus using a breeding aquarium.
[Explanation of symbols]
  1,1 'inorganic foam
  1a substrate
  1b Shell residue
  1c bubbles
  2 Inorganic base layer
  3 Low specific gravity foam layer
  3a interface
  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 Water purification material evaluation test equipment
  11 columns
  12 Inorganic foam
  13 Beakers
  14 Aqueous solution
  15, 16 Liquid circuit
  17 Pump
  20 test equipment
  21 rearing tank
  22 Water purification material layer
  23 Wire mesh
  24 divider
  25 Glass grain layer
  26 soil grain
  27 Submersible pump
  28 Water injection pipe
  29 water

Claims (8)

An inorganic foam composition containing 100 parts by weight of an inorganic powder obtained by pulverizing a glassy waste material and 1 to 15 parts by weight of a shell powder obtained by pulverizing a shell is contained in the shell. Calcium carbonate that decomposes, generates carbon dioxide gas, foams the molten inorganic powder to form bubbles, and is cooled to form a plate, lump, or long, in which shell residue containing calcium and magnesium is dispersed An inorganic foam characterized by comprising a molten melt-like body.   The inorganic foam according to claim 1, wherein the molten foam is cut or crushed.   The inorganic foam according to claim 1 or 2, wherein a particle size of the inorganic powder is 0.01 to 3000 µm.   The inorganic foam according to any one of claims 1 to 3, wherein the shell powder has a particle size of 0.1 to 3000 µm.   The inorganic foam according to any one of claims 1 to 3, wherein the shell powder has a particle size of 0.1 to 1000 µm.   The inorganic foam according to any one of claims 1 to 3, wherein the shell powder has a particle size of 0.01 to 50 µm. Inorganic base layer obtained by heating and melting inorganic powder obtained by pulverizing glassy waste material, 100 parts by weight of inorganic powder obtained by pulverizing glassy waste material, and shell powder 1 to 15 weights The shell containing the calcium and magnesium containing the calcium and magnesium is cooled by foaming the inorganic powder that is melted by decomposition of the calcium carbonate contained in the shell when the homogeneous mixture is heated and carbon dioxide is decomposed to generate carbon dioxide and is melted. An inorganic foam, comprising: a low specific gravity foam layer in which a residue is dispersed and integrated with the inorganic base layer to have a specific gravity smaller than that of the inorganic base layer. A mixing step of mixing an inorganic foam composition containing 100 parts by weight of an inorganic powder obtained by pulverizing a glassy waste material and 1 to 15 parts by weight of a shell powder obtained by pulverizing a shell; Then, the mixed powder obtained in the mixing step is filled or deposited in a mold, or a molded body obtained by molding is heated to 750 to 1100 ° C. to decompose calcium carbonate contained in the shell. A heating foaming step of obtaining a melted foam in which bubbles are formed by foaming the inorganic powder melted by generating carbon dioxide gas, and cooling the melted foam to contain calcium and magnesium. A method for producing an inorganic foam, comprising obtaining a plate-like, lump-like, or elongated inorganic foam in which residues are dispersed .

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