JP4649361B2 - Composite material utilizing industrial waste liquid, solid-liquid separation method of industrial waste liquid, and storage method of industrial waste liquid - Google Patents

Description

  The present invention relates to a technique for effectively utilizing industrial waste liquid, and more particularly to a novel composite material utilizing industrial waste liquid, a solid-liquid separation method and storage method for industrial waste liquid, and a method for producing livestock feed from industrial waste liquid.

  Ocean dumping of shochu waste liquid after removing shochu is totally prohibited because it causes marine pollution. Therefore, the shochu waste liquid is separated into solid and liquid, and the solid part (organic solids) is dried and used for livestock feed and fertilizer for agricultural products, or incinerated, and the liquid part is anaerobic fermentation. Then, after generating methane gas, it is generally performed by the activated sludge method to discharge below the effluent standard value. In addition, for wastewater from factories, slaughterhouses, and farms of cattle, horses, pigs, etc., solid-liquid separation is carried out, and the solid part is incinerated, composted, or industrial waste disposal contractor, and most of the liquid part. Generally, it is treated with an activated sludge method and discharged below the effluent standard value.

  However, since the solid part (organic solid content) in the shochu waste liquid is fine particles, the solid-liquid separation of the shochu waste liquid is not simple, the equipment is complicated, and the number of processes is increased, so the running cost is high. There is.

  Moreover, in activated sludge treatment of the liquid part of shochu waste liquid and the waste water part from factories and slaughterhouses, it is difficult to control the activated sludge fungus in winter (it is difficult to maintain activated sludge), and the treatment liquid is cloudy There is a problem such as a foul odor that makes fish rotten. Also, shochu waste liquor is very perishable, and in the summer the waste liquid in the morning will rot in the afternoon, leaving it untreated and causing environmental pollution such as the generation of odors. The establishment of technology to prevent corruption is also regarded as important. For example, the production of shochu is the peak in September-December, when the production of Satsuma is concentrated, and the shochu waste liquor produced during this period cannot be treated in a lump and naturally requires a standing period.粕 If we can establish waste liquid anti-corrosion technology, waste liquid treatment can be carried out on average throughout the year.

In addition, as described above, the solid part (shochu) in the shochu liquor is used for livestock feed, but there is also a problem of bad odor due to rot and the like in the shochu and a large amount of shochu is produced. The problem of malodor becomes obvious. Accordingly, it is desired to expand applications other than shochu livestock feed and crop fertilizers. For example, Patent Document 1 described below describes using shochu as a NOx generation suppressing material in a firing furnace. Yes.
JP 2001-321754 A

In view of the above circumstances, the present invention relatively reduces industrial waste liquid containing organic solid parts such as liquor manufacturing waste liquid such as shochu waste liquid and waste water from factories and slaughterhouses and cattle, horses, pig farms, etc. An object of the present invention is to provide a method for treating industrial waste liquid that can be easily separated into solid and liquid.
Another object of the present invention is to provide a method for storing industrial waste liquid that enables long-term storage without causing the industrial waste liquid to decay.
In addition, the present invention provides a novel composite material that can be obtained without solid-liquid separation of the industrial waste liquid or by utilizing the liquid part that has been subjected to solid-liquid separation, thereby making it unnecessary to dispose of the industrial waste liquid. The purpose is to do.
Moreover, an object of this invention is to provide the manufacturing method of the novel livestock feed which can utilize the said industrial waste liquid, without carrying out solid-liquid separation.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have dissolved polyvinyl alcohol (hereinafter also referred to as “PVA”) in an industrial waste liquid containing organic components such as a shochu waste liquid, and further used a shirasu balloon. When mixed and stirred, industrial waste liquid is separated into solid and liquid. Also, a solution in which polyvinyl alcohol is dissolved in an industrial waste liquid such as a shochu waste liquid (gel-like material), the polyvinyl alcohol contains the industrial waste liquid. It has the effect of reducing contact with air, and the kneaded product of a solution (gel-like product) in which polyvinyl alcohol is dissolved in such industrial waste liquid (or its liquid part) and volcanic ejecta material has sufficient moldability. The solidified product obtained by drying and solidifying the molded product has a lightweight and stable strength, and becomes a highly functional material having various functions such as water absorption, water retention and heat resistance. Heading, as a result of further extensive research, it has led to the completion of the present invention.

That is, the present invention is as follows.
(1) A method for solid-liquid separation of industrial waste liquid, wherein polyvinyl alcohol is dissolved in industrial waste liquid, and then volcanic ejecta material is mixed and stirred in the solution.
(2) The method according to (1) above, wherein the volcanic ejecta material is a shirasu balloon.
(3) A method for preserving industrial waste liquid, characterized in that polyvinyl alcohol is dissolved in industrial waste liquid to form a gel.
(4) A composite material obtained by drying and solidifying a kneaded material containing volcanic ejecta material, industrial waste liquid and polyvinyl alcohol.
(5) The composite material according to (4) above, wherein the kneaded product is a kneaded product further containing industrial waste incineration ash and / or coal incineration ash, and is obtained by drying and solidifying the kneaded product.
(6) The composite material according to (4) above, wherein the kneaded material is a kneaded material further containing charcoal and / or activated carbon, and obtained by drying and solidifying the kneaded material.
(7) The composite material according to (4), wherein the kneaded material is a kneaded material further containing an organic fertilizer and / or a synthetic fertilizer, and is obtained by drying and solidifying the kneaded material.
(8) The composite material according to any one of (4) to (7), wherein the composite material is a granular composite material obtained by forming the kneaded product into a granular shape, drying, and solidifying.
(9) The composite material according to (8) above, wherein plant seeds are fixed on the particle surface.
(10) A panel-shaped composite material obtained by forming the kneaded material into a panel shape, drying and solidifying the same, and holding plant seeds on at least one surface layer thereof (4) to (4) above The composite material according to any one of (7).
(11) The composite material according to any one of (4) to (10), which is for a greening material.
(12) The composite material according to any one of (4) to (11), wherein the industrial waste liquid is a liquor production waste liquid.
(13) The composite material according to any one of (4) to (12), wherein the volcanic ejecta material is a shirasu balloon.
(14) A liquid obtained by solid-liquid separation from industrial waste liquid by the method described in (1) or (2) above, polyvinyl alcohol, volcanic ejecta material, and Portland cement and / or alumina cement. A heat insulating material for walls obtained by drying and solidifying a kneaded product.
(15) A method for producing livestock feed from liquor production waste liquor, comprising drying and solidifying a solution in which polyvinyl alcohol is dissolved in liquor production waste liquor.

  According to the solid-liquid separation method of the industrial waste liquid of the present invention, even if the industrial waste liquid contains a relatively large amount of organic components (organic solids) such as liquor manufacturing waste liquid such as shochu waste liquid, complicated equipment is required. In addition, solid-liquid separation can be easily performed without requiring work.

  Moreover, according to the method for preserving industrial waste liquid of the present invention, for example, even an industrial waste liquid that easily perishes and contains a relatively large amount of organic components (organic solids) such as liquor manufacturing waste liquid such as shochu waste liquid. Long-term storage is possible. Therefore, when a large amount of industrial waste liquid is generated and cannot be processed at once, problems such as the generation of malodor can be prevented by leaving (preserving) such a method.

  Further, according to the composite material of the present invention, industrial waste liquid can be utilized without solid-liquid separation, so that the operation of solid-liquid separation of industrial waste liquid in order to utilize industrial waste liquid as in the past becomes insoluble, Since the composite material retains the organic component (organic solid) in the industrial waste liquid and has good water absorption, water retention and air permeability, it can be suitably used particularly as a greening material. Furthermore, by making seeds retained, planting can be performed by laying them in a space where desired greening is desired and watering them.

  Moreover, since the heat insulating material for walls of the present invention is lightweight, excellent in heat insulating properties and humidity control properties, and has an appropriate elasticity, it becomes a highly functional and high strength heat insulating material for walls.

  Further, according to the method for producing livestock feed of the present invention, the industrial waste liquid can be utilized without solid-liquid separation, so that it is efficient and the production operation is extremely simple.

Hereinafter, the present invention will be described in more detail.
In the present invention, “industrial waste liquid” refers to waste liquid produced by the production of alcoholic beverages such as shochu waste liquid (type production waste liquid), wastewater discharged from slaughterhouses, cattle, horses, pig farms, and the like, and discharged from factories. Dissolves organic matter (organic solids) discharged in various industrial fields such as sludge water that does not contain harmful substances, and sludge liquids that have been treated with activated sludge (hereinafter also referred to as “activated sludge liquid”). It means an aqueous liquid material for disposal that is contained in a dispersed state.

  In the present invention, “volcanic ejecta material” means volcanic ejecta and / or volcanic ejecta foam particles.

  Here, "volcanic ejecta" is volcanic ejecta such as volcanic ash, volcanic gravel, and volcanic rock blocks, or pulverized granular material of the volcanic ejecta (including those that have been classified as necessary). Are shirasu, pulverized granules of pumice, mullet, obsidian and the like. In addition, the “volcanic ejecta foam granules” is a known foam granule obtained from a volcanic ejecta or a pulverized product thereof, for example, a foamed granule obtained by firing and foaming a volcanic ejecta or a crushed product thereof. Body, pressure-foamed foam particles and the like. Specific examples include, for example, shirasu balloons (shirasu baked foam granules / pumice foam granules), perlite (sintered obsidian baked foam granules), and the like. In this invention, volcanic ejecta material can use 1 type (s) or 2 or more types.

  Since the volcanic ejecta material is a natural product (processed product), it is advantageous in terms of safety and environmental impact compared to artificial synthetic organic materials. In the implementation of the method of the present invention described in detail below, In the composite material of the present invention, which is mainly composed of volcanic ejecta material together with PVA, the volcanic ejecta material is harmless together with PVA, so it is extremely harmful to the global environment. It becomes a gentle material.

  The solid-liquid separation method for industrial waste liquid according to the present invention is characterized in that after the polyvinyl alcohol is dissolved in the industrial waste liquid, the volcanic ejecta material is mixed and stirred in the solution. For example, among industrial waste liquids, shochu waste liquid is a suspension in which the solid portion (shochu) is in the form of fine particles and the organic component in the form of fine particles is dispersed in an aqueous liquid medium. Even in the case of liquid industrial waste liquid, by dissolving polyvinyl alcohol in the suspension and further mixing and stirring the volcanic ejecta material, the fine solid part is adsorbed and settled on the volcanic ejecta material. Liquid separation is performed. That is, the waste liquid containing organic matter (organic solid) is adsorbed (attached) to the surface of the volcanic ejecta material (the outer surface of the particles and the inner surface of many vacancies) in a state of being enclosed by polyvinyl alcohol. At the same time, organic matter (organic solid) settles and solid-liquid separation is performed.

  In the said method, although the usage-amount of PVA changes with kinds of industrial waste liquid, 1-10 g per liter of industrial waste liquid is preferable, Most preferably, it is 3-5 g. If the amount of PVA used is less than 1 g, the organic matter in the industrial waste liquid cannot be contained, and even if it settles, the separation is bad. If the amount of PVA used is more than 10 g, the industrial waste liquid itself becomes a gel, causing volcanic eruption. The thing does not settle and is not preferable.

  The dissolution of PVA is preferably carried out while heating the industrial waste liquid, and the heating temperature of the industrial waste liquid is preferably 70 to 90 ° C, particularly preferably 80 to 90 ° C. If the temperature of the industrial waste liquid is less than 70 ° C., the industrial waste liquid and PVA do not dissolve, and if the temperature of the industrial waste liquid exceeds 90 ° C., the PVA will burn, which is not preferable.

  The volcanic ejecta material used in the method is preferably a volcanic ejecta with a high specific gravity in order to promote subsidence, and shirasu is particularly preferred.

  In this method, it is particularly preferable to use a volcanic ejecta having a particle size in the range of 10 to 50 μm from the viewpoint of increasing the speed of subsidence.

  Stirring operation can be performed with a well-known stirring apparatus, for example, a concrete mixer etc. can be mentioned.

  The amount of volcanic ejecta material used varies depending on the type of industrial waste liquid, but is preferably 50 to 300 g, particularly preferably 150 to 200 g, per 10 liters of industrial waste liquid. If the amount of volcanic ejecta material used is less than 50 g, the volcanic ejecta will not spread sufficiently in the industrial waste liquid and the sedimentation of organic matter will be worse, and if the amount of volcanic ejecta material used is greater than 300 g, The amount increases, which is not preferable.

  The sediment in the liquid after solid-liquid separation by the stirring operation (composite in which PVA and solid portion (organic content) are adsorbed on the volcanic ejecta material) is 100 volcanic foam foams per 1 kg of sediment. Mixing and stirring about ˜300 g, for example, drying at a temperature of 500 ° C. or less, preferably 100 to 300 ° C. (more preferably 100 to 200 ° C.) with a hot air drier, etc. It becomes a thing. Since the solidified product contains a large amount of organic components and the volcanic ejecta material is harmless, it can be effectively used as a fertilizer for planting by pulverizing and granulating. Moreover, it can utilize as a soil substitute material by fermenting etc. and solidifying this solidified material. In addition, it is not preferable to perform the above heat treatment at a temperature exceeding 500 ° C. because PVA is carbonized, and a temperature below 100 ° C. is not preferable because it takes a lot of time for drying and increases costs.

  On the other hand, the liquid part after solid-liquid separation is diluted with water and discharged to the discharge reference value. The liquid portion after the solid-liquid separation has a sufficiently low organic component, and can be set to the discharge standard value by diluting to about 3 to 5 times. It should be noted that PVA can be dissolved in the liquid portion after solid-liquid separation, and further mixed with volcanic ejecta foam and Portland cement and / or alumina cement in the PVA solution and used as a thermal insulation for spraying. . That is, the PVA solution is mixed with volcanic eruption foam and Portland cement and / or alumina cement, and this is coated on the wall (base) and dried and solidified, so that many fine pores are formed. It becomes the porous layer which the volcanic ejecta foam which it has gathers in a chain form, and becomes a heat insulating material for walls. Here, PVA is preferably about 5 to 20 g per liter of liquid portion, and particularly preferably 5 to 10 g. The amount of volcanic ejecta foam used is preferably 50 to 200 kg, more preferably 100 to 150 kg per kg of PVA solution. Further, the amount of Portland cement and / or alumina cement used is preferably about 30 to 150 g, more preferably 50 to 100 g, per kg of the PVA solution.

  The heat insulating material for walls of the present invention thus obtained is lightweight and excellent in heat insulating properties, has an appropriate elasticity, and has excellent humidity control properties by including a volcanic ejecta foam. Moreover, it is excellent in adhesiveness with wooden board | plate materials, such as a gypsum board and a veneer board, a steel plate, etc., and can be used suitably especially for the wall material etc. of a building. As this type of conventional heat insulating material, for example, diatomaceous earth or the like is known, and superior heat insulating properties can be obtained as compared with such conventional heat insulating materials. By producing this heat insulating material, it is possible to effectively use the liquid part of the industrial waste liquid which has been separated into solid and liquid without discharging.

  The method for preserving industrial waste liquid according to the present invention is characterized in that polyvinyl alcohol is dissolved in industrial waste liquid to form a gel. That is, by dissolving PVA in an industrial waste liquid to form a gel, the industrial waste liquid is sealed in a PVA aqueous solution (gel), and contact with the air is extremely reduced. As a result, it does not rot for a long time. Can be saved. Therefore, when a large amount of industrial waste liquid cannot be processed at once, the industrial waste liquid can be gelled and left (stored) by the method to prevent environmental pollution such as generation of bad odor due to decay.

  In the said method, although the usage-amount of PVA changes with kinds of industrial waste liquid, 5-300g per liter of industrial waste liquid is preferable, Most preferably, it is 100-200g. If the amount of PVA used is less than 5 g, gelation becomes insufficient and the anti-corrosion effect tends to be reduced, and if the amount of PVA used is more than 300 g, it is too hard to be transferred to a storage container. It becomes difficult and undesirable.

  The dissolution of PVA is preferably carried out while heating the industrial waste liquid, and the heating temperature of the industrial waste liquid is preferably 70 to 90 ° C, particularly preferably 80 to 90 ° C. When the temperature of the industrial waste liquid is less than 70 ° C., it becomes difficult to dissolve the PVA, and when the temperature of the industrial waste liquid exceeds 90 ° C., it is burnt when the PVA is dissolved.

  In this method, a boric acid metal salt or the like may be added (dissolved) together with PVA. By adding (dissolving) the borate metal salt, borate ions bind PVA in a network form, so that the sealing effect of the waste liquid is improved and the anti-corruption effect of the waste liquid can be further enhanced, which is preferable. Although it does not specifically limit as a boric-acid metal salt, Sodium borate (sodium tetraborate) is preferable from points, such as the solubility to water.

  In this method, after adding PVA to the waste liquid, it is necessary to stir the waste liquid well. That is, the agitation promotes the containment of water molecules between the polymer chains of PVA. Such stirring can be performed with a known stirring device, and examples thereof include a jacket humidifying dissolver.

  The preservation method can obtain a sufficient anti-corruption effect even with respect to shochu liquor having a particularly high organic content concentration among industrial wastes.

  The 1st composite material which concerns on this invention consists of a solidified material which dried and solidified the kneaded material containing volcanic ejecta material, industrial waste liquid, and polyvinyl alcohol.

  That is, the composite material is produced by kneading a concentrated solution of PVA in which PVA is dissolved in industrial waste liquid and volcanic ejecta material, and molding the obtained kneaded material into a desired shape, followed by heating and drying. At the stage of the kneaded product, the particles of the volcanic ejecta material are bonded by the gelled product of PVA, and the gelled product has entered the surface and internal pores of the individual particles. By drying, the particles of the volcanic ejecta material are connected to each other by PVA polymer chains, the water in the waste liquid is volatilized to the outside, and the organic content (organic solid) in the waste liquid is taken into the bulk together with PVA. Will be. Accordingly, in the process of producing the composite material, the industrial waste liquid is treated, and the organic component (organic solid) of the industrial waste liquid is used as a material constituting the composite material, so that the industrial waste liquid can be effectively used. .

  The composite material is a lump body in which particles of a volcanic ejecta material (granular material) having a light weight and relatively high strength are connected by PVA, and is lightweight and strong in strength, and the volcanic ejecta material. By virtue of the porous property of PVA and the water absorption and water retention properties of PVA, a porous body having good air permeability, water absorption properties and water retention properties can be obtained. Further, the composite material is a material that is friendly to the global environment because PVA is biodegradable and volcanic ejecta material is harmless per se.

  The form of the composite material is appropriately determined according to the purpose of use, and examples thereof include a panel form, a block form, a granular form, and a sheet form.

  Applications of the composite material include soil improvement (modification) materials, greening materials, spraying materials, and the like. Here, soil improvement (modification) material means a material that is mixed with soil that is not specifically intended to be planted or used as a substitute for soil. It is a material used as a substitute for the soil mixed with the target soil, and the spraying material means a material that can form a planting surface by spraying it on a site intended for planting. Recently, attention has been paid to creating an environment that emphasizes greenery in office buildings and homes, and greening movements are thriving (especially rooftop greening has been reported to have an effect of reducing radiant heat (preventing heat island phenomenon), It is expected that it will greatly contribute to saving air conditioning costs.) However, there are many attempts to cultivate natural plants indoors, rooftops, verandas and terraces of houses and buildings. If the soil is spread on the indoor or rooftop of such a home garden or veranda building, problems such as scattering of the soil, scattering of the sprinkled water, and outflow are caused. Therefore, there is a need for a greening material that can grow plants without hindrance, without causing soil or water scattering, water outflow, and the like. The composite material of the present invention is particularly suitable for greening materials because it is harmless and has good air permeability, water absorption and water retention.

When used for soil improvement (reformation) materials, greening materials, etc., for example, the composite material is granulated and spread in a desired space, or the composite material is molded into a panel shape and is desired to be greened It is preferable to lay in the space. When used as a greening material, the sprinkled water is absorbed and retained in the pores and PVA of the material, so that it is not scattered around and is effectively used for seed germination and plant growth. Moreover, since it is porous, aeration can also be ensured, and the plant can be grown well without insufficient ventilation to the roots of the plant. Moreover, the organic component (organic solid) of the industrial waste liquid present in the composite material becomes a fertilizer and promotes plant growth. In the case of a granular material, the particle size is preferably about 0.5 to ³⁰ mm, and the bulk density is preferably about ³ to 6 g / cm ³ .

  The composite material prepares a PVA concentrated solution (gel) in which about 100 to 300 kg of PVA is dissolved per liter of industrial waste liquid, and about 0.7 to 1.2 parts by weight of volcanic eruption per 1 part by weight of the PVA concentrated solution. It can be obtained by adding a material and kneading to prepare a plastic kneaded product, molding the plastic kneaded product into a desired shape, and drying by heating.

The molding method of the kneaded product is not particularly limited, but it is preferable to put the kneaded product into a mold having a desired shape and press-mold, and the press pressure in the press molding is about 15 to 40 kg / cm ^2. preferable. When the press pressure exceeds 40 kg / cm ² , the volcanic ejecta material (particularly volcanic ejecta foam particles) is destroyed, the density of the composite material is increased, and not only the weight reduction is impaired, but also the air permeability, It may also interfere with water absorption and water retention. Moreover, when the press pressure is less than 15 kg / cm ² , the adhesion and strength between the PVA solution and the volcanic ejecta foam granules are weak, which is not preferable.

  Moreover, what is necessary is just to granulate using the well-known granulator currently used in field | areas, such as granulation of a ceramic, when shape | molding to a granule. In addition, if the seeds of plants are fixed on the surface of the molded product by applying the seeds to the surface of the molded product at the final stage of the granular molding process, the granular composite material obtained by drying is a soil substitute, and The seeds are also provided, which can be planted by simply spreading the seeds in a desired space and watering them.

  In the preparation of the PVA concentrated solution, when the amount of PVA used in the PVA concentrated solution per liter of industrial waste liquid is less than the above range, the adhesion between the PVA solution and the volcanic ejecta foam is poor and the strength is not high, and the amount is large. In this case, the PVA solution becomes hard and stirring with the volcanic ejecta foam cannot be performed uniformly.

  It is preferable to dissolve the PVA in the industrial waste liquid while heating the industrial waste liquid to about 70 to 90 ° C.

  Preparation of the kneaded product of the PVA concentrated solution (gel) and the volcanic ejecta material can be performed, for example, with a stirrer of a concrete mixer. Moreover, when the usage-amount per 1 weight part of PVA concentrated solution of the volcanic ejecta material knead | mixed with a PVA concentrated solution is less than the said range, the intensity | strength of the composite material formed does not go up, and when it is large, When the composite material is formed into a granular material, it is not preferable because it sticks to the granulator and cannot be granulated.

  The heat drying temperature of the kneaded product is preferably 100 to 500 ° C, more preferably 100 to 200 ° C. Heating to a temperature exceeding 500 ° C. is not preferable because PVA is carbonized. Moreover, since the drying time is required at a temperature lower than 100 ° C., productivity is not improved, which is not preferable. Moreover, it is preferable to perform heat drying with a hot air dryer, a hot air rotary dryer, etc. from a viewpoint of preventing the carbonization of PVA.

  In the composite material, the composition (quantity ratio) of the volcanic ejecta material and PVA in the final product after heat drying varies depending on the use of the composite material, but generally the weight ratio (volcanic ejecta material: PVA). ) Is preferably 1: 0.5 to 0.7.

  In the composite material, when the PVA concentrated solution and the volcanic ejecta material are kneaded, the coal incineration ash that comes out of the power plant and the industrial waste incineration ash that comes out from the industrial waste treatment (dioxin, In addition to industrial waste liquid, coal incineration ash, industrial waste incineration ash, etc. can be effectively utilized by adding and kneading them without adding harmful substances such as lead and cadmium. Silica and alumina occupy the components of coal incineration ash and have the same composition as shirasu. By mixing coal incineration ash, the strength of the composite material can be further increased. Moreover, since industrial waste incineration ash contains much phosphorus, when using a composite material for a soil substitute, the fertilizer content (nutrient) in a composite material can be raised. The addition amount of coal incineration ash and / or industrial incineration ash is preferably about 0.3 to 1.0 part by weight per part by weight of volcanic ejecta material.

  Further, when the composite material is used as a greening material, when the PVA concentrated solution and the volcanic ejecta material are kneaded, the fertilizer content can be further increased by adding organic fertilizer and / or synthetic fertilizer and kneading. Soil substitute (greening material) can be obtained. In this case, the amount of organic fertilizer and / or synthetic fertilizer added is preferably about 0.01 to 0.03 parts by weight per part by weight of volcanic ejecta material.

  Moreover, when kneading a PVA concentrated solution and volcanic ejecta material, charcoal (charcoal, bamboo charcoal, etc.) and / or activated carbon is further added and kneaded to obtain a composite material containing charcoal and / or activated carbon. In such a composite material, deodorizing property is further imparted. In this case, the addition amount of charcoal and / or activated carbon is preferably about 0.1 to 0.3 parts by weight per part by weight of volcanic ejecta material.

  The volcanic ejecta material used in the composite material is preferably a volcanic ejecta foam particle from the viewpoint of strength and water retention, and among them, a shirasu balloon is particularly preferred. Moreover, it is especially preferable to use the volcanic ejecta foam particles having a particle diameter in the range of 50 to 200 μm in the present composite material.

  Further, the industrial waste liquid is preferably a liquor production waste liquid having a particularly high organic content (organic nutrient) concentration, and particularly preferably a shochu waste liquid. By using a shochu waste liquid, a composite material containing a large amount of organic components (organic nutrients) can be obtained, which is more preferable as a soil substitute (greening material).

  Moreover, as a preferable embodiment of the composite material, a panel with seeds can be exemplified. That is, the seed-containing panel is obtained by molding a kneaded material containing at least the above volcanic ejecta material, industrial waste liquid and polyvinyl alcohol into a panel shape, and then drying and solidifying the kneaded material when forming the panel shape. The plant seeds are held on at least one surface layer of the panel by mixing plant seeds in part of the panel.

  If it is such a panel with seeds, it can be planted by simply laying it in a garden area of a home, a veranda of a house or a building structure, a rooftop, or a planned greening area indoors and watering the area. Moreover, since it is lightweight, the expansion and removal thereof can be easily performed, and the greening area can be easily expanded and reduced. Although the shape of a panel is not specifically limited, A square, a rectangle, etc. are preferable.

  The seed-containing panel is preferably manufactured as follows. That is, a PVA concentrated solution in which PVA is dissolved in an industrial waste liquid is prepared, and about 0.7 to 1.0 part by weight of volcanic ejecta material per 1 part by weight of the PVA concentrated solution is added and kneaded. A kneaded material is prepared. Then, this plastic kneaded product is divided into two, and one kneaded product is press-molded to obtain a panel (base material panel), while the other kneaded product is further kneaded with seeds of a desired plant. A kneaded material is prepared, and the seed kneaded material is spread and formed on at least one surface of the panel (base material panel) so as to form a uniform layer, and then the laminate is heated and dried with a hot air dryer or the like. And solidify.

  The pressing pressure at the time of forming the panel is preferably within the above numerical range for the same reason as described above. Moreover, it is preferable to perform also the temperature in heat drying within the said numerical range for the same reason as the above.

  The total thickness of the panel is preferably about 3 to 10 cm, and the thickness of the surface layer on which the seed is held is preferably about 0.3 to 1 mm.

  The seeds of plants that can be used in the present invention are seeds of various plants such as turf (Western turf, Korean turf), flowers, vegetables, rice, etc., and are not particularly limited.

  The livestock feed according to the present invention comprises a solidified product obtained by drying and solidifying a PVA solution in which polyvinyl alcohol is dissolved in a liquor production waste liquid. That is, among the industrial waste liquids, the liquor production waste liquid contains an organic component (organic solid) at a high concentration, and the PVA solution in which PVA is dissolved in the liquor production waste liquid is solidified by natural drying or heat drying. The water in the liquor production waste liquid is volatilized, and the organic component (organic solid) in the liquor production waste liquid is mixed in the solidified product. Therefore, the liquor production waste liquid can be utilized without solid-liquid separation to obtain a nutrient-rich livestock feed.

  The liquor production waste liquid is not limited and can be used without particular limitation as long as it is produced from the production of sake, beer, shochu, wine, etc. Among them, shochu waste liquid (shochu waste liquid) contains a lot of plant fiber. This is preferable.

  Moreover, in this livestock feed, the amount of PVA dissolved varies depending on the concentration of liquor production waste liquor, but is about 3 to 10 g, preferably 3 to 5 g, per liter of liquor production waste liquor.

The particle diameter measurement of the volcanic ejecta material (particulate matter) in this specification was performed by the following method (sieving method).
5 to 10 stages of standard sieves were attached to an electromagnetic sieve shaker (manufactured by Inoue Seiei Co., Ltd.), and the samples were classified by shaking and measured by the weight ratio of each particle category. That is, the standard sieves were stacked one on top of the other with a large mesh opening, 20 g of the sample was placed in the upper stage, shaken for 15 minutes, the weight of the sample for each mesh was measured, and the particle size distribution was determined.

The average particle diameter is calculated by calculating the ratio (% by weight) of the sieved particles for each mesh to the entire sample, and adding the ratio (% by weight) for each mesh from the top, before the value exceeds 50%. [D], a numerical value exceeding 50% is [e], and an under value (μm) of the mesh not exceeding 50% is [a]. Then, a mesh exceeding 50% was identified, and the weight average particle diameter was determined from the following formula (I), with the over value (μm) of the mesh being [b] and the under value being [c].
Average particle diameter (μm) = a − [(bc) × {(50−d) / e}] (I)

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited at all by the Example shown below.

Example 1
Mix 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Brewery Co., Ltd.) and heat to 70-80 ° C. while stirring to dissolve evenly. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohazu Nao Co., Ltd., average particle size of 180 μm, bulk density of 1.8 g / cm ³ ) was added to 5 kg of this polyvinyl alcohol aqueous solution, and a stirrer (Koyo Machine Industry ( A plastic kneaded product was obtained by thoroughly kneading with a mortar mixer (manufactured by Co. Ltd.). 2 kg of the obtained kneaded product was put into a 30 cm × 30 cm × 5 cm mold and press-molded at a pressure of 20 kgf / cm ² to obtain a panel-shaped molded product. And this panel-shaped molded object was taken out from the mold, and it heat-dried at 500 degreeC for 30 minute (s) in the hot air drying furnace, and solidified, and obtained the panel-shaped composite material whose density is 2.5 g / cm < ³ >.

Example 2
To 5 kg of the polyvinyl alcohol aqueous solution prepared in Example 1, a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyokazu Nao Co., Ltd.) and 2 kg of coal incineration ash (provided by Togaku) from a thermal power plant is added. A plastic kneaded product was obtained by thoroughly kneading with a stirrer. The kneaded product was molded, dried and solidified in the same manner as in Example 1 to produce a panel-shaped composite material having a density of 4.0 g / cm ³ .

Example 3
Mixing 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of shochu shochu waste liquid (manufactured by Akashi Sake Co., Ltd.) and heating to 70-80 ° C. while stirring to dissolve evenly By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) was added to 5 kg of this polyvinyl alcohol aqueous solution, and kneaded well with a stirrer to obtain a plastic kneaded product. The obtained kneaded product was divided into 1.8 kg and 0.2 kg, and 2 kg of 1.8 kg kneaded product was put into a 30 cm × 30 cm × 5 cm mold, press-molded at 20 kgf / cm ² , and 0.2 kg kneaded. 3 g of Western turf (Takii Seed Co., Ltd.) seeds were mixed uniformly into the product, and then all the seed kneaded product was developed on the surface of the press-molded product so as to form a uniform layer, and again 20 kg / cm ^2. Press molding was performed at a press pressure of. Thereafter, the press-molded product is taken out from the mold, dried by heating at 100 ° C. for 2 hours in a hot air drying furnace, and solidified to obtain a panel-like composite material containing seeds having a density of 2.8 g / cm ^3. It was. When 3 liters of water was sprayed on the panel-like composite material containing seeds, uniform germination was obtained on the 25th after spraying.

Example 4
3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed with 10 liters of barley shochu waste liquid (manufactured by Akashi Sake Co., Ltd.), and dissolved uniformly by heating to 70-80 ° C. with stirring. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of this polyvinyl alcohol aqueous solution was added with a mixture of 4 kg of Shirasu Balloon (“SKB-6000” produced by Toyohada Nao Co., Ltd.) and 2 kg of coal incineration ash (provided by Togaku) from a thermal power plant. By thoroughly kneading, a plastic kneaded product was obtained. The obtained kneaded material was divided into 1.8 kg and 0.2 kg, and thereafter a panel-shaped composite material having a density of 3.8 g / cm ³ was obtained under the same conditions as in Example 3.

Example 5
Mix 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Co., Ltd.) and dissolve evenly by stirring at 70-80 ° C. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) and 2 kg of charcoal incineration ash (provided by Toyosin Co., Ltd.) is added to 5 kg of this polyvinyl alcohol aqueous solution, and the mixture may be mixed with a stirrer. A plastic kneaded product was obtained by kneading. The obtained kneaded product was molded and heat-dried under the same conditions as in Example 1 to obtain a panel-shaped composite material having a density of 3.1 g / cm ³ .

Example 6
Mix 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Co., Ltd.) and dissolve evenly by stirring at 70-80 ° C. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) and 2 kg of charcoal incineration ash (provided by Toyosin Co., Ltd.) is added to 5 kg of this polyvinyl alcohol aqueous solution, and the mixture may be mixed with a stirrer. A plastic kneaded product was obtained by kneading. The obtained kneaded material was divided into 1.8 kg and 0.2 kg, and thereafter, molding and heat drying were performed under the same conditions as in Example 3 to obtain a panel-shaped composite material having a density of 3.3 g / cm ³ . .

Example 7
3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed with 10 liters of barley shochu waste liquid (manufactured by Akashi Sake Co., Ltd.), and dissolved uniformly by heating to 70-80 ° C. with stirring. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, a mixture of 5 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyokazu Nao Co., Ltd.) and 5 g of universal fertilizer (provided by Top Co., Ltd.) is added to 5 kg of this polyvinyl alcohol aqueous solution and kneaded well with a stirrer. As a result, a plastic kneaded product was obtained. Dividing the obtained kneaded material into 1.8 kg and 0.2 kg, dividing the obtained kneaded material into 1.8 kg and 0.2 kg, and thereafter performing molding and heat drying under the same conditions as in Example 3, A panel-shaped composite material having a density of 2.9 g / cm ³ was obtained.

Example 8
3 liters of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed in 10 liters of activated sludge liquid (manufactured by Koyu Shokutori Co., Ltd.), and uniformly dissolved by heating to 70-80 ° C. with stirring. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) was added to 5 kg of this polyvinyl alcohol aqueous solution, and kneaded well with a stirrer to obtain a plastic kneaded product. The obtained kneaded material was molded and heat-dried under the same conditions as in Example 1 to obtain a panel-shaped composite material having a density of 2.9 g / cm ³ .

Example 9
3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed in 10 liters of activated sludge liquid of shochu waste liquid (manufactured by Satsuma Processing Co., Ltd.) and heated to 70-80 ° C. with stirring. By dissolving uniformly, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) was added to 5 kg of this polyvinyl alcohol aqueous solution, and kneaded well with a stirrer to obtain a plastic kneaded product. The obtained kneaded product was molded and heat-dried under the same conditions as in Example 1 to obtain a panel-shaped composite material having a density of 3.0 g / cm ³ .

Example 10
3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed in 10 liters of activated sludge liquid of shochu waste liquid (manufactured by Satsuma Processing Co., Ltd.) and heated to 70-80 ° C. with stirring. By dissolving uniformly, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohazu Nao Co., Ltd.) and 2 kg of charcoal incineration ash (provided by Toyosin Co., Ltd.) is added to 5 kg of this polyvinyl alcohol aqueous solution and kneaded well with a stirrer. By doing so, a plastic kneaded product was obtained. The obtained kneaded material was divided into 1.8 kg and 0.2 kg, and thereafter a panel-like composite material containing seeds having a density of 2.9 g / cm ³ was obtained in the same manner as in Example 3.

Example 11
Mix 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Co., Ltd.) and dissolve evenly by stirring at 70-80 ° C. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of this polyvinyl alcohol aqueous solution was added with a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyokazu Nao Co., Ltd.) and 2 kg of coal incineration ash (provided by Dennogi Giken Co., Ltd.). By thoroughly kneading, a plastic kneaded product was obtained. The obtained kneaded material was formed into a granular material having a particle size range of 3 to 15 mm with a granulator (Umeki Seisakusho Co., Ltd., same disk system). Then, the granular material was heated and dried at 500 ° C. for 30 minutes in a rotary hot air drying furnace to produce a granular composite material. The bulk density of this granular composite material was 2.7 g / cm ³ .

Here, the bulk density (g / cm ³ ) is a so-called tapping density. After 50 g of a sample is put into a 200 cc cylinder and shaken for 5 minutes with an electromagnetic sieve shaker, the sample is taken from the scale of the cylinder. The volume (cm ³ ) (= cc) was read and the sample weight was divided by the volume.

Example 12
Mix 3 kg of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) with 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Co., Ltd.) and dissolve evenly by stirring at 70-80 ° C. By doing this, a concentrated polyvinyl alcohol aqueous solution was obtained. Next, 5 kg of this polyvinyl alcohol aqueous solution was added with a mixture of 4 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohada Nao Co., Ltd.) and 2 kg of coal incineration ash (provided by Togaku), and kneaded well with a stirrer. A plastic kneaded product was obtained. The resulting kneaded product was formed into granules having a particle size range of 3 to 10 mm with a granulator, and finally 600 g of seeds of Western turf (Takii Seedling Co., Ltd.) was uniformly sprinkled to fix the particles on the surface of the particles. Then, the granular material was heated and dried at 100 ° C. for 30 minutes in a rotary hot air drying furnace to obtain a granular composite material with seeds having a bulk density of 3.0 g / cm ³ .

Example 13
300 g of polyvinyl alcohol (“GOHSENOL N300” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is mixed in 10 liters of rice shochu waste liquid (manufactured by Akashi Sake Co., Ltd.), and uniformly dissolved by heating to 70-80 ° C. with stirring. By doing this, an aqueous polyvinyl alcohol solution was obtained. In this aqueous solution, 1 kg of shirasu raw material (manufactured by Wakamatsu Shoten Co., Ltd.) was uniformly mixed and stirred, and allowed to stand for 12 hours to separate 30% of organic matter and 70% of water. The sediment was dried by a hot air dryer at 500 ° C. or lower to form agglomerates, and the separated water was diluted 2.0 times with tap water to the discharge standard value.

Example 14
PVA 500 g was dissolved in 10 liter of the liquid portion obtained by separation in Example 13, and Portland cement (Asano) was previously added to 1 kg of Shirasu Balloon (“SKB-6000” manufactured by Toyohazu Nao Co., Ltd.) in this solution. A mixture in which 700 g (made by Cement Co., Ltd.) had been mixed was mixed and stirred, and this mixture was coated on the wall to a thickness of 3 mm with a trowel finish, and dried to produce a heat insulating wall material.

Experimental example 1
The granular composite material produced in Example 11 was spread on a 50 cm × 50 cm × 7 cm mold so as to have a thickness of about 5 cm, and then the seed-containing granular composite material obtained in Example 12 had a thickness of about 1 cm. After spreading, when 5 liters of water was sprayed, uniform germination was obtained 2 weeks after spraying.

Experimental example 2
The panel-shaped composite material (1.2 kg) of 30 cm × 30 cm × 5 cm produced in Example 10 was immersed in water for 30 minutes and then weighed. As a result, the weight was 4.3 kg, and the water absorption was 3.1 kg. It was. Therefore, 0.69 g water was absorbed per 1 cm ^3, and an excellent water absorbing ability was confirmed.

Experimental example 3
When the panel-like composite material in which water was absorbed in Experimental Example 2 was left in the factory (temperature 13 to 18 ° C., humidity 50 to 70%) for 40 days with almost the entire surface open, about 0.8 kg Was holding water. Therefore, it was confirmed that the combination of PVA and volcanic ejecta material has a sufficiently low water evaporation rate and exhibits excellent water retention.

Example 15
To 10 liter of waste liquid (wheat shochu waste liquid), 1 kg of PVA was added and dissolved while stirring at 80 to 90 ° C., and it was confirmed that PVA and the waste liquid were sufficiently mixed (40 minutes), and then a storage container ( Transferred to a plastic container). Although this operation was carried out on March 1, no spoilage or odor was observed until April 5, about a month later.

Test example 1 (bending strength test)
As shown in FIG. 1, the panel-shaped composite material produced in Example 10 is supported at two points (distance between fulcrums of 30 cm), a load is applied to the center position of the panel-shaped composite material, and bending is performed based on the following formula: The strength (kg / cm ² ) was calculated and found to be 30 kg / cm ² .

  In the formula, w is a load (kgf), l is a distance between fulcrums (cm), h is a member cross section length (cm), and b member cross section width (cm).

  Therefore, it was confirmed that the composite material had sufficient bending strength and was excellent in terms of mountability and handleability (transportation and workability).

It is a figure explaining the measuring method of the bending strength of a panel-like composite material.

Explanation of symbols

w Load l Distance between fulcrums h Member vertical section

Claims (9)

After dissolving polyvinyl alcohol in alcoholic beverages production waste, characterized by mixing and stirring the volcanic material consisting of shirasu balloons in the solution, solid-liquid separation process producing an alcoholic beverage waste. A composite material for greening material obtained by drying and solidifying a kneaded material containing volcanic ejecta material made of shirasu balloon , liquor production waste liquid and polyvinyl alcohol. The composite material according to claim 2 , wherein the kneaded product is a kneaded product further containing industrial waste incineration ash and / or coal incineration ash, and is obtained by drying and solidifying the kneaded product. The composite material according to claim 2 , wherein the kneaded material is a kneaded material further containing charcoal and / or activated carbon, and obtained by drying and solidifying the kneaded material. The composite material according to claim 2 , wherein the kneaded material is a kneaded material further containing an organic fertilizer and / or a synthetic fertilizer, and obtained by drying and solidifying the kneaded material. The composite material according to any one of claims 2 to 5 , which is a granular composite material obtained by molding the kneaded product into a granule, followed by drying and solidification. The composite material according to claim 6 , wherein plant seeds are fixed on the particle surface. After molding the kneaded product into panel-like, dried, a panel-like composite material obtained by solidifying, made to hold the at least one side of the surface layer of the seeds, any one of claims 2 to 5 The composite material according to one item. A concentrated polyvinyl alcohol solution in which 100 to 300 kg of polyvinyl alcohol is dissolved per liter of liquor production waste liquid, and a volcanic ejecta material consisting of 0.7 to 1.2 parts by weight of a shirasu balloon per 1 part by weight of the polyvinyl alcohol concentrated solution. The resulting kneaded product is molded into a desired shape, heated and dried, and is a lump of volcanic ejector material composed of shirasu balloons connected by polyvinyl alcohol polymer chains. A method for producing a composite material for a greening material comprising a lump in which organic components in the liquor production waste liquid are incorporated .

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