WO2020184882A1 - Porous body for improving water quality and method for manufacturing same - Google Patents

Porous body for improving water quality and method for manufacturing same Download PDF

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Publication number
WO2020184882A1
WO2020184882A1 PCT/KR2020/002954 KR2020002954W WO2020184882A1 WO 2020184882 A1 WO2020184882 A1 WO 2020184882A1 KR 2020002954 W KR2020002954 W KR 2020002954W WO 2020184882 A1 WO2020184882 A1 WO 2020184882A1
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Prior art keywords
porous body
genus
water quality
improving water
specific gravity
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PCT/KR2020/002954
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French (fr)
Korean (ko)
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권병현
권혁대
최병태
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권병현
권혁대
최병태
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Publication of WO2020184882A1 publication Critical patent/WO2020184882A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents

Definitions

  • the present invention relates to a porous body for improving water quality and a method of manufacturing the same, and in detail, as a porous body for improving water quality including loess, silicate, and a foaming agent, the porous body has a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, ratio It is characterized in that the surface area is 1 to 1,000 m 2 /g.
  • the color of the water becomes green, brown, red, etc., and it blocks photosynthesis to produce harmful substances, so it causes great damage to rivers, freshwater or aquaculture by killing fish or shellfish. .
  • loess when a large amount of loess is sprayed, suspended matter increases temporarily, causing breathing disorders due to gill closure of fish and mortality of fish and shellfish due to precipitation of loess, requiring cumbersome work to remove these loess deposits. It will cause side effects such as.
  • the present invention has been conceived to solve the above problems, and an object of the present invention is to provide a method for producing a molded article having pores by molding a composition containing loess, silicate and a foaming agent, and then firing the composition.
  • Another aspect of the present invention is to provide a porous body for improving water quality that can effectively remove floating oil by being precipitated in water.
  • Another object of the present invention is to provide a porous body for improving water quality provided so that the molded body in which the pores are formed is configured to have a strength of more than a certain level and is not easily destroyed.
  • Another object of the present invention is to provide a porous body for improving water quality that does not require recollection after the sprayed molded body is reduced to sand as time passes.
  • the present invention relates to a porous body for improving water quality and a method of manufacturing the same.
  • One aspect of the present invention is a porous body for improving water quality
  • a porous body for improving water quality comprising an inorganic coagulant containing a metal oxide, a silicate, and a foaming agent, the porous body has a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, a specific surface area of 1 to 1,000 m2 It relates to a porous body for improving water quality, characterized in that /g.
  • the silicate is characterized by having a structure represented by the following formula (1).
  • A is any one selected from sodium, potassium, lithium, rubidium, and cesium, and n is an integer of 1 to 5.
  • the blowing agent is nitrostyrene, methoxystyrene, ⁇ -methylstyrene, o-, m-, p-methylstyrene, methylsilylstyrene, vinylnaphthalene, vinylbiphenyl, vinylanthracene, vinylchloride, vinylthiophene , Vinylpyrrolidone, vinylpyridine, sulfoxystyrene, styrenesuloxida, cyanostyrene, aminostyrene, ethylstyrene, ⁇ -ethylstyrene, carboxystyrene, chlorostyrene, any one selected from phenylstyrene and hydroxystyrene Or a vinyl resin in which a plurality of monomers are polymerized,
  • the blowing agent is characterized in that it further comprises one or a plurality of weight agents selected from copper sulfate, copper oxide, silver nitrate, boron oxide, zinc oxide, thorium dioxide, magnesium oxide, titanium dioxide, tricalcium phosphate, aluminum oxide and graphite. do.
  • the porous body is characterized in that it contains any one or a plurality of specific gravity control agents selected from calcium chloride, magnesium chloride, and lithium chloride inside, and in more detail, the specific gravity control agent is an aluminophosphate zeolite, ferroaluminophosphate zeolite. And any one or more zeolites selected from silicoaluminophosphate zeolites.
  • the porous body has on the surface Acinetobacter genus, Atrobacter genus, Rhodococcy genus, Mycobacterium genus, Pseudomonas genus, Xanthobacter genus, Lactobacillus genus, Saccharomyces genus, Rhodo pseudomonas genus, Streptomyces
  • a coating agent containing any one or a plurality of strains selected from the genus Sess Dimonas, Strombidnoxis, Corenensis and Pantoea is coated, and in more detail, the strains are Atrobacter genus and Xantho It is characterized in that the genus Bacter and the genus Pantoea are mixed.
  • the molded body includes any one or a plurality of strains selected from the genus Atrobacter, genus Xanthobacter, genus Lactobacillus, genus Saccharomyces, genus Rhodomonas, genus Streptomyces, and genus Pantoea. Characterized in that.
  • the porous body according to the present invention has a specific gravity in the range of 0.5 to 1.5 and is configured to gradually sink in water, thereby effectively removing pollutants that are precipitated and suspended in water.
  • the porous body is configured to have a strength of a certain or more so that it is not easily destroyed, it is possible to exhibit a longer-term water purification power.
  • the porous body sprayed on the contaminated area is reduced to sand over time, preventing secondary pollution by the porous body, and providing a porous body for improving water quality that does not require recollection after spraying.
  • first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term.
  • a component is described as being “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to that other component, but another component between each component It should be understood that elements may be “connected”, “coupled” or “connected”.
  • step a) is to prepare a molded article by mixing an inorganic coagulant including a metal oxide, a silicate, and a foaming agent, and processability may be further improved by mixing a solvent such as water and ethanol in the composition.
  • the green algae phenomenon that occurs in summer occurs mainly in rivers or lakes with very low flow rates, and makes the water look dark green.
  • blue-green algae which occur from early summer to autumn, mainly cause hydration and cause water pollution problems such as reduced dissolved oxygen, fish resource death, taste and taste, and water purification problems.
  • water pollution problems such as reduced dissolved oxygen, fish resource death, taste and taste, and water purification problems.
  • liver and neurotoxins such as microcysteine and anatoxin.
  • the National Academy of Environmental Sciences has designated four species, Microcystis, Anabaena, Oscillatoria, and Aphanizomenon, as harmful blue-green algae (NIER, 2016).
  • the inorganic coagulant plays the most important role in resolving the green algae phenomenon as described above, and plankton co-precipitates by coagulation or adsorption on colloidal particles, or nutrients existing in the water environment due to physical or chemical adsorption. It plays a role in controlling the green algae by removing them.
  • the metal oxide is a main component of the soil, and the content may vary depending on the type of soil, but silica (SiO 2 ), alumina (Al 2 O 3 ), iron oxide (III) (Fe 2 O 3 ), Iron (II) oxide (FeO), titanium dioxide (TiO 2 ), manganese oxide (MnO), lime (CaO) and magnesium oxide (MgO) may include any one or more selected from.
  • the inorganic coagulant containing the metal oxide is preferably loess.
  • the loess has a large amount of calcium carbonate, and the calcium carbonate exhibits viscosity upon contact with water, making it easy to form. It also contains a component called illite, which has the effect of adsorbing and decomposing pollutants.
  • the loess is a honeycomb structure with a wide surface, and a number of spaces form a multi-layered structure, and this space serves to adsorb plankton, nutrients, and other toxins produced by green algae.
  • the loess is yellow to reddish brown weathered soil or weathered sediments formed due to chemical weathering of rocks, and means a sediment composed of soil particles having most of the particle diameters of 0.002 to 0.02 mm.
  • the loess is determined according to the kind of minerals it contains, examples of the minerals include kaolinite, haloysite, illite, vermiculite, chlorite, and the like, and the present invention is not limited to the kind of these minerals. Any type that is recognized as loess can be used.
  • the loess when the loess is mixed with a solvent, it is preferable to add 60 to 80 parts by weight based on 100 parts by weight of the solvent. In the above range, it is preferable because it is possible to adsorb organic substances, which are inherent characteristics of loess, and to maintain the mechanical strength of the porous body itself.
  • the silicate is a kind of adhesive that holds the loess particles, which varies depending on the component, but has a low melting point and is melted by heating, and then combined with the loess and cooled to make the porous body have a certain strength.
  • the silicate may have a structure represented by the following formula (1).
  • A is any one selected from sodium, potassium, lithium, rubidium, and cesium, and n is an integer of 1 to 5.
  • the above silicate reacts with an acid or the like, it exhibits strong alkalinity and causes a violent reaction.
  • the mechanical properties of the porous body can be increased by three-dimensionally arranging the basic oxygen that forms the glass phase and forms the structure.
  • the silicate is preferably added in the form of water glass.
  • water glass can be obtained by melting a mixture of silica sand and soda ash at 1,300 to 1,500°C and treating it in a high-pressure steam cooker. Since it absorbs carbon dioxide in the air and precipitates gel-like silicic acid, it exhibits strong adhesion.
  • Such water glass is a silica gel that is neutralized with acid and dried with an acid, and is used as a drying agent. In addition, if moisture is evaporated from the water glass or heated water glass anhydride and a small amount of water, hydrated water glass is formed. This water-containing glass becomes a raw material for adhesives, bonding agents, and refractory cement.
  • Water glass has a tetrahedral structure that is common to many other forms of silica or crystalline silica, which share oxygen in the form of silicate tetrahedral monomolecules or Si-O-Si bridges, and thus have a polymer form.
  • the overall structure of water-soluble sodium silicate is an irregular arrangement of molecules of Na 2 O and SiO 4 , which are shared cations. Since it has such a structure, water glass exhibits the property of expanding during the expansion process, and foaming occurs. Such foaming creates pores in the molded body when mixed with loess, and has the effect of adsorbing organic matter, green algae, toxic components, and oil.
  • the water glass it is preferable to add 20 to 40 parts by weight of the water glass based on 100 parts by weight of the solvent. If it is less than the above range, the mechanical properties of the porous body are deteriorated due to the decrease in adhesive properties, and when it is added in excess of 40 parts by weight, it is difficult to control the specific gravity of the porous body due to excessive foaming.
  • the foaming agent is to form pores in the porous body separately from the water glass, and it is possible to form pores by generating gas through a chemical reaction or by being mixed with the loess or silicate in the form of particles and then removed during firing. have.
  • foaming agent in the present invention examples include nitrostyrene, methoxystyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, methylsilylstyrene, vinylnaphthalene, vinylbiphenyl, vinylanthracene , Vinyl chloride, vinylthiophene, vinylpyrrolidone, vinylpyridine, sulfoxystyrene, cyanostyrene, aminostyrene, ethylstyrene, ⁇ -ethylstyrene, carboxystyrene, chlorostyrene, phenylstyrene and hydroxystyrene monomers It may include a polymerized vinyl-based resin, and organic solvents such as alcohols and esters may be further included therein.
  • the blowing agent is normal hexane, normal heptane, methylcyclohexanol, 1-butanol, 2-butanol, cyclopentanone, cyclohexanone, cyclohexanol, cyclohexane, 2-ethyl-1 -Swelling agents such as hexanol and ethylbenzene may be further included, and these may also be used by mixing with an organic solvent.
  • the foaming agent may further include a weighting agent that adjusts the specific gravity of the porous body, if necessary.
  • the weight agent is a metal compound, and has an additional sterilizing effect in addition to increasing the specific gravity of the porous body by using metals such as copper, silver, boron, zinc, and magnesium as a main component, which have inhibitory power against microorganisms or strains.
  • weight agent examples include copper sulfate, copper oxide, silver nitrate, boron oxide, zinc oxide, thorium dioxide, magnesium oxide, titanium dioxide, tricalcium phosphate, aluminum oxide and graphite, and these may be used alone or in two or more It can be mixed and used.
  • the weight agent is preferably mixed with the foaming agent, and the amount of the foaming agent and the weight agent is not limited, but in the case of the foaming agent, it is preferable to add 1 to 5 parts by weight based on 100 parts by weight of the solvent, and the weight agent Substituting and mixing 10 to 20% by weight of the foaming agent is preferable because it can satisfy both the specific gravity control and foaming effect.
  • the solvent is a liquid for mixing the loess, silicate, foaming agent, etc.
  • the type is not limited, but water or methanol, 1-butanol, 2-butanol, ethanol, isobutyl alcohol, isopropyl alcohol Alcohols such as isopentyl alcohol, propan-1-ol, and propan-2-ol; Ethers such as dimethyl ether, ethyl ether, and tetrahydrofuran; Ketones such as methylbutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, acetone, etc. can be used, and in addition, glycol ether, aldehyde, ester, or a mixed solvent thereof can be used.
  • step a) may be performed by mixing loess, silicate, foaming agent, and the like, and molding it into a spherical molded body.
  • the molding method is not limited in the present invention, but a method of putting in a mold or cutting after spinning may be applied, and the particle diameter is also not limited, but is preferably 1 to 30 mm.
  • At least one specific gravity control agent may be further added in step a) so that the manufactured porous body can slowly sink.
  • yellow soil is sprayed in the form of particles when green algae occurs as described above, but when spraying the red soil in a general manner, secondary ecosystem disturbances such as damage to benthic organisms caused by the settled red soil It is a concern, and it is important to ensure the removal time of plankton by allowing the loess to float on the water surface for a certain period of time or more, as it may cause aesthetic contamination when spraying in large quantities, and then the removed plankton may be reactivated after a certain period of time. .
  • the present invention is formed on the surface by adding a component capable of adsorbing moisture to increase the specific gravity by absorbing moisture penetrating into the pores of the porous body, and allowing the porous body to gradually sink due to the increased specific gravity. It secures time to remove harmful components such as green algae, oil, and toxins, and at the same time, it can exert water purification power for a certain period of time while the adsorbed porous body sinks to the bottom.
  • the specific gravity control agent may be one or more metal chlorides, preferably any one or more selected from calcium chloride, magnesium chloride, and lithium chloride. Since the metal chloride has high deliquescent properties, it easily reacts with water and dissolves in a liquid state, and its specific gravity increases compared to the original material. Accordingly, the specific gravity of the entire porous body is increased, and the porous body sinks in water over time.
  • the specific gravity control agent when the specific gravity control agent is liquefied due to the high deliquescent properties as described above, the specific gravity control agent may dissolve and leak out of the porous body.
  • aluminophosphate zeolite, ferroaluminophosphate zeolite, and silicoaluminophosphate type It is preferable to solidify by impregnating at least one zeolite such as zeolite.
  • zeolite it has a specific gravity or more, and pores are formed on the surface to easily impregnate the metal chloride, and at the same time, the hygroscopicity of the metal chloride may be combined to cause a synergistic effect.
  • the specific gravity control agent is preferably formed inside rather than on the surface of the porous body, and more preferably, the zeolite impregnated with the metal chloride is used as the interior, and the surface of the zeolite is again coated with a mixture of ocher, silicate, and a foaming agent to form an outer layer. Forming is good because it secures a movement time of moisture moving inside the porous layer for a certain amount or more, prevents a rapid increase in specific gravity, and at the same time secures the mechanical properties of the porous body.
  • the amount of the specific gravity control agent is not limited, and when it is added in the form of a core, it is preferable to add it so as to be 5 to 15% by volume of the total porous body, since the specific gravity increase and mechanical properties can be satisfied.
  • the molded body When the molded body is manufactured as described above, it can be dried at a certain temperature before firing. The drying is to remove moisture inside the molded body, particularly moisture adsorbed to the pores, to maintain a constant specific gravity, and at the same time, it is possible to prevent weakening of physical properties such as expansion, breakage, cracking, etc. due to rapid heating of the molded body.
  • step b) is preferably carried out at 300 to 500° C. for 2 to 5 hours after putting the molded body in a kiln or dryer. If it is less than the above range, the porous body may be broken during firing due to insufficient drying time, and when heating exceeding the above range, all internal organic matters are deteriorated prior to stabilization of the porous body, and mechanical properties may be reduced.
  • the dried molded body can be baked at 800 to 1,000° C. for 5 to 10 hours to complete the porous body.
  • the foaming agent is deteriorated and vaporized to form pores, and silicates such as water glass are also melted and recrystallized to physically bond with loess to create a porous body that maintains a certain or more breaking strength.
  • loess may be coated on the surface of the porous body to adjust the specific gravity of the fired porous body.
  • the loess is a reddish natural soil containing hydrated iron oxide and anhydrous iron oxide, and contains materials such as SiO 2 , Al 2 O 3 , Fe 2 O 3 , Na 2 O, CaO, TiO 2 , MgO, etc. It contains a large amount and can exert beneficial effects on the human body.
  • This loess has various eco-friendly properties such as decomposition power, self-cleaning power, and far-infrared rays emitted from the loess, antibacterial, insect repellent, air purification and deodorization.
  • the specific gravity of the loess may be increased or decreased by adjusting the content of iron oxide according to the specific gravity of the porous body.
  • silica SiO 2
  • CaO calcium oxide
  • aluminum oxide aluminum oxide
  • iron oxide has a specific gravity of 4.5 to 5.2, which is much higher than other metal oxides, so the content of iron oxide is higher.
  • By adjusting the specific gravity can be easily increased or decreased.
  • the content of iron oxide in the loess is 2 to 5% by weight, it is preferable to determine the amount of iron oxide added within the above range.
  • the specific gravity of the loess it is preferable to increase or decrease the specific gravity of the loess depending on the purpose of use. For example, in the case of removing oil, it is desirable to increase the specific gravity of the loess so that the oil-adsorbed porous body quickly sinks from the surface while adsorbing in a large amount as quickly as possible floating on the water surface. This is because underwater bacteria induce decomposition of oil adsorbed on the porous body, and if the porous body floats on the surface for a long time, it may interfere with the exchange of gas and block light, which may adversely affect the ecosystem.
  • green algae and red algae are floating algae, it is preferable to lower the specific gravity of the loess so that they stay on the water surface for as long as possible to adsorb algae.
  • the ocher After the ocher is coated on the surface of the porous body as described above, it is dried at room temperature to cure the coated ocher. At this time, since the covered loess cracks when exposed to sunlight, it is preferable to dry it in the shade, and the drying time is not limited, but it is preferable to sufficiently dry it under appropriate humidity so that water can be completely removed.
  • the surface of the porous body may be coated with a coating agent.
  • the coating agent is a mixture of a polymer that forms a film on the surface of the porous body with a strain capable of digesting, absorbing, and removing harmful components such as green algae, red algae, toxins, and other oils, and one or more cellulose polymers
  • the strain of may be coated.
  • the cellulose polymer is a natural polymer obtained from cotton, wood, grain, etc., and may preferably include water-soluble cellulose or modified starch reacted with one or more ethers.
  • the natural cellulose forms a film on the surface of the porous body to provide nutrients that the strain can decompose and solubilize, and at the same time maintain the viscosity of the coating agent.
  • the modified starch is generally used as a gelling agent, a coating agent, and the like, and may perform a role of fixing a strain and supplying nutrients.
  • the coating agent is preferably modified starch. This makes it easy to control the dissolution and emulsification time in water, thereby preventing the strain from being dispersed and lost in water. In addition, nutrients such as sugars can be effectively supplied to the strain.
  • the cellulose polymer it is preferable to add 10 to 50 parts by weight of the cellulose polymer based on 100 parts by weight of the solvent. If it is less than the above range, the viscosity of the coating agent may not be sufficiently maintained, so that the thickness of the coating agent may be formed thin, and when added in excess of the above range, the strain may not be properly exposed to green algae or the strain may disappear due to a rapid increase in viscosity. .
  • the strain is for adsorption, digestion, and removal of algae such as green algae and red algae, and other suspended matters such as oil and toxins, for example, Acinetobacter genus, Atrobacter genus, Rhodococsay genus, Mycobacterium Genus, Pseudomonas genus, Xanthobacter genus, Lactobacillus genus, Saccharomyces genus, Rhodo Pseudomonas genus, Streptomyces genus, and Pantoea genus may be mentioned.
  • Acinetobacter genus Atrobacter genus, Rhodococsay genus
  • Mycobacterium Genus Pseudomonas genus
  • Xanthobacter genus Xanthobacter genus
  • Lactobacillus genus Saccharomyces genus
  • Rhodo Pseudomonas genus Streptomyces gen
  • the strain may be varied depending on the location and purpose of the porous body to be prepared. For example, for purification of wastewater and adsorption of targel, it is recommended to mix Acinetobacter genus, Atrobacter genus, Rodococci genus, Mycobacterium genus, Pseudomonas genus, etc. It is good to mix the genus Bacter, the genus Xanthobacter, the genus Dimonas, the genus Stromboid Noxis, and the genus Coriansis. In addition, for digestion of crude oil, etc., Atrobacter genus or pantoea genus to remove toxins may be added.
  • the strain is more preferably a mixture of the genus Atrobacter, the genus Xanthobacter, and the genus Pantoea.
  • the strains of the genus Atrobacter can effectively remove contaminants such as crude oil, and the strains of the genus Xanthobacter have the highest acaricidal activity and high algal activity in all growth stages of algae.
  • the genus Pantoea can remove neurotoxins or liver poisons generated by the algae.
  • the strain may be added in an amount of 1 to 5 parts by weight relative to 100 parts by weight of the solvent, and when one or more strains are added as described above, particularly when Atrobacter genus, Xanthobacter genus, and Pantoea genus are mixed, the amount of each strain added It is preferable to satisfy this 0.5 to 1 part by weight.
  • the coating agent may be further added to one or more aromatic oils to enhance nutrient supply to strains to be mixed together and to remove liver poison generated by algae along with the pantoea genus.
  • the aromatic oil is extracted from the fruits, leaves, stems, etc. of plants through steam distillation, hot water distillation, oil adsorption, etc., for example, citronellal, geranyl acetate, citronellyl acetate, citronellol, krypton , Linalul, cuminol, nonanoic acid, naringin, geranial, piperitone, and the like.
  • the aromatic oil may be a mixture of linalul and naringin.
  • the linalul increases the activity of the strains of the genus Pantoea so that toxins are removed from the strain, and Naringin can also inhibit apoptosis caused by hepatotoxicity in addition to increasing the activity of the strain and supplying nutrients.
  • the aromatic oil as described above contains 0.1 to 1 parts by weight of 100 parts by weight of the solvent, and when mixing naringin and linalul, mixing at a ratio of 1:1 to 2 by weight is preferable because the above effect can be further maximized.
  • the solvent is for dissolving or mixing the strain, cellulose polymer, aromatic oil, and the like, and water or a mixture of water and alcohol is preferably used.
  • the ingredients are first stirred and mixed to prepare a coating agent, and then the fired molded body is immersed in the coating agent, and then dried.
  • the coating conditions are not limited in the present invention, but can be completed by immersing at room temperature (20 to 25°C) for about 30 minutes, then taking it out and drying it at 30 to 40°C until a film is formed on the surface of the molded body. .
  • the present invention includes a porous body for improving water quality prepared as described above.
  • the porous body for improving water quality may have a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, and a specific surface area of 1 to 1,000 m2/g.
  • green algae, red algae, oil bands in rivers or seas After adsorbing harmful components such as toxins and other toxins, contaminants can be effectively removed by gradually sinking into water.
  • the submerged porous body as described above contains natural components such as loess and silicate, it is reduced to sand over time to prevent secondary contamination by the porous body and prevent labor input such as recollection after use. It's economical.
  • a molded body 70 parts by weight of loess, 30 parts by weight of water-soluble sodium silicate, and 3 parts by weight of a nitrostyrene polymer (weight average molecular weight 3,000) as a blowing agent are added to 100 parts by weight of water, and 10% by weight (0.3 parts by weight) of the blowing agent. ) was replaced with copper sulfate.
  • the molded body composition was mixed and molded into spheres with a diameter of 15 mm, then put into a drying furnace, dried at 350° C. for 3 hours, taken out, and cooled to room temperature. Then, the molded body was again put into a heat treatment furnace and fired at 900° C. for 8 hours, and then the surface of the molded body was covered with loess and dried to complete the molded body.
  • Example 1 when manufacturing the porous body, a specific gravity control agent was further added. Specifically, zeolite with a diameter of 1.5 mm was added to a solution in which calcium chloride and water were mixed in a weight ratio of 1:2. And after sufficiently stirring this, it was put into a 200 °C oven and completely dried for 24 hours. The molded body composition prepared in Example 1 was applied to the dried specific gravity control agent on the surface to have a spherical shape of 15 mm. Except for the same method, a porous body for improving water quality was manufactured.
  • a porous body for improving water quality was prepared in the same manner as in Example 2, except that a coating solution obtained by mixing 1 part by weight of each culture solution of Arthrobacter chlorophenolicus, xanthobacter autotrophicus, and Pantoea agglomerans as strains was used.
  • a porous body for improving water quality was prepared in the same manner as in Example 3, except that 0.5 parts by weight of linalul as a fragrance oil was added to the coating solution when preparing the porous body.
  • a porous body for improving water quality was prepared in the same manner as in Example 4, except that 0.5 parts by weight of aroma oil mixed in a 1.5:1 weight ratio of linalul and naringin was added.
  • Example 1 in which the specific gravity control agent was not further added to the porous body did not show a significant difference in the water quality improvement effect from Example 2, but the porous body did not sink, so it was not aesthetically pleasing, and when applied to a general lake or sea, It is concerned that it could adversely affect the aquatic ecosystem by blocking the transmitted sunlight.
  • Example 3 in which three strains were mixed and added, there was an increase in the amount of dissolved oxygen, the total amount of phosphorus, and the amount of nitrogen, and in particular, it can be seen that the rate of reduction in the amount of crude oil increased significantly.
  • Example 4 in which linalul was further added as aromatic oil, and Example 5 in which linalul and naringin were further added, increased the activity of the strain and increased toxin removal rate, showing excellent results in the fish toxicity test items.

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Abstract

Manufactured to have the specific gravity range from 0.5 to 1.5, a porous body according to the present invention is configured to gradually sink in water, thereby effectively removing pollutants which are deposited and float in water. In addition, the porous body has a certain strength sufficient not to be readily destroyed, thus exhibiting water purification performance for a long period of time. Furthermore, the porous body which has been applied to a polluted area is reverted to sand over time so that the secondary pollution by the porous body can be prevented. Thus, a porous body that needs not to be recollected after application can be provided.

Description

수질 개선용 다공체 및 이의 제조방법Porous body for water quality improvement and manufacturing method thereof
본 발명은 수질 개선용 다공체 및 이의 제조방법에 관한 것으로, 상세하게는 황토, 규산염 및 발포제를 포함하는 수질 개선용 다공체로, 상기 다공체는 비중이 0.5 내지 1.5이며, 기공율이 10 내지 60%, 비표면적이 1 내지 1,000㎡/g인 것을 특징으로 한다.The present invention relates to a porous body for improving water quality and a method of manufacturing the same, and in detail, as a porous body for improving water quality including loess, silicate, and a foaming agent, the porous body has a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, ratio It is characterized in that the surface area is 1 to 1,000 m 2 /g.
일반적으로 가정의 생활하수 또는 가축의 배설물 및 유조선의 기름 등이 하천에 유입되면 수질의 부영양화가 진행되고, 부유성 조류 즉, 식물성 플랑크론이 과다 증식되어 수질을 오염시키게 된다.In general, when household sewage or livestock excrement and oil from tankers enter the river, eutrophication of the water quality proceeds, and floating algae, that is, phytoplancron, is excessively proliferated, contaminating the water quality.
식물성 플랑크톤은 그 종류에 따라 수질의 색깔이 녹색, 갈색, 적색 등을 띄게 되고, 광합성을 차단하여 유해물질을 생성하게 되므로, 어류 또는 어패류 등을 폐사시켜 강, 담수 또는 양식장 등에 큰 피해를 주게 된다.Depending on the type of phytoplankton, the color of the water becomes green, brown, red, etc., and it blocks photosynthesis to produce harmful substances, so it causes great damage to rivers, freshwater or aquaculture by killing fish or shellfish. .
한편, 근래 세계 각국의 녹, 적조 발생 후 제거 대책에 대한 연구 동향으로서, 황산구리 등의 화학약품 또는 해양식물에서 추출한 물질을 살포하거나 초음파를 방사하여 적조생물을 죽이는 방법 또는 오존으로 적조생물의 특성을 중화하는 방법, 천적을 이용하여 적조생물을 죽이는 방법 등이 개발되고 있으나 황토를 살포하는 방법은 비용이 저렴하면서도 상대적으로 효과가 우수하여 가장 경제성 있는 방법으로 평가받고 있다.Meanwhile, as a recent research trend on measures to remove rust and red tide after the occurrence of rust and red tide in countries around the world, a method of killing red tide creatures by spraying chemicals such as copper sulfate or substances extracted from marine plants or radiating ultrasonic waves, or the characteristics of red tide creatures with ozone A method of neutralizing and killing red tide creatures using natural enemies is being developed, but the method of spraying loess is evaluated as the most economical method because it is inexpensive and relatively effective.
국내의 경우 1996년부터 지방자치단체와 국립수산진흥원을 중심으로 황토를 대량으로 살포하여 녹조 및 적조 방제 대책을 수립하고 있으나, 황토 살포 시기 및 방법에 대한 정량적인 연구가 미흡한 실정이며, 실제적으로는 적조 발생 시 황토를 삽 또는 수압을 이용하여 오염지역에 대량 살포함으로써 오염물질을 침전시키고 있다.In Korea, since 1996, local governments and the National Fisheries Promotion Agency have established measures to control green algae and red tide by spraying large amounts of loess, but quantitative research on the timing and method of spraying loess is insufficient. In the event of red tide, pollutants are precipitated by spraying the loess over the contaminated area using a shovel or water pressure.
그러나 상기와 같은 방법으로 황토를 살포할 경우 많은 인력과 시간이 소요되며 넓은 오염범위에 황토를 고루 살포하는 것이 어려울 뿐만 아니라, 살포된 황토가 유해 플랑크톤과 함께 수중에 침전되어 바닥에 서식하는 어패류 등에 피해를 주는 2차 오염을 발생시키고 있다.However, when spraying the loess in the above manner, it takes a lot of manpower and time, and it is difficult to evenly spray the loess over a wide range of pollution, and the sprayed loess is settled in the water along with harmful plankton, so that fish and shellfish living on the bottom are It is generating secondary pollution that causes damage.
또한, 황토를 대량으로 살포할 경우 부유물질이 일시적으로 증가하게 되어 어류의 아가미 폐쇄로 인한 호흡장애 및 황토의 침전으로 인한 어패류 폐사 등을 유발하게 되어 이러한 황토 퇴적층을 제거해야 하는 번거로운 작업이 요구되는 등의 부작용을 발생시키게 된다.In addition, when a large amount of loess is sprayed, suspended matter increases temporarily, causing breathing disorders due to gill closure of fish and mortality of fish and shellfish due to precipitation of loess, requiring cumbersome work to remove these loess deposits. It will cause side effects such as.
현재 식수의 경우에도 식수원에 분포된 수질 요염 물질과 녹조로 인해 그 정화에 어려움을 겪고 있으며, 수질의 정화를 위해 살포된 다량의 황토를 강바닥으로부터 다시 제거하여야 하는 어려움이 있다.Even in the case of current drinking water, it is difficult to purify the water due to pollutant substances and green algae distributed in the drinking water source, and there is a difficulty in removing a large amount of red soil sprayed from the river bed again to purify the water quality.
또한, 유조선의 기름유출 사고와 같은 상황이 발생 될 경우, 타르겔과 같은 중등유가 해저로 침전되며, 조류나 파도에 따라 이동하면서 광범위한 범위로 확대되어 방제에 대한 어려움이 가중되고 있다.In addition, when a situation such as an oil spill from an oil tanker occurs, secondary oil such as targel is deposited on the sea floor, and it is expanded to a wide range as it moves along with currents and waves, increasing the difficulty in control.
이에, 침전된 타르겔에 부착된 채로 기름 성분을 용이하게 분해시키고 정화시킬 수 있는 성형체의 필요성이 요구되고 있는 실정이다.Accordingly, there is a need for a molded body capable of easily decomposing and purifying oil components while adhering to the precipitated targel.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로, 황토, 규산염 및 발포제를 포함하는 조성물을 성형한 후, 이를 소성하여 기공을 갖는 성형체를 제조하는 방법의 제공을 목적으로 한다.The present invention has been conceived to solve the above problems, and an object of the present invention is to provide a method for producing a molded article having pores by molding a composition containing loess, silicate and a foaming agent, and then firing the composition.
본 발명의 다른 양태는 물속에 침전되어 부유하는 기름을 효과적으로 제거할 수 있는 수질 개선용 다공체를 제공하는 것이다.Another aspect of the present invention is to provide a porous body for improving water quality that can effectively remove floating oil by being precipitated in water.
본 발명의 또 다른 목적은, 상기 기공이 형성된 성형체가 일정이상의 강도로 구성되어 용이하게 파괴되지 않도록 마련된 수질 개선용 다공체를 제공하는 것이다.Another object of the present invention is to provide a porous body for improving water quality provided so that the molded body in which the pores are formed is configured to have a strength of more than a certain level and is not easily destroyed.
본 발명의 또 다른 목적은, 살포된 성형체가 시간이 흐름에 따라 모래로 환원되어 살포 후, 재수거가 필요 없는 수질 개선용 다공체를 제공하는 것이다.Another object of the present invention is to provide a porous body for improving water quality that does not require recollection after the sprayed molded body is reduced to sand as time passes.
본 발명은 수질 개선용 다공체 및 이의 제조방법에 관한 것이다.The present invention relates to a porous body for improving water quality and a method of manufacturing the same.
본 발명의 일 양태는 금속산화물을 포함하는 무기응집제, 규산염 및 발포제를 포함하는 수질 개선용 다공체로, 상기 다공체는 비중이 0.5 내지 1.5이며, 기공율이 10 내지 60%, 비표면적이 1 내지 1,000㎡/g인 것을 특징으로 하는 수질 개선용 다공체에 관한 것이다.One aspect of the present invention is a porous body for improving water quality comprising an inorganic coagulant containing a metal oxide, a silicate, and a foaming agent, the porous body has a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, a specific surface area of 1 to 1,000 ㎡ It relates to a porous body for improving water quality, characterized in that /g.
본 발명에서 상기 규산염은 하기 화학식 1의 구조를 갖는 것을 특징으로 한다.In the present invention, the silicate is characterized by having a structure represented by the following formula (1).
[화학식 1][Formula 1]
A2O-nSiO2 A 2 O-nSiO 2
(상기 화학식 1에서 A는 나트륨, 칼륨, 리튬, 루비듐 및 세슘에서 선택되는 어느 하나이며, 상기 n은 1 내지 5의 정수이다.)(In Formula 1, A is any one selected from sodium, potassium, lithium, rubidium, and cesium, and n is an integer of 1 to 5.)
또한 본 발명에서 상기 발포제는 니트로스티렌, 메톡시스티렌, β-메틸스티렌, o-, m-, p-메틸스티렌, 메틸실릴스티렌, 비닐나프탈렌, 비닐비페닐, 비닐안트라센, 비닐클로라이드, 비닐티오펜, 비닐피롤리돈, 비닐피리딘, 술폭시스티렌, 스티렌술 산소다, 시아노스티렌, 아미노스티렌, 에틸스티렌, β-에틸스티렌, 카르복시스티렌, 클로로스티렌, 페닐스티렌 및 하이드록시스티렌에서 선택되는 어느 하나 또는 복수의 모노머가 중합된 비닐계 수지를 포함하는 것을 특징으로 하며,In addition, in the present invention, the blowing agent is nitrostyrene, methoxystyrene, β-methylstyrene, o-, m-, p-methylstyrene, methylsilylstyrene, vinylnaphthalene, vinylbiphenyl, vinylanthracene, vinylchloride, vinylthiophene , Vinylpyrrolidone, vinylpyridine, sulfoxystyrene, styrenesuloxida, cyanostyrene, aminostyrene, ethylstyrene, β-ethylstyrene, carboxystyrene, chlorostyrene, any one selected from phenylstyrene and hydroxystyrene Or a vinyl resin in which a plurality of monomers are polymerized,
상기 발포제는 황산구리, 산화구리, 질산은, 산화붕소, 산화아연, 이산화토륨, 산화마그네슘, 이산화티타늄, 인산삼칼슘, 산화알루미늄 및 흑연에서 선택되는 어느 하나 또는 복수의 중량제를 더 포함하는 것을 특징으로 한다.The blowing agent is characterized in that it further comprises one or a plurality of weight agents selected from copper sulfate, copper oxide, silver nitrate, boron oxide, zinc oxide, thorium dioxide, magnesium oxide, titanium dioxide, tricalcium phosphate, aluminum oxide and graphite. do.
또한 상기 다공체는 내부에 염화칼슘, 염화마그네슘 및 염화리튬에서 선택되는 어느 하나 또는 복수의 비중조절제를 포함하는 것을 특징으로 하며, 더욱 상세하게 상기 비중조절제는 알루미노포스페이트계 제올라이트, 페로알루미노포스페이트계 제올라이트 및 실리코알루미노포스페이트계 제올라이트에서 선택되는 어느 하나 또는 복수의 제올라이트가 더 포함되는 것을 특징으로 한다.In addition, the porous body is characterized in that it contains any one or a plurality of specific gravity control agents selected from calcium chloride, magnesium chloride, and lithium chloride inside, and in more detail, the specific gravity control agent is an aluminophosphate zeolite, ferroaluminophosphate zeolite. And any one or more zeolites selected from silicoaluminophosphate zeolites.
또한 상기 다공체는 표면에 아시네토박터 속, 아트로박터 속, 로도콕사이 속, 마이코박테리움 속, 슈도모나스 속, 잔토박터 속, 락토바실러스 속, 사카로마이세스 속, 로도슈도모나스 속, 스트렙토마이세스 속 디모나스 속, 스트롬비드녹시스, 코레안시스 속 및 판토에아 속에서 선택되는 어느 하나 또는 복수의 균주가 포함된 코팅제가 피복된 것이며, 더욱 상세하게 상기 균주는 아트로박터 속과 잔토박터 속 및 판토에아 속이 혼합된 것을 특징으로 한다.In addition, the porous body has on the surface Acinetobacter genus, Atrobacter genus, Rhodococcy genus, Mycobacterium genus, Pseudomonas genus, Xanthobacter genus, Lactobacillus genus, Saccharomyces genus, Rhodo pseudomonas genus, Streptomyces A coating agent containing any one or a plurality of strains selected from the genus Sess Dimonas, Strombidnoxis, Corenensis and Pantoea is coated, and in more detail, the strains are Atrobacter genus and Xantho It is characterized in that the genus Bacter and the genus Pantoea are mixed.
본 발명의 다른 양태는,Another aspect of the present invention,
a) 금속산화물을 포함하는 무기응집제, 규산염, 물유리 및 발포제를 혼합하여 성형체를 제조하는 단계;a) preparing a molded article by mixing an inorganic coagulant containing a metal oxide, a silicate, a water glass, and a foaming agent;
b) 상기 성형체를 300 내지 500℃에서 2 내지 5시간 동안 건조하는 단계;b) drying the molded body at 300 to 500°C for 2 to 5 hours;
c) 상기 건조된 성형체를 800 내지 1,000℃에서 5 내지 10시간 동안 소성하는 단계; c) firing the dried molded body at 800 to 1,000°C for 5 to 10 hours;
d) 상기 소성된 성형체를 원하는 비중에 맞춰 점성이 있는 황토로 피복하는 단계; 및d) coating the fired molded body with viscous loess according to a desired specific gravity; And
e) 상기 성형체를 균주가 포함된 코팅제에 침지시키는 단계;를 포함하는 수질 개선용 다공체의 제조방법에 관한 것이다.e) immersing the molded body in a coating agent containing the strain; relates to a method of manufacturing a porous body for improving water quality, including.
상기 제조방법에서 상기 성형체는 아트로박터 속, 잔토박터 속, 락토바실러스 속, 사카로마이세스 속, 로도슈도모나스 속, 스트렙토마이세스 속 및 판토에아 속에서 선택되는 어느 하나 또는 복수의 균주를 포함하는 것을 특징으로 한다.In the above manufacturing method, the molded body includes any one or a plurality of strains selected from the genus Atrobacter, genus Xanthobacter, genus Lactobacillus, genus Saccharomyces, genus Rhodomonas, genus Streptomyces, and genus Pantoea. Characterized in that.
본 발명에 따른 다공체는 비중이 0.5 내지 1.5의 범위로 제조되어 점진적으로 물에 가라앉게 구성함으로써, 물속에 침전되어 부유하는 오염물질을 효과적으로 제거할 수 있다.The porous body according to the present invention has a specific gravity in the range of 0.5 to 1.5 and is configured to gradually sink in water, thereby effectively removing pollutants that are precipitated and suspended in water.
또한, 상기 다공체가 일정이상의 강도로 구성되어 용이하게 파괴되지 않도록 함으로써, 보다 장기간의 수질 정화력을 발휘할 수 있다.In addition, since the porous body is configured to have a strength of a certain or more so that it is not easily destroyed, it is possible to exhibit a longer-term water purification power.
여기에 오염지역에 살포된 다공체가 시간이 흐름에 따라 모래로 환원되어 다공체에 의한 2차 오염을 방지할 수 있고, 살포 후 재수거가 필요 없는 수질 개선용 다공체를 제공할 수 있다.Here, the porous body sprayed on the contaminated area is reduced to sand over time, preventing secondary pollution by the porous body, and providing a porous body for improving water quality that does not require recollection after spraying.
이하 구체예들을 참조하여 본 발명에 따른 수질 개선용 다공체를 상세히 설명한다. 다음에 소개되는 구체예들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다.Hereinafter, a porous body for improving water quality according to the present invention will be described in detail with reference to specific examples. Specific examples introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art.
따라서 본 발명은 이하 제시되는 구체예들에 한정되지 않고 다른 형태로 구체화될 수도 있으며, 이하 제시되는 구체예들은 본 발명의 사상을 명확히 하기 위해 기재된 것일 뿐, 본 발명이 이에 제한되는 것은 아니다. Accordingly, the present invention is not limited to the specific examples presented below and may be embodied in other forms, and the specific examples presented below are only described to clarify the spirit of the present invention, and the present invention is not limited thereto.
이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.At this time, unless there are other definitions in the technical and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of possible known functions and configurations will be omitted.
또한 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.In addition, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다. In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, the component may be directly connected or connected to that other component, but another component between each component It should be understood that elements may be “connected”, “coupled” or “connected”.
제조방법을 중심으로 본 발명에 따른 수질 개선용 다공체를 설명하면,When explaining the porous body for improving water quality according to the present invention, focusing on the manufacturing method,
a) 황토, 규산염, 물유리 및 발포제를 혼합하여 성형체를 제조하는 단계;a) preparing a molded article by mixing loess, silicate, water glass, and a foaming agent;
b) 상기 성형체를 300 내지 500℃에서 2 내지 5시간 동안 건조하는 단계;b) drying the molded body at 300 to 500°C for 2 to 5 hours;
c) 상기 건조된 성형체를 800 내지 1,000℃에서 5 내지 10시간 동안 소성하는 단계; c) firing the dried molded body at 800 to 1,000°C for 5 to 10 hours;
d) 상기 소성된 성형체를 원하는 비중에 맞춰 점성이 있는 황토로 피복하는 단계; 및d) coating the fired molded body with viscous loess according to a desired specific gravity; And
e) 상기 성형체를 균주가 포함된 코팅제에 침지시키는 단계;e) immersing the molded body in a coating agent containing the strain;
의 단계를 통해 제조할 수 있다.It can be manufactured through the steps of.
본 발명에서 상기 a) 단계는 금속산화물을 포함하는 무기응집제, 규산염 및 발포제를 혼합하여 성형체를 제조하는 것으로, 상기 조성물에 물과 에탄올 등과 같은 용매를 혼합하여 가공성을 더욱 높일 수 있다.In the present invention, step a) is to prepare a molded article by mixing an inorganic coagulant including a metal oxide, a silicate, and a foaming agent, and processability may be further improved by mixing a solvent such as water and ethanol in the composition.
일반적으로 여름철 발생하는 녹조현상은 유속이 매우 낮은 하천이나 호소에 주로 발생하며, 물빛을 진한 녹색으로 보이게 한다. 이와 관련된 조류는 초여름에서 가을까지 발생하는 남조류가 주로 수화를 일으키며 용존산소 감소, 어류자원 폐사, 이취미 발생, 정수장애 등과 같은 수질오염문제를 발생시킨다. 뿐만 아니라 마이크로시스틴이나 아나톡신 등 간 및 신경독소를 배출하여 공중위생에 심각한 문제를 야기한다. 국립환경과학원은 Microcystis, Anabaena, Oscillatoria, Aphanizomenon의 4종을 유해 남조류로 지정하고 있다(NIER, 2016).In general, the green algae phenomenon that occurs in summer occurs mainly in rivers or lakes with very low flow rates, and makes the water look dark green. As for the related algae, blue-green algae, which occur from early summer to autumn, mainly cause hydration and cause water pollution problems such as reduced dissolved oxygen, fish resource death, taste and taste, and water purification problems. In addition, it causes serious problems in public health by releasing liver and neurotoxins such as microcysteine and anatoxin. The National Academy of Environmental Sciences has designated four species, Microcystis, Anabaena, Oscillatoria, and Aphanizomenon, as harmful blue-green algae (NIER, 2016).
본 발명에서 상기 무기응집제는 상기와 같은 녹조현상을 해소하는 가장 중요한 역할을 수행하는 것으로, 콜로이드 입자에 플랑크톤이 응집 또는 흡착하여 공침강하거나, 물리적 또는 화학적 흡착에 기인하여 수환경 내 존재하는 영양염류를 제거함으로써 녹조를 방제하는 역할을 한다.In the present invention, the inorganic coagulant plays the most important role in resolving the green algae phenomenon as described above, and plankton co-precipitates by coagulation or adsorption on colloidal particles, or nutrients existing in the water environment due to physical or chemical adsorption. It plays a role in controlling the green algae by removing them.
본 발명에서 상기 금속산화물은 토양을 이루는 주성분으로, 토양의 종류에 따라 함량에 차이가 있을 수 있으나 실리카(SiO2), 알루미나(Al2O3), 산화철(Ⅲ)(Fe2O3), 산화철(Ⅱ)(FeO), 이산화티탄(TiO2), 산화망간(MnO), 석회(CaO) 및 산화마그네슘(MgO) 등에서 선택되는 어느 하나 또는 복수를 포함할 수 있다.In the present invention, the metal oxide is a main component of the soil, and the content may vary depending on the type of soil, but silica (SiO 2 ), alumina (Al 2 O 3 ), iron oxide (III) (Fe 2 O 3 ), Iron (II) oxide (FeO), titanium dioxide (TiO 2 ), manganese oxide (MnO), lime (CaO) and magnesium oxide (MgO) may include any one or more selected from.
이 중 상기 금속산화물을 포함하는 무기응집제로 바람직하게는 황토를 들 수 있다. 상기 황토는 다량의 탄산칼슘을 가지고 있고, 이 탄산칼슘에 의해 물과 접촉 시 점성이 발현되어 성형이 용이하다. 또한 일라이트라는 성분을 함유하여 오염물질을 흡착하고 분해하는 효과를 가진다. Among these, the inorganic coagulant containing the metal oxide is preferably loess. The loess has a large amount of calcium carbonate, and the calcium carbonate exhibits viscosity upon contact with water, making it easy to form. It also contains a component called illite, which has the effect of adsorbing and decomposing pollutants.
또한 상기 황토는 표면이 넓은 벌집구조로 수많은 공간이 복층구조를 이루고 있고, 이러한 공간이 플랑크톤, 영양염류, 기타 녹조가 생산한 독소 등을 흡착하는 역할을 한다.In addition, the loess is a honeycomb structure with a wide surface, and a number of spaces form a multi-layered structure, and this space serves to adsorb plankton, nutrients, and other toxins produced by green algae.
본 발명에서 상기 황토는 암석의 화학적 풍화작용으로 인해 형성된 황색 내지 적갈색의 풍화토 또는 풍화퇴적물로서, 대부분의 입자 지름이 0.002 내지 0.02㎜인 토양입자로 이루어진 퇴적물을 의미한다. 또한 상기 황토는 함유하는 광물의 종류에 따라 결정되는 바, 상기 광물의 예로는 캐올리나이트, 할로이사이트, 일라이트, 질석, 녹니석 등을 들 수 있으며, 본 발명은 이러한 광물의 종류에 제한하지 않고 황토로 인정되는 모든 종류를 사용할 수 있다.In the present invention, the loess is yellow to reddish brown weathered soil or weathered sediments formed due to chemical weathering of rocks, and means a sediment composed of soil particles having most of the particle diameters of 0.002 to 0.02 mm. In addition, the loess is determined according to the kind of minerals it contains, examples of the minerals include kaolinite, haloysite, illite, vermiculite, chlorite, and the like, and the present invention is not limited to the kind of these minerals. Any type that is recognized as loess can be used.
본 발명에서 상기 황토는 용매와 같이 혼합 시 용매 100 중량부를 기준으로 60 내지 80 중량부 첨가하는 것이 좋다. 상기 범위에서 황토의 고유 특성인 유기물질 등의 흡착 및 다공체 자체의 기계적인 강도를 유지할 수 있어 바람직하다.In the present invention, when the loess is mixed with a solvent, it is preferable to add 60 to 80 parts by weight based on 100 parts by weight of the solvent. In the above range, it is preferable because it is possible to adsorb organic substances, which are inherent characteristics of loess, and to maintain the mechanical strength of the porous body itself.
본 발명에서 상기 규산염은 상기 황토 입자를 잡아주는 일종의 접착제로, 성분에 따라 다르나 용융점이 낮은 특징을 가지며 가열에 의해 용융된 후, 상기 황토와 결합, 냉각되어 다공체가 일정한 강도를 갖도록 하는 것으로, 바람직하게 상기 규산염은 하기 화학식 1의 구조를 가질 수 있다.In the present invention, the silicate is a kind of adhesive that holds the loess particles, which varies depending on the component, but has a low melting point and is melted by heating, and then combined with the loess and cooled to make the porous body have a certain strength. Thus, the silicate may have a structure represented by the following formula (1).
[화학식 1][Formula 1]
A2O-nSiO2 A 2 O-nSiO 2
(상기 화학식 1에서 A는 나트륨, 칼륨, 리튬, 루비듐 및 세슘에서 선택되는 어느 하나이며, 상기 n은 1 내지 5의 정수이다.)(In Formula 1, A is any one selected from sodium, potassium, lithium, rubidium, and cesium, and n is an integer of 1 to 5.)
상기와 같은 규산염은 산 등을 반응시키면, 강한 알칼리성을 띠므로 격렬한 반응을 일으킨다. 이러한 반응을 통해 유리상을 만들고 구조를 형성하는 기본산소를 입체적으로 배열하여 다공체의 기계적 물성을 증가시킬 수 있다.When the above silicate reacts with an acid or the like, it exhibits strong alkalinity and causes a violent reaction. Through this reaction, the mechanical properties of the porous body can be increased by three-dimensionally arranging the basic oxygen that forms the glass phase and forms the structure.
또한 상기 규산염은 물유리의 형태로 첨가하는 것이 좋다. 일반적으로 물유리는 규사와 소다회의 혼합물을 1,300 내지 1,500℃에서 용융해서 생긴 것을 고압 증기솥에서 처리하면 얻을 수 있다. 공기 속에서는 이산화탄소를 흡수해서 겔 모양의 규산이 석출되므로 강한 접착력을 보이는 특성을 가진다.In addition, the silicate is preferably added in the form of water glass. In general, water glass can be obtained by melting a mixture of silica sand and soda ash at 1,300 to 1,500°C and treating it in a high-pressure steam cooker. Since it absorbs carbon dioxide in the air and precipitates gel-like silicic acid, it exhibits strong adhesion.
이와 같은 물유리는 강알칼리성으로 산으로 중화시켜 생성된 침전을 건조시킨 것이 실리카겔이며 건조제로 사용된다. 또 물유리에서 수분을 증발시키거나 또는 물유리 무수물과 소량의 물을 가열하면 함수 물유리가 생긴다. 이러한 함수 물유리는 접착제, 접합제, 내화 시멘트 등의 원료가 된다.Such water glass is a silica gel that is neutralized with acid and dried with an acid, and is used as a drying agent. In addition, if moisture is evaporated from the water glass or heated water glass anhydride and a small amount of water, hydrated water glass is formed. This water-containing glass becomes a raw material for adhesives, bonding agents, and refractory cement.
물유리는 실리카나 결정 실리카의 여러 다른 형태에 공통적으로 나타나는 사면체 구조를 가지고 있는데, 이것은 실리케이트 사면체 단분자나 Si-O-Si 브리지 형태로 산소를 공유하여 고분자 형태를 갖는다. 그러나 수용성 규산나트륨의 전체적인 구조는 공유된 양이온인 Na2O와 SiO4 분자의 불규칙한 배열이다. 이와 같은 구조를 가지고 있기 때문에 물유리는 팽창하는 과정 중에 팽창하는 특성을 보이고, 발포가 발생한다. 이러한 발포는 황토와 혼합 시 성형체에 기공을 형성하여 유기물과 녹조, 독성성분, 기름 등을 흡착하는 효과를 가져온다.Water glass has a tetrahedral structure that is common to many other forms of silica or crystalline silica, which share oxygen in the form of silicate tetrahedral monomolecules or Si-O-Si bridges, and thus have a polymer form. However, the overall structure of water-soluble sodium silicate is an irregular arrangement of molecules of Na 2 O and SiO 4 , which are shared cations. Since it has such a structure, water glass exhibits the property of expanding during the expansion process, and foaming occurs. Such foaming creates pores in the molded body when mixed with loess, and has the effect of adsorbing organic matter, green algae, toxic components, and oil.
본 발명에서 상기 물유리는 용매 100 중량부 대비 20 내지 40 중량부 첨가하는 것이 좋다. 상기 범위 미만인 경우 접착 특성 저하로 인해 다공체의 기계적 물성이 저하되며, 40 중량부 초과 첨가하는 경우 과도한 발포로 인해 다공체의 비중을 조절하기 어렵다.In the present invention, it is preferable to add 20 to 40 parts by weight of the water glass based on 100 parts by weight of the solvent. If it is less than the above range, the mechanical properties of the porous body are deteriorated due to the decrease in adhesive properties, and when it is added in excess of 40 parts by weight, it is difficult to control the specific gravity of the porous body due to excessive foaming.
본 발명에서 상기 발포제는 상기 물유리와는 별개로 다공체에 기공을 형성하기 위한 것으로, 화학적 반응을 통해 가스를 생성하거나, 상기 황토 또는 규산염과 입자 형태로 혼합된 다음 소성 시 제거됨으로써 기공을 형성할 수도 있다.In the present invention, the foaming agent is to form pores in the porous body separately from the water glass, and it is possible to form pores by generating gas through a chemical reaction or by being mixed with the loess or silicate in the form of particles and then removed during firing. have.
본 발명에서 상기 발포제의 예를 들면, 니트로스티렌, 메톡시스티렌, β-메틸스티렌, o-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 메틸실릴스티렌, 비닐나프탈렌, 비닐비페닐, 비닐안트라센, 비닐클로라이드, 비닐티오펜, 비닐피롤리돈, 비닐피리딘, 술폭시스티렌, 시아노스티렌, 아미노스티렌, 에틸스티렌, β-에틸스티렌, 카르복시스티렌, 클로로스티렌, 페닐스티렌 및 하이드록시스티렌 등의 모노머가 중합된 비닐계 수지를 포함할 수 있으며, 여기에 알콜류, 에스테르류 등의 유기용매가 추가로 더 포함될 수 있다.Examples of the foaming agent in the present invention include nitrostyrene, methoxystyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, methylsilylstyrene, vinylnaphthalene, vinylbiphenyl, vinylanthracene , Vinyl chloride, vinylthiophene, vinylpyrrolidone, vinylpyridine, sulfoxystyrene, cyanostyrene, aminostyrene, ethylstyrene, β-ethylstyrene, carboxystyrene, chlorostyrene, phenylstyrene and hydroxystyrene monomers It may include a polymerized vinyl-based resin, and organic solvents such as alcohols and esters may be further included therein.
또한 상기 발포제는 상기 비닐계 수지의 가교 시 노말헥산, 노말헵탄, 메틸사이클로헥사놀, 1-부탄올, 2-부탄올, 사이클로펜타논, 사이클로헥사논, 사이클로헥사놀, 사이클로헥산, 2-에틸-1-헥사놀, 에틸벤젠 등의 팽윤제가 더 포함될 수 있으며, 이들 또한 유기용매와 혼합하여 사용될 수 있다.In addition, the blowing agent is normal hexane, normal heptane, methylcyclohexanol, 1-butanol, 2-butanol, cyclopentanone, cyclohexanone, cyclohexanol, cyclohexane, 2-ethyl-1 -Swelling agents such as hexanol and ethylbenzene may be further included, and these may also be used by mixing with an organic solvent.
또한 상기 발포제는 필요에 따라 상기 다공체의 비중을 조절하는 중량제를 더 첨가하여도 좋다. 상기 중량제는 금속화합물로, 미생물 또는 균주에 대한 억제력을 갖는 구리, 은, 붕소, 아연, 마그네슘 등의 금속을 주성분으로 하여 다공체의 비중을 증가시키는 것 이외에도 추가적인 살균 효과를 가진다.Further, the foaming agent may further include a weighting agent that adjusts the specific gravity of the porous body, if necessary. The weight agent is a metal compound, and has an additional sterilizing effect in addition to increasing the specific gravity of the porous body by using metals such as copper, silver, boron, zinc, and magnesium as a main component, which have inhibitory power against microorganisms or strains.
상기 중량제의 예를 들면, 황산구리, 산화구리, 질산은, 산화붕소, 산화아연, 이산화토륨, 산화마그네슘, 이산화티타늄, 인산삼칼슘, 산화알루미늄 및 흑연 등을 들 수 있으며, 이들은 단독으로 또는 둘 이상 혼합하여 사용하여도 무방하다.Examples of the weight agent include copper sulfate, copper oxide, silver nitrate, boron oxide, zinc oxide, thorium dioxide, magnesium oxide, titanium dioxide, tricalcium phosphate, aluminum oxide and graphite, and these may be used alone or in two or more It can be mixed and used.
상기 중량제는 상기 발포제와 함께 혼합하여 사용하는 것이 좋으며, 상기 발포제 및 중량제의 첨가량을 한정하지는 않으나, 상기 발포제의 경우 용매 100 중량부 대비 1 내지 5 중량부 첨가하는 것이 좋으며, 상기 중량제는 발포제의 10 내지 20 중량%를 치환하여 혼합하는 것이 비중 조절 및 발포 효과를 모두 만족할 수 있어 바람직하다.The weight agent is preferably mixed with the foaming agent, and the amount of the foaming agent and the weight agent is not limited, but in the case of the foaming agent, it is preferable to add 1 to 5 parts by weight based on 100 parts by weight of the solvent, and the weight agent Substituting and mixing 10 to 20% by weight of the foaming agent is preferable because it can satisfy both the specific gravity control and foaming effect.
본 발명에서 상기 용매는 상기 황토, 규산염, 발포제 등을 혼합하기 위한 액체류로, 그 종류를 한정하는 것은 아니나, 물 또는 메탄올, 1-부탄올, 2-부탄올, 에탄올, 이소부틸알코올, 이소프로필알코올, 이소펜틸알코올, 프로판-1-올, 프로판-2-올 등의 알콜류; 에테르류인 디메틸에테르, 에틸에테르, 테트라하이드로퓨란; 케톤류인 메틸부틸케톤, 메틸에틸케톤, 메틸이소부틸케톤, 메틸이소프로필케톤, 아세톤 등을 사용할 수 있으며, 이외에도 글리콜에테르, 알데히드, 에스테르 또는 이들의 혼합 용매를 사용할 수 있다.In the present invention, the solvent is a liquid for mixing the loess, silicate, foaming agent, etc., and the type is not limited, but water or methanol, 1-butanol, 2-butanol, ethanol, isobutyl alcohol, isopropyl alcohol Alcohols such as isopentyl alcohol, propan-1-ol, and propan-2-ol; Ethers such as dimethyl ether, ethyl ether, and tetrahydrofuran; Ketones such as methylbutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, acetone, etc. can be used, and in addition, glycol ether, aldehyde, ester, or a mixed solvent thereof can be used.
본 발명에서 상기 a) 단계는 황토, 규산염, 발포제 등을 혼합하고, 이를 구형의 성형체로 성형할 수 있다. 성형 방법은 본 발명에서 한정하지 않으나 주형에 넣거나 방사 후 절단하는 방식을 적용할 수 있으며, 입경 또한 한정하지 않으나 1 내지 30㎜인 것이 바람직하다.In the present invention, step a) may be performed by mixing loess, silicate, foaming agent, and the like, and molding it into a spherical molded body. The molding method is not limited in the present invention, but a method of putting in a mold or cutting after spinning may be applied, and the particle diameter is also not limited, but is preferably 1 to 30 mm.
또한 본 발명에 따른 제조방법은 제조된 다공체가 서서히 가라앉을 수 있도록 상기 a) 단계에서 하나 이상의 비중조절제를 더 첨가할 수도 있다.In addition, in the manufacturing method according to the present invention, at least one specific gravity control agent may be further added in step a) so that the manufactured porous body can slowly sink.
일반적으로 황토의 경우 앞서 설명한 바와 같이 녹조가 발생한 경우에 입자 형태로 살포되나, 상기와 같은 황토를 일반적인 방법으로 살포하는 경우 침강한 황토에 의한 저서생물의 피해가 발생하는 등, 이차적인 생태계 교란이 우려되고, 대량 살포 시 심미적 오염을 유발하여 살포 후 일정 시간이 경과하면 제거되었던 플랑크톤이 재활성화되는 경우도 있으므로, 일정 시간 이상 황토가 수표면에 부유하도록 하여 플랑크톤의 제거 시간을 확보하는 것이 중요하다. In general, yellow soil is sprayed in the form of particles when green algae occurs as described above, but when spraying the red soil in a general manner, secondary ecosystem disturbances such as damage to benthic organisms caused by the settled red soil It is a concern, and it is important to ensure the removal time of plankton by allowing the loess to float on the water surface for a certain period of time or more, as it may cause aesthetic contamination when spraying in large quantities, and then the removed plankton may be reactivated after a certain period of time. .
본 발명은 상기와 같은 문제점을 해결하기 위해 수분을 흡착할 수 있는 성분을 더 첨가함으로써 다공체의 기공으로 스며드는 수분을 흡수하여 비중을 높이고, 높아진 비중에 의해 다공체가 서서히 가라앉을 수 있도록 하여 표면에 형성된 녹조, 기름, 독소와 같은 유해성분을 제거할 시간을 확보함과 동시에 흡착이 끝난 다공체가 바닥에 가라앉으면서 일정 시간 동안 수질 정화력을 발휘할 수 있다.In order to solve the above problems, the present invention is formed on the surface by adding a component capable of adsorbing moisture to increase the specific gravity by absorbing moisture penetrating into the pores of the porous body, and allowing the porous body to gradually sink due to the increased specific gravity. It secures time to remove harmful components such as green algae, oil, and toxins, and at the same time, it can exert water purification power for a certain period of time while the adsorbed porous body sinks to the bottom.
본 발명에서 상기 비중조절제는 하나 이상의 금속염화물일 수 있으며, 바람직하게는 염화칼슘, 염화마그네슘 및 염화리튬에서 선택되는 어느 하나 또는 복수일 수 있다. 상기 금속 염화물은 높은 조해성을 가짐으로 물과 쉽게 반응하여 액체 상태로 용해되며 원래 물질에 비해 비중이 증가하게 된다. 따라서 전체 다공체의 비중을 상승시키게 되고, 다공체가 시간이 지남에 따라 물에 가라앉게 된다.In the present invention, the specific gravity control agent may be one or more metal chlorides, preferably any one or more selected from calcium chloride, magnesium chloride, and lithium chloride. Since the metal chloride has high deliquescent properties, it easily reacts with water and dissolves in a liquid state, and its specific gravity increases compared to the original material. Accordingly, the specific gravity of the entire porous body is increased, and the porous body sinks in water over time.
다만, 상기와 같은 높은 조해성으로 인해 비중조절제의 액체화가 진행될 경우 비중조절제가 용해되어 다공체 밖으로 유출될 수 있으므로, 이를 잡아주기 위해 알루미노포스페이트계 제올라이트, 페로알루미노포스페이트계 제올라이트 및 실리코알루미노포스페이트계 제올라이트 등과 같은 하나 이상의 제올라이트에 함침시켜 고체화하는 것이 바람직하다. 특히 상기와 같은 제올라이트의 경우 일정 이상의 비중을 가지며, 표면에 기공이 형성되어 금속염화물을 쉽게 함침함과 동시에 금속염화물의 흡습성이 복합화되어 상승작용을 일으킬 수 있다.However, when the specific gravity control agent is liquefied due to the high deliquescent properties as described above, the specific gravity control agent may dissolve and leak out of the porous body.Therefore, aluminophosphate zeolite, ferroaluminophosphate zeolite, and silicoaluminophosphate type It is preferable to solidify by impregnating at least one zeolite such as zeolite. In particular, in the case of the above zeolite, it has a specific gravity or more, and pores are formed on the surface to easily impregnate the metal chloride, and at the same time, the hygroscopicity of the metal chloride may be combined to cause a synergistic effect.
상기 비중조절제는 다공체 표면보다는 내부에 형성되는 것이 바람직하며, 더욱 바람직하게는 상기 금속염화물이 함침된 제올라이트를 내부로 하고, 상기 제올라이트의 표면에 다시 황토, 규산염, 발포제 등의 혼합물을 발라 외부층을 형성하는 것이 다공층 내부로 이동하는 수분의 이동시간을 일정 이상 확보하여 급격한 비중 증가를 막으며, 동시에 다공체의 기계적 물성을 확보할 수 있어 좋다.The specific gravity control agent is preferably formed inside rather than on the surface of the porous body, and more preferably, the zeolite impregnated with the metal chloride is used as the interior, and the surface of the zeolite is again coated with a mixture of ocher, silicate, and a foaming agent to form an outer layer. Forming is good because it secures a movement time of moisture moving inside the porous layer for a certain amount or more, prevents a rapid increase in specific gravity, and at the same time secures the mechanical properties of the porous body.
상기 비중조절제는 첨가량을 한정하지는 않으며, 내부에 코어 형태로 첨가하는 경우 전체 다공체 중 5 내지 15 부피%가 되도록 첨가하는 것이 비중 증가 및 기계적 물성을 만족할 수 있어 바람직하다.The amount of the specific gravity control agent is not limited, and when it is added in the form of a core, it is preferable to add it so as to be 5 to 15% by volume of the total porous body, since the specific gravity increase and mechanical properties can be satisfied.
상기와 같이 성형체를 제조하면, 이를 소성하기 전에 일정 온도에서 건조할 수 있다. 상기 건조는 성형체 내부의 수분, 특히 기공에 흡착된 수분을 제거하여 비중을 일정하게 유지하기 위함이며, 동시에 성형체의 급격한 가열에 따른 팽창, 파손, 갈라짐 등과 같은 물성의 약화를 방지할 수 있다.When the molded body is manufactured as described above, it can be dried at a certain temperature before firing. The drying is to remove moisture inside the molded body, particularly moisture adsorbed to the pores, to maintain a constant specific gravity, and at the same time, it is possible to prevent weakening of physical properties such as expansion, breakage, cracking, etc. due to rapid heating of the molded body.
본 발명에서 상기 b)단계는 성형체를 소성로 또는 건조기 등에 투입하고 300 내지 500℃에서 2 내지 5시간 동안 진행하는 것이 바람직하다. 상기 범위 미만인 경우 부족한 건조시간으로 인해 소성 시 다공체가 깨질 수 있으며, 상기 범위를 초과하여 가열하는 경우 내부의 유기물이 다공체의 안정화 이전에 전부 열화되어 오히려 기계적 물성이 감소할 수 있다. In the present invention, step b) is preferably carried out at 300 to 500° C. for 2 to 5 hours after putting the molded body in a kiln or dryer. If it is less than the above range, the porous body may be broken during firing due to insufficient drying time, and when heating exceeding the above range, all internal organic matters are deteriorated prior to stabilization of the porous body, and mechanical properties may be reduced.
다음으로 건조가 끝난 성형체를 800 내지 1,000℃에서 5 내지 10시간 동안 소성하여 다공체를 완성할 수 있다. 상기 범위에서의 소성을 통해 내부에 발포제가 열화, 기화되어 기공을 형성하며, 물유리와 같은 규산염 또한 용융 및 재결정화하여 황토와 물리적으로 결합되어 일정 이상의 파괴강도를 유지하는 다공체가 만들어지게 된다. Next, the dried molded body can be baked at 800 to 1,000° C. for 5 to 10 hours to complete the porous body. Through the firing in the above range, the foaming agent is deteriorated and vaporized to form pores, and silicates such as water glass are also melted and recrystallized to physically bond with loess to create a porous body that maintains a certain or more breaking strength.
다음으로 상기 제조된 다공체를 상온까지 식혀 안정화한 후, 상기 소성된 다공체의 비중을 조절하기 위해 다공체 표면에 황토를 피복할 수 있다.Next, after the prepared porous body is cooled to room temperature and stabilized, loess may be coated on the surface of the porous body to adjust the specific gravity of the fired porous body.
상기 황토는 함수산화철과 무수산화철을 함유한 규토로 붉은색을 띈 자연상태의 흙으로서, SiO2, Al2O3, Fe2O3, Na2O, CaO, TiO2, MgO 등의 물질을 다량 함유하고 있으며, 인체에 유익한 효능을 발휘할 수 있다. 이러한 황토는 분해력, 자정력, 그리고 황토에서 내뿜는 원적외선, 항균, 방충, 공기정화 및 탈취 등의 다양한 친환경적인 성질을 가진다.The loess is a reddish natural soil containing hydrated iron oxide and anhydrous iron oxide, and contains materials such as SiO 2 , Al 2 O 3 , Fe 2 O 3 , Na 2 O, CaO, TiO 2 , MgO, etc. It contains a large amount and can exert beneficial effects on the human body. This loess has various eco-friendly properties such as decomposition power, self-cleaning power, and far-infrared rays emitted from the loess, antibacterial, insect repellent, air purification and deodorization.
상기 황토는 다공체의 비중에 따라 산화철의 함량을 조절하여 비중을 증감할 수 있다. 예를 들어 실리카(SiO2)의 경우 비중이 2.21, 산화칼슘(CaO)이 3.3, 산화알루미늄이 3.4 내지 4인데 반해 산화철의 비중은 4.5 내지 5.2로 다른 금속산화물에 비해 훨씬 높으므로 산화철의 함량을 조절함으로써 쉽게 비중을 증감할 수 있다. 이때 상기 황토에서 산화철의 함량은 2 내지 5 중량%이므로 상기 범위 내에서 산화철의 첨가량을 정하는 것이 바람직하다. The specific gravity of the loess may be increased or decreased by adjusting the content of iron oxide according to the specific gravity of the porous body. For example, silica (SiO 2 ) has a specific gravity of 2.21, calcium oxide (CaO) of 3.3, and aluminum oxide of 3.4 to 4, whereas iron oxide has a specific gravity of 4.5 to 5.2, which is much higher than other metal oxides, so the content of iron oxide is higher. By adjusting the specific gravity can be easily increased or decreased. At this time, since the content of iron oxide in the loess is 2 to 5% by weight, it is preferable to determine the amount of iron oxide added within the above range.
상기 황토는 사용 목적에 따라서도 비중을 증감하는 것이 바람직하다. 예를 들어 기름을 제거하는 경우, 수면에 부유하는 최대한 빠르게 대량으로 흡착하되, 기름을 흡착한 다공체가 표면에서 빠르게 가라앉도록 황토의 비중을 높이는 것이 바람직하다. 이는 수중 박테리아가 다공체에 흡착된 기름을 분해하도록 유도하며, 다공체가 수면에 오랜 시간 부유하는 경우 기체의 교환을 방해하고 빛을 차단하여 오히러 생태계에 악영향을 줄 수 있기 때문이다.It is preferable to increase or decrease the specific gravity of the loess depending on the purpose of use. For example, in the case of removing oil, it is desirable to increase the specific gravity of the loess so that the oil-adsorbed porous body quickly sinks from the surface while adsorbing in a large amount as quickly as possible floating on the water surface. This is because underwater bacteria induce decomposition of oil adsorbed on the porous body, and if the porous body floats on the surface for a long time, it may interfere with the exchange of gas and block light, which may adversely affect the ecosystem.
이와는 대조적으로 녹조나 적조는 부유성의 조류이므로, 수면에 최대한 오래 머물러 조류를 흡착하도록 상기 황토의 비중을 낮추는 것이 바람직하다.In contrast, since green algae and red algae are floating algae, it is preferable to lower the specific gravity of the loess so that they stay on the water surface for as long as possible to adsorb algae.
상기와 같이 다공체 표면에 황토를 피복한 후, 피복된 황토가 경화되도록 상온에서 건조시킨다. 이때 햇볕을 받게 되면 피복된 황토가 갈라져 버리므로, 그늘에서 말리는 것이 바람직하며, 건조 시간 또한 한정하지 않으나, 물기가 완전히 제거될 수 있도록 적절한 습도 하에서 충분히 건조시키는 것이 바람직하다.After the ocher is coated on the surface of the porous body as described above, it is dried at room temperature to cure the coated ocher. At this time, since the covered loess cracks when exposed to sunlight, it is preferable to dry it in the shade, and the drying time is not limited, but it is preferable to sufficiently dry it under appropriate humidity so that water can be completely removed.
상기와 같이 다공체가 완성되면 상기 다공체의 표면에 코팅제로 피복할 수 있다. When the porous body is completed as described above, the surface of the porous body may be coated with a coating agent.
상기 코팅제는 상기 다공체 표면에 피막을 형성하는 고분자에 녹조류, 적조류, 독소류 및 기타 기름과 같은 유해성분을 소화, 흡수, 제거할 수 있는 균주가 혼합된 것으로, 하나 이상의 셀룰로스 고분자에 하나 또는 복수의 균주가 코팅된 것일 수 있다.The coating agent is a mixture of a polymer that forms a film on the surface of the porous body with a strain capable of digesting, absorbing, and removing harmful components such as green algae, red algae, toxins, and other oils, and one or more cellulose polymers The strain of may be coated.
상기 셀룰로스 고분자는 면화, 목재, 곡류 등에서 얻어진 천연 고분자로, 바람직하게는 하나 이상의 에테르로 반응시킨 수용성 셀룰로스 또는 변성 전분을 포함할 수 있다.The cellulose polymer is a natural polymer obtained from cotton, wood, grain, etc., and may preferably include water-soluble cellulose or modified starch reacted with one or more ethers.
상기 천연 셀룰로스는 다공체 표면에 피막을 형성하여 상기 균주가 분해, 가용화할 수 있는 영양성분을 제공하며, 동시에 코팅제의 점도를 유지할 수 있다. 또한 상기 변성 전분은 일반적으로 겔화제, 피막제 등으로 사용되는 것으로, 균주의 고정 및 영양 공급 등의 역할을 수행할 수 있다.The natural cellulose forms a film on the surface of the porous body to provide nutrients that the strain can decompose and solubilize, and at the same time maintain the viscosity of the coating agent. In addition, the modified starch is generally used as a gelling agent, a coating agent, and the like, and may perform a role of fixing a strain and supplying nutrients.
보다 바람직하게 상기 코팅제는 변성 전분인 것이 바람직하다. 이는 수중에서 용해 및 유화되는 시간을 조절하기 용이하며, 이를 통해 균주가 수중으로 분산 및 유실되는 것을 방지할 수 있다. 또한 균주에게 당류 등의 영양분을 효과적으로 공급할 수 있다.More preferably, the coating agent is preferably modified starch. This makes it easy to control the dissolution and emulsification time in water, thereby preventing the strain from being dispersed and lost in water. In addition, nutrients such as sugars can be effectively supplied to the strain.
본 발명에서 상기 셀룰로스 고분자는 용매 100 중량부 대비 10 내지 50 중량부 첨가하는 것이 좋다. 상기 범위 미만인 경우 코팅제의 점도를 충분히 유지하지 못해 코팅제의 두께가 얇게 형성될 수 있으며, 상기 범위 초과하여 첨가하는 경우 점도의 급격한 상승으로 인해 균주가 녹조 등에 제대로 노출되지 못하거나 균주가 소멸할 수 있다.In the present invention, it is preferable to add 10 to 50 parts by weight of the cellulose polymer based on 100 parts by weight of the solvent. If it is less than the above range, the viscosity of the coating agent may not be sufficiently maintained, so that the thickness of the coating agent may be formed thin, and when added in excess of the above range, the strain may not be properly exposed to green algae or the strain may disappear due to a rapid increase in viscosity. .
상기 균주는 녹조, 적조 등과 같은 조류 및 기름, 독소와 같은 기타 부유물을 흡착, 소화, 제거하기 위한 것으로 이들의 예를 들면 아시네토박터 속, 아트로박터 속, 로도콕사이 속, 마이코박테리움 속, 슈도모나스 속, 잔토박터 속, 락토바실러스 속, 사카로마이세스 속, 로도슈도모나스 속, 스트렙토마이세스 속 및 판토에아 속 등을 들 수 있다.The strain is for adsorption, digestion, and removal of algae such as green algae and red algae, and other suspended matters such as oil and toxins, for example, Acinetobacter genus, Atrobacter genus, Rhodococsay genus, Mycobacterium Genus, Pseudomonas genus, Xanthobacter genus, Lactobacillus genus, Saccharomyces genus, Rhodo Pseudomonas genus, Streptomyces genus, and Pantoea genus may be mentioned.
상기 균주는 제조되는 다공체의 투입 위치, 목적에 따라 달리할 수 있다. 예를 들어 오폐수 정화, 타르겔 흡착 등을 위한 경우 아시네토박터 속, 아트로박터 속, 로도콕사이 속, 마이코박테리움 속, 슈도모나스 속 등을 혼합하는 것이 좋으며, 녹조 제거를 위한 경우 아트로박터 속, 잔토박터 속, 디모나스 속, 스트롬비드녹시스, 코레안시스 속 등을 혼합하는 것이 좋다. 또한 원유 등의 소화를 위해 아트로박터 속이나 독소 등을 제거하기 위한 판토에아 속을 더 첨가할 수도 있다.The strain may be varied depending on the location and purpose of the porous body to be prepared. For example, for purification of wastewater and adsorption of targel, it is recommended to mix Acinetobacter genus, Atrobacter genus, Rodococci genus, Mycobacterium genus, Pseudomonas genus, etc. It is good to mix the genus Bacter, the genus Xanthobacter, the genus Dimonas, the genus Stromboid Noxis, and the genus Coriansis. In addition, for digestion of crude oil, etc., Atrobacter genus or pantoea genus to remove toxins may be added.
본 발명에서 상기 균주로 더욱 바람직하게는 아트로박터 속과 잔토박터 속 및 판토에아 속이 혼합된 것이 좋다. 상기 아트로박터 속 균주는 원유 등과 같은 오염원을 효과적으로 제거할 수 있으며, 상기 잔토박터 속 균주는 가장 높은 살조능을 가지며, 조류의 모든 성장단계에서 높은 살조능을 보인다. 또한 판토에아 속은 상기 조류가 생성한 신경독이나 간독을 제거할 수 있다. In the present invention, the strain is more preferably a mixture of the genus Atrobacter, the genus Xanthobacter, and the genus Pantoea. The strains of the genus Atrobacter can effectively remove contaminants such as crude oil, and the strains of the genus Xanthobacter have the highest acaricidal activity and high algal activity in all growth stages of algae. In addition, the genus Pantoea can remove neurotoxins or liver poisons generated by the algae.
상기 균주는 용매 100 중량부 대비 1 내지 5 중량부 첨가할 수 있으며, 상기와 같이 균주가 하나 이상 첨가되는 경우, 특히 아트로박터 속과 잔토박터 속 및 판토에아 속이 혼합되는 경우 각 균주의 첨가량이 0.5 내지 1 중량부를 만족하는 것이 바람직하다.The strain may be added in an amount of 1 to 5 parts by weight relative to 100 parts by weight of the solvent, and when one or more strains are added as described above, particularly when Atrobacter genus, Xanthobacter genus, and Pantoea genus are mixed, the amount of each strain added It is preferable to satisfy this 0.5 to 1 part by weight.
또한 상기 코팅제는 함께 혼합되는 균주에 대한 영양 공급을 강화하고, 상기 판토에아 속과 함께 조류가 생성한 간독을 제거하기 위해 하나 이상의 방향유를 더 첨가할 수 있다. In addition, the coating agent may be further added to one or more aromatic oils to enhance nutrient supply to strains to be mixed together and to remove liver poison generated by algae along with the pantoea genus.
상기 방향유는 식물의 과일, 잎, 줄기 등에서 증기 증류, 열수 증류, 유지 흡착 등을 통해 추출하는 것으로, 이들의 예를 들면, 시트로넬랄, 게라닐 아세테이트, 시트로넬릴 아세테이트, 시트로넬롤, 크립톤, 리날룰, 쿠미놀, 노난산, 나린진, 게라니알 및 피페리톤 등에서 선택되는 어느 하나 또는 복수일 수 있다.The aromatic oil is extracted from the fruits, leaves, stems, etc. of plants through steam distillation, hot water distillation, oil adsorption, etc., for example, citronellal, geranyl acetate, citronellyl acetate, citronellol, krypton , Linalul, cuminol, nonanoic acid, naringin, geranial, piperitone, and the like.
상기 방향유로 더욱 바람직하게는 리날룰과 나린진의 혼합물일 수 있다. 상기 리날룰은 상기 판토에아 속 균주의 활성을 증가시켜 균주의 독소 제거가 활발해지며, 나린진 또한 균주의 활성 증가, 영양분 공급 이외에 간독에 의한 세포자살을 억제할 수 있다. More preferably, the aromatic oil may be a mixture of linalul and naringin. The linalul increases the activity of the strains of the genus Pantoea so that toxins are removed from the strain, and Naringin can also inhibit apoptosis caused by hepatotoxicity in addition to increasing the activity of the strain and supplying nutrients.
상기와 같은 방향유는 용매 100 중량부 중 0.1 내지 1 중량부 포함하는 것이 바람직하며, 나린진과 리날룰을 혼합하는 경우 1 : 1 내지 2 중량비로 혼합하는 것이 상기 효과를 더욱 극대화할 수 있어 바람직하다.It is preferable that the aromatic oil as described above contains 0.1 to 1 parts by weight of 100 parts by weight of the solvent, and when mixing naringin and linalul, mixing at a ratio of 1:1 to 2 by weight is preferable because the above effect can be further maximized.
상기 용매는 상기 균주, 셀룰로스 고분자, 방향유 등을 용해 또는 혼합하기 위한 것으로, 물 또는 물과 알콜류의 혼합물을 사용하는 것이 좋다.The solvent is for dissolving or mixing the strain, cellulose polymer, aromatic oil, and the like, and water or a mixture of water and alcohol is preferably used.
상기 e) 단계는 상기 성분들을 먼저 교반, 혼합하여 코팅제로 제조한 후, 상기 코팅제에 소성된 성형체를 침지시킨 후, 이를 건조하여 완료하는 것이 좋다. 이때 코팅 조건은 본 발명에서 한정하는 것은 아니나, 상온(20 내지 25℃)에서 30분 내외로 침지한 후, 이를 꺼내어 30 내지 40℃에서 성형체의 표면에 피막이 형성될 때까지 건조시켜 완성할 수 있다.In the step e), the ingredients are first stirred and mixed to prepare a coating agent, and then the fired molded body is immersed in the coating agent, and then dried. At this time, the coating conditions are not limited in the present invention, but can be completed by immersing at room temperature (20 to 25°C) for about 30 minutes, then taking it out and drying it at 30 to 40°C until a film is formed on the surface of the molded body. .
본 발명은 상기와 같이 제조된 수질 개선용 다공체를 포함한다. 상기 수질 개선용 다공체는 비중이 0.5 내지 1.5이며, 기공율이 10 내지 60%, 비표면적이 1 내지 1,000㎡/g일 수 있으며, 상기와 같은 특성을 통해 하천 또는 바다에서 녹조류, 적조류, 기름띠 및 기타 독소 등의 유해성분을 흡착한 후, 점진적으로 물에 가라앉게 구성함으로써 오염물질을 효과적으로 제거할 수 있다. 또한 상기와 같이 가라앉은 다공체는 천연 성분인 황토, 규산염 등을 포함함으로써 시간이 흐름에 따라 모래로 환원되어 다공체에 의한 2차 오염을 방지할 수 있고, 사용 후 재수거와 같은 노동력 투입을 막을 수 있어 경제적이다.The present invention includes a porous body for improving water quality prepared as described above. The porous body for improving water quality may have a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, and a specific surface area of 1 to 1,000 ㎡/g. Through the above characteristics, green algae, red algae, oil bands in rivers or seas After adsorbing harmful components such as toxins and other toxins, contaminants can be effectively removed by gradually sinking into water. In addition, since the submerged porous body as described above contains natural components such as loess and silicate, it is reduced to sand over time to prevent secondary contamination by the porous body and prevent labor input such as recollection after use. It's economical.
이하 실시예 및 비교예를 들어 본 발명을 더욱 상세히 설명한다. 다만 하기 실시예 및 비교예는 본 발명을 더욱 상세히 설명하기 위한 하나의 예시일 뿐, 본 발명이 하기 실시예 및 비교예에 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for describing the present invention in more detail, and the present invention is not limited to the following Examples and Comparative Examples.
(실시예 1)(Example 1)
먼저 성형체를 제조하기 위해 물 100 중량부에 황토 70 중량부, 수용성 규산나트륨 30 중량부, 발포제로 니트로스티렌 중합체(중량평균분자량 3,000) 3 중량부를 첨가하되, 상기 발포제의 10 중량%(0.3 중량부)를 황산구리로 치환하였다. 상기 성형체 조성물을 혼합하여 직경 15㎜ 구체로 성형한 후, 건조로에 투입하여 350℃에서 3시간 건조하고 이를 꺼내어 상온으로 식혔다. 그리고 성형체를 다시 열처리로에 투입하고 900℃에서 8시간 동안 소성한 후, 상기 성형체 표면에 황토를 피복하고 건조하여 성형체를 완성하였다. First, in order to prepare a molded body, 70 parts by weight of loess, 30 parts by weight of water-soluble sodium silicate, and 3 parts by weight of a nitrostyrene polymer (weight average molecular weight 3,000) as a blowing agent are added to 100 parts by weight of water, and 10% by weight (0.3 parts by weight) of the blowing agent. ) Was replaced with copper sulfate. The molded body composition was mixed and molded into spheres with a diameter of 15 mm, then put into a drying furnace, dried at 350° C. for 3 hours, taken out, and cooled to room temperature. Then, the molded body was again put into a heat treatment furnace and fired at 900° C. for 8 hours, and then the surface of the molded body was covered with loess and dried to complete the molded body.
이와는 별개로 물과 에탄올이 1 : 1 중량비로 혼합된 용매 100 중량부에 변성전분(초산전분) 20 중량부 및 균주가 배양된 배양액 3 중량부를 혼합하고 교반하였다. 코팅액의 점도가 상승하면 상기 성형체를 코팅액에 투입하고 30분간 정치한 후, 이를 꺼내고 35℃에서 2시간 건조하여 수질 개선용 다공체를 제조하였다. Separately, 20 parts by weight of denatured starch (starch acetate) and 3 parts by weight of the culture medium in which the strain was cultured were mixed and stirred in 100 parts by weight of a solvent in which water and ethanol were mixed in a 1:1 weight ratio. When the viscosity of the coating solution increased, the molded article was added to the coating solution and allowed to stand for 30 minutes, then taken out and dried at 35° C. for 2 hours to prepare a porous article for improving water quality.
(실시예 2)(Example 2)
상기 실시예 1에서 다공체 제조 시 비중조절제를 더 첨가하였다. 구체적으로 직경 1.5㎜의 제올라이트를 염화칼슘과 물이 1 : 2 중량비로 혼합된 용액에 투입하였다. 그리고 이를 충분히 교반한 후, 200℃ 오븐에 투입하고 24시간 동안 완전히 건조하였다. 건조된 비중조절제에 상기 실시예 1에서 제조된 성형체 조성물을 표면에 도포하여 15㎜의 구형이 되도록 하였다. 이외에는 동일한 방법으로 수질 개선용 다공체를 제조하였다.In Example 1, when manufacturing the porous body, a specific gravity control agent was further added. Specifically, zeolite with a diameter of 1.5 mm was added to a solution in which calcium chloride and water were mixed in a weight ratio of 1:2. And after sufficiently stirring this, it was put into a 200 ℃ oven and completely dried for 24 hours. The molded body composition prepared in Example 1 was applied to the dried specific gravity control agent on the surface to have a spherical shape of 15 mm. Except for the same method, a porous body for improving water quality was manufactured.
(실시예 3)(Example 3)
상기 실시예 2에서 다공체 제조 시 균주로 Arthrobacter chlorophenolicus, xanthobacter autotrophicus, Pantoea agglomerans 배양액을 각각 1 중량부 혼합한 코팅액을 사용한 것을 제외하고 동일한 방법으로 수질 개선용 다공체를 제조하였다.A porous body for improving water quality was prepared in the same manner as in Example 2, except that a coating solution obtained by mixing 1 part by weight of each culture solution of Arthrobacter chlorophenolicus, xanthobacter autotrophicus, and Pantoea agglomerans as strains was used.
(실시예 4)(Example 4)
상기 실시예 3에서 다공체 제조 시 코팅액에 방향유로 리날룰을 0.5 중량부 더 첨가한 것을 제외하고 동일한 방법으로 수질 개선용 다공체를 제조하였다.A porous body for improving water quality was prepared in the same manner as in Example 3, except that 0.5 parts by weight of linalul as a fragrance oil was added to the coating solution when preparing the porous body.
(실시예 5)(Example 5)
상기 실시예 4에서 리날룰과 나린진이 1.5 : 1 중량비로 혼합된 방향유 0.5 중량부 첨가한 것을 제외하고 동일한 방법으로 수질 개선용 다공체를 제조하였다.A porous body for improving water quality was prepared in the same manner as in Example 4, except that 0.5 parts by weight of aroma oil mixed in a 1.5:1 weight ratio of linalul and naringin was added.
(실험예)(Experimental example)
충남대 연못에서 실시예 별로 각 30㎏씩 수득하고, 이를 반으로 나누어 한쪽에는 5,000 ppm의 원유를 투입하였다. 원유가 투입된 시료와 투입되지 않은 시료의 수소이온농도, 용존산소량, 총 인량, 총 질소량, 원유량을 측정하였으며, 시료에 실시예 1 내지 5에서 제조된 시편을 각 300개씩 투입한 후 30일간 방치하였다. 방치 후 수소이온농도, 용존산소량, 총 인량, 총 질소량, 원유량을 측정하였으며, 그 변화량을 하기 표 1에 기재하였다. 여기에 추가적으로 방치 후 시료를 이용하여 어독성시험(OECD TG 203, 송사리 10마리, 96시간 후 LC50 측정)을 실시하였다.30 kg each was obtained for each example in a pond at Chungnam National University, divided in half, and 5,000 ppm of crude oil was added to one side. The hydrogen ion concentration, dissolved oxygen, total phosphorus, total nitrogen, and crude oil were measured in the samples to which crude oil was added and the samples to which the crude oil was added, and 300 samples prepared in Examples 1 to 5 were added to each sample and left for 30 days. After standing, the hydrogen ion concentration, dissolved oxygen amount, total phosphorus amount, total nitrogen amount, and crude oil amount were measured, and the amount of change is shown in Table 1 below. In addition to this, a fish toxicity test (OECD TG 203, 10 killifish, LC 50 measurement after 96 hours) was performed using the sample after standing.
[표 1][Table 1]
Figure PCTKR2020002954-appb-I000001
Figure PCTKR2020002954-appb-I000001
상기 표 1과 같이 본 발명에 따라 제조된 다공체는 녹조 개선 및 수질 개선 효과가 우수한 것을 알 수 있다. 구체적으로 다공체 내에 비중조절제를 더 첨가하지 않은 실시예 1은 그렇지 않은 실시예 2와 수질 개선 효과에서는 큰 차이를 보이지 않았으나, 다공체가 가라앉지 않아 미관상 좋지 않았으며 일반 호수나 바다에 적용 시 물 속으로 전달되는 햇빛을 차단하여 수중 생태계에 악영향을 줄 수 있을 것으로 우려된다. As shown in Table 1 above, it can be seen that the porous body manufactured according to the present invention has excellent effects of improving green algae and improving water quality. Specifically, Example 1 in which the specific gravity control agent was not further added to the porous body did not show a significant difference in the water quality improvement effect from Example 2, but the porous body did not sink, so it was not aesthetically pleasing, and when applied to a general lake or sea, It is concerned that it could adversely affect the aquatic ecosystem by blocking the transmitted sunlight.
또한 세 종류의 균주를 혼합하여 첨가한 실시예 3은 용존산소량, 총 인량 및 질소량 감소율의 상승이 있었으며, 특히 원유량 감소율이 크게 상승한 것을 알 수 있다. 여기에 방향유로 리날룰이 더 첨가된 실시예 4, 리날룰과 나린진이 더 첨가된 실시예 5는 균주의 활성 증가 및 독소 제거율이 증가하여 어독성 시험 항목에서 우수한 결과를 보이고 있다.In addition, in Example 3, in which three strains were mixed and added, there was an increase in the amount of dissolved oxygen, the total amount of phosphorus, and the amount of nitrogen, and in particular, it can be seen that the rate of reduction in the amount of crude oil increased significantly. Example 4 in which linalul was further added as aromatic oil, and Example 5 in which linalul and naringin were further added, increased the activity of the strain and increased toxin removal rate, showing excellent results in the fish toxicity test items.
상술한 바와 같이, 본 발명의 바람직한 실시예 및 시험예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, although the description has been made with reference to the preferred embodiments and test examples of the present invention, those skilled in the art can vary the present invention within the scope not departing from the spirit and scope of the present invention described in the following claims. You will understand that it can be modified and changed.

Claims (10)

  1. 금속산화물을 포함하는 무기응집제, 규산염 및 발포제를 포함하는 수질 개선용 다공체로, 상기 다공체는 비중이 0.5 내지 1.5이며, 기공율이 10 내지 60%, 비표면적이 1 내지 1,000㎡/g인 것을 특징으로 하는 수질 개선용 다공체.A porous body for improving water quality comprising an inorganic coagulant containing a metal oxide, a silicate, and a blowing agent, wherein the porous body has a specific gravity of 0.5 to 1.5, a porosity of 10 to 60%, and a specific surface area of 1 to 1,000 ㎡/g. Porous body for improving water quality.
  2. 제 1항에 있어서,The method of claim 1,
    상기 규산염은 하기 화학식 1의 구조를 갖는 것을 특징으로 하는 수질 개선용 다공체.The silicate is a porous body for improving water quality, characterized in that it has the structure of the following formula (1).
    [화학식 1][Formula 1]
    A2O-nSiO2 A 2 O-nSiO 2
    (상기 화학식 1에서 A는 나트륨, 칼륨, 리튬, 루비듐 및 세슘에서 선택되는 어느 하나이며, 상기 n은 1 내지 5의 정수이다.)(In Formula 1, A is any one selected from sodium, potassium, lithium, rubidium, and cesium, and n is an integer of 1 to 5.)
  3. 제 1항에 있어서,The method of claim 1,
    상기 발포제는 니트로스티렌, 메톡시스티렌, β-메틸스티렌, o-, m-, p-메틸스티렌, 메틸실릴스티렌, 비닐나프탈렌, 비닐비페닐, 비닐안트라센, 비닐클로라이드, 비닐티오펜, 비닐피롤리돈, 비닐피리딘, 술폭시스티렌, 시아노스티렌, 아미노스티렌, 에틸스티렌, β-에틸스티렌, 카르복시스티렌, 클로로스티렌, 페닐스티렌 및 하이드록시스티렌에서 선택되는 어느 하나 또는 복수의 모노머가 중합된 비닐계 수지를 포함하는 것을 특징으로 하는 수질 개선용 다공체.The blowing agent is nitrostyrene, methoxystyrene, β-methylstyrene, o-, m-, p-methylstyrene, methylsilylstyrene, vinylnaphthalene, vinylbiphenyl, vinylanthracene, vinylchloride, vinylthiophene, vinylpyrroly A vinyl-based polymer in which one or more monomers selected from money, vinylpyridine, sulfoxystyrene, cyanostyrene, aminostyrene, ethylstyrene, β-ethylstyrene, carboxystyrene, chlorostyrene, phenylstyrene and hydroxystyrene A porous body for improving water quality, comprising a resin.
  4. 제 1항에 있어서,The method of claim 1,
    상기 발포제는 황산구리, 산화구리, 질산은, 산화붕소, 산화아연, 이산화토륨, 산화마그네슘, 이산화티타늄, 인산삼칼슘, 산화알루미늄 및 흑연에서 선택되는 어느 하나 또는 복수의 중량제를 더 포함하는 것을 특징으로 하는 수질 개선용 다공체.The blowing agent is characterized in that it further comprises one or a plurality of weight agents selected from copper sulfate, copper oxide, silver nitrate, boron oxide, zinc oxide, thorium dioxide, magnesium oxide, titanium dioxide, tricalcium phosphate, aluminum oxide and graphite. Porous body for improving water quality.
  5. 제 1항에 있어서,The method of claim 1,
    상기 다공체는 내부에 염화칼슘, 염화마그네슘 및 염화리튬에서 선택되는 어느 하나 또는 복수의 비중조절제를 포함하는 것을 특징으로 하는 수질 개선용 다공체.The porous body for improving water quality, characterized in that the porous body contains one or a plurality of specific gravity control agents selected from calcium chloride, magnesium chloride and lithium chloride therein.
  6. 제 5항에 있어서,The method of claim 5,
    상기 비중조절제는 알루미노포스페이트계 제올라이트, 페로알루미노포스페이트계 제올라이트 및 실리코알루미노포스페이트계 제올라이트에서 선택되는 어느 하나 또는 복수의 제올라이트가 더 포함되는 것을 특징으로 하는 수질 개선용 다공체.The specific gravity control agent is a porous body for improving water quality, characterized in that it further comprises any one or a plurality of zeolites selected from aluminophosphate zeolite, ferroaluminophosphate zeolite, and silicoaluminophosphate zeolite.
  7. 제 1항에 있어서,The method of claim 1,
    상기 다공체는 표면에 아시네토박터 속, 아트로박터 속, 로도콕사이 속, 마이코박테리움 속, 슈도모나스 속, 잔토박터 속, 락토바실러스 속, 사카로마이세스 속, 로도슈도모나스 속, 스트렙토마이세스 속, 디모나스 속, 스트롬비드녹시스, 코레안시스 속 및 판토에아 속에서 선택되는 어느 하나 또는 복수의 균주가 포함된 코팅제가 피복된 것을 특징으로 하는 수질 개선용 다공체.The porous body is on the surface of the genus Acinetobacter, Atrobacter, Rhodocoxi, Mycobacterium, Pseudomonas, Xanthobacter, Lactobacillus, Saccharomyces, Rhodopseudomonas, Streptomyces. Porous body for improving water quality, characterized in that the coating agent containing any one or a plurality of strains selected from the genus, Dimonas, Stromvidnoxis, Koreensis and Pantoea is coated.
  8. 제 7항에 있어서,The method of claim 7,
    상기 균주는 아스로박터 속과 잔토박터 속 및 판토에아 속이 혼합된 것을 특징으로 하는 수질 개선용 다공체.The strain is a porous body for improving water quality, characterized in that a mixture of Asrobacter genus, Xanthobacter genus, and Pantoea genus.
  9. a) 금속산화물을 포함하는 무기응집제, 규산염, 물유리 및 발포제를 혼합하여 성형체를 제조하는 단계;a) preparing a molded article by mixing an inorganic coagulant containing a metal oxide, a silicate, a water glass, and a foaming agent;
    b) 상기 성형체를 300 내지 500℃에서 2 내지 5시간 동안 건조하는 단계;b) drying the molded body at 300 to 500°C for 2 to 5 hours;
    c) 상기 건조된 성형체를 800내지 1,000℃에서 5 내지 10시간 동안 소성하는 단계; c) firing the dried molded article at 800 to 1,000° C. for 5 to 10 hours;
    d) 상기 소성된 성형체를 황토로 피복하는 단계; 및d) covering the fired molded body with loess; And
    e) 상기 성형체를 균주가 포함된 코팅제에 침지시키는 단계;e) immersing the molded body in a coating agent containing the strain;
    를 포함하는 수질 개선용 다공체의 제조방법.A method of manufacturing a porous body for improving water quality comprising a.
  10. 제 9항에 있어서,The method of claim 9,
    상기 성형체는 아트로박터 속, 잔토박터 속, 락토바실러스 속, 사카로마이세스 속, 로도슈도모나스 속, 스트렙토마이세스 속 및 판토에아 속에서 선택되는 어느 하나 또는 복수의 균주를 포함하는 것을 특징으로 하는 수질 개선용 다공체의 제조방법.The shaped body is characterized in that it comprises any one or a plurality of strains selected from the genus Atrobacter, genus Xanthobacter, genus Lactobacillus, genus Saccharomyces, genus Rhodo Pseudomonas, genus Streptomyces, and genus Pantoea. A method of manufacturing a porous body for improving water quality.
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