WO2023053985A1 - Véhicule de microorganismes immobilisés pour le traitement des eaux - Google Patents

Véhicule de microorganismes immobilisés pour le traitement des eaux Download PDF

Info

Publication number
WO2023053985A1
WO2023053985A1 PCT/JP2022/034514 JP2022034514W WO2023053985A1 WO 2023053985 A1 WO2023053985 A1 WO 2023053985A1 JP 2022034514 W JP2022034514 W JP 2022034514W WO 2023053985 A1 WO2023053985 A1 WO 2023053985A1
Authority
WO
WIPO (PCT)
Prior art keywords
flexible polyurethane
polyurethane foam
water
carrier
microorganism
Prior art date
Application number
PCT/JP2022/034514
Other languages
English (en)
Japanese (ja)
Inventor
一宏 大西
雅弘 内藤
惣一郎 廣川
Original Assignee
日清紡ケミカル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日清紡ケミカル株式会社 filed Critical 日清紡ケミカル株式会社
Priority to JP2023551305A priority Critical patent/JPWO2023053985A1/ja
Publication of WO2023053985A1 publication Critical patent/WO2023053985A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C12N11/093—Polyurethanes

Definitions

  • the present invention relates to a microorganism-immobilizing carrier for water treatment (hereinafter also simply referred to as "carrier").
  • Patent Document 1 describes a hollow tubular plastic carrier with a large specific surface area as a carrier. The introduction of water-soluble polymers containing microorganisms into the pores of the material is disclosed.
  • Patent Document 2 a porous resin obtained by extruding and foaming a thermoplastic resin is preheated, and a coating material extruded from an extruder is adhered to the outer surface of the resin.
  • a carrier that suppresses the deformation of the porous resin and the accompanying increase in water flow resistance is described.
  • the carrier described in Patent Document 1 has a risk that the water-soluble polymer may peel off during water treatment due to physical stirring or the like, and it is difficult to maintain the organic wastewater treatment performance for a long time, and it does not have sufficient durability. I wouldn't say I did.
  • the water-soluble polymer containing microorganisms has a small contact area between the water-soluble polymer portion and the organic wastewater, and the organic wastewater treatment capacity is not sufficient.
  • the carrier described in Patent Document 2 is obtained by bonding a porous resin and a coating material made of a thermoplastic resin, and the pore (cell) structure of the preheated porous resin allows microorganisms to reach the inside of the carrier. A uniform state that facilitates penetration was not maintained, and it could not be said that the organic wastewater treatment performance was good.
  • the present invention was made in order to solve such problems, and aims to provide a microorganism immobilization carrier for water treatment that has excellent durability while maintaining organic wastewater treatment performance.
  • the present invention is based on the discovery that by integrating a predetermined flexible polyurethane foam with a hard member, it is possible to obtain a microorganism-immobilizing carrier for water treatment that has excellent durability while maintaining organic wastewater treatment performance. It is a thing.
  • a flexible polyurethane foam and a hard member harder than the flexible polyurethane foam are integrated, and the flexible polyurethane foam has a swelling density of 20 to 70 kg/m 3 when swollen with water, and an average A microorganism-immobilizing carrier for water treatment, having a pore number of 2 to 8/5 mm and a volume swelling rate by water swelling of more than 100% and 1000% or less.
  • the flexible polyurethane foam has a time of 1 hour or less until all cubic pieces of the flexible polyurethane foam with a side length of 5 mm dropped on the surface of distilled water at 25° C. sink below the surface of the water.
  • [3] The microorganism-immobilizing carrier for water treatment according to [1] or [2] above, wherein the flexible polyurethane foam is a columnar body.
  • [4] The microorganism-immobilizing carrier for water treatment according to [3] above, wherein the hard member is a cylindrical body or a slitted cylindrical body covering the side peripheral surface of the columnar body of the flexible polyurethane foam.
  • the hard member contains a thermoplastic resin.
  • a microorganism-immobilizing carrier for water treatment that has excellent durability while maintaining organic wastewater treatment performance is provided.
  • FIG. 1 is a perspective view showing one embodiment of a microorganism-immobilizing carrier for water treatment of the present invention.
  • FIG. Fig. 2 is a perspective view showing another embodiment of the microorganism-immobilizing carrier for water treatment of the present invention.
  • a flexible polyurethane foam and a hard member harder than the flexible polyurethane foam are integrated, and the flexible polyurethane foam has a swelling density of 20 to 70 kg when swollen with water. /m 3 , the average number of pores when swollen with water is 2 to 8/5 mm, and the volume swelling ratio expressed by the ratio of the volume when swollen with water to the volume in the absolute dry state is more than 100% and 1000% or less.
  • the carrier as described above maintains the organic wastewater treatment performance of the flexible polyurethane foam, and has good durability against physical agitation by stirring blades and the like, impact by water flow, and self-weight pressure in a fixed bed. .
  • Flexible polyurethane foams are thermosetting, have excellent heat resistance compared to thermoplastic resins, and have good flexibility with excellent adhesiveness to microorganisms, and are suitably used as carriers. be able to.
  • the flexible polyurethane foam defined in the present invention having predetermined physical properties has excellent hydrophilicity and a cell structure with excellent adhesion to microorganisms, and can exhibit excellent organic wastewater treatment performance.
  • the flexible polyurethane foam used in the present invention has a swelling density when swollen with water of 20 to 70 kg/m 3 , preferably 25 to 65 kg/m 3 , more preferably 30 to 70 kg/m 3 . 60 kg/ m3 .
  • swelling density refers to a value obtained by dividing the absolute-dry mass of flexible polyurethane foam by the volume when swollen with water.
  • the "absolutely dry state” is also referred to as an absolutely dry state, and refers to a state in which the flexible polyurethane foam is dried at 110°C, which is the heat-resistant temperature of the polyurethane resin or less, and no weight reduction is observed.
  • “When swollen with water” refers to a state in which the flexible polyurethane foam is immersed in pure water at 25°C for 1 hour.
  • the flexible polyurethane foam preferably has an absolute dry density of 30 to 100 kg/m 3 , more preferably 35 to 95 kg/m 3 , still more preferably 40 to 90 kg/m 3 from the viewpoint of a moderate volume swelling rate. be.
  • the flexible polyurethane foam has a volume swelling ratio of more than 100% to 1000% or less, preferably 105 to 600%, more preferably 110 to 300%.
  • volume swelling rate refers to a value expressed by the ratio of the volume of a flexible polyurethane foam when swollen with water to the volume of the flexible polyurethane foam in an absolutely dry state.
  • the absolute dry volume includes the volume of the pores (cells) of the flexible polyurethane foam, and is the volume determined based on the external dimensions. For example, if the outer shape is a rectangular parallelepiped or a cube, the value is calculated as the product of the length, width and height of the three sides.
  • the volume when swollen with water is also the volume determined based on the external dimensions, and includes the volume of water inside and the cells of the flexible polyurethane foam.
  • the cell structure of the flexible polyurethane foam should be a continuous pore structure from the viewpoint of allowing microorganisms, oxygen, and substrates that serve as nutrients for microorganisms in water to penetrate sufficiently into the interior of the foam, thereby facilitating the immobilization of microorganisms on the carrier. is preferred.
  • the polyurethane skeleton constituting the cell structure has a so-called wall structure in which adjacent cells are partially film-like and partitioned by wall surfaces having a large surface area.
  • the average number of pores when swollen with water is 2 to 8/5 mm, preferably 3 to 7/5 mm, and more preferably 4 to 6/5 mm.
  • the term "average number of pores" as used herein refers to the average number of pores existing on a straight line of arbitrary three lengths of 5 mm in flexible polyurethane foam when swollen with water.
  • the average pore size of the flexible polyurethane foam when swollen with water is preferably 0.2 to 5 mm, more preferably 0.4 to 3 mm, still more preferably 0.5 to 2 mm.
  • the average pore diameter is the average diameter of 50 pores, assuming that the pores in the microscopic image are perfect circles whose diameter is the average value of the long and short diameters.
  • the flexible polyurethane foam preferably exhibits good hydrophilicity, and the settling time in water can be used as an index to express the hydrophilicity.
  • the "underwater settling time" in the present invention refers to the time required for a cubic piece of flexible polyurethane foam with a side length of 5 mm dropped on the surface of distilled water at 25° C. to settle in water.
  • the flexible polyurethane foam preferably has a settling time in water of 1 hour or less, more preferably 30 minutes or less, and even more preferably 15 minutes or less.
  • Flexible polyurethane foam is mainly composed of polyurethane resin (the content ratio is the largest), and optional components such as inorganic fillers, colorants, etc., and curing agents and Other ingredients may be included, such as ingredients derived from blowing agents, foam stabilizers, surfactants, catalysts, and the like.
  • the content of these other components in the flexible polyurethane foam is within a range that does not interfere with the effects of the present invention.
  • the production method of the flexible polyurethane foam is not particularly limited. be.
  • a flexible polyurethane foam composition containing a urethane prepolymer, a polyisocyanate compound, a curing agent and a foaming agent, and optionally other components such as a foam stabilizer and a catalyst is preferably used.
  • a flexible polyurethane foam is obtained by foaming and curing the flexible polyurethane foam composition.
  • the polyisocyanate compound is referred to as "polyisocyanate compound (a)" in order to distinguish it from the polyisocyanate compound that is a raw material for synthesizing the urethane prepolymer, which will be described later. It may be described as "polyisocyanate compound (b)".
  • the urethane prepolymer is a polymer obtained by reacting a polyol compound with an amount of polyisocyanate compound (b) in which the molar equivalent ratio of the isocyanate group to the hydroxyl group of the polyol compound is excessive. has two or more isocyanate groups.
  • the urethane prepolymer may be used alone or in combination of two or more. By using such a prepolymer as a raw material component, the production reaction of a flexible polyurethane foam is facilitated, and a flexible polyurethane foam having excellent homogeneity with little variation in cell structure can be easily obtained.
  • the urethane prepolymer is preferably a reaction product of a polyether polyol and a polyisocyanate compound (b), and is a polyether urethane prepolymer having two or more isocyanate groups in one molecule.
  • Both polyether polyols and polyester polyols can impart hydrophilicity to the resulting flexible polyurethane foams, but polyether polyols are superior in hydrolysis resistance to polyester polyols. Since flexible polyurethane foams are used in water, polyether polyols are preferable to polyester polyols as the polyol compound used as the raw material for synthesizing the urethane prepolymer from the viewpoint of the durability of the carrier.
  • Polyether polyols include, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. These are obtained by ring-opening polymerization of cyclic ether compounds such as ethylene oxide (hereinafter referred to as "EO"), propylene oxide (hereinafter referred to as "PO”) and tetrahydrofuran. Polyether polyols may be used singly or in combination of two or more. A copolymer of a cyclic ether compound may also be used, and an EO-PO copolymer is preferable from the viewpoint of the flexibility and hydrophilicity of the resulting flexible polyurethane foam.
  • the monomer composition ratio of EO and PO in the EO-PO copolymer is preferably 90/10 to 10/90, more preferably 85/15 to 15/85, and still more preferably 80/20 in mass ratio. ⁇ 20/80.
  • the polyether polyol preferably has a viscosity that is not too high, and preferably has a number average molecular weight of 1,000 to 8,000, more preferably 2,000 to 7,000, and still more preferably 2,500 to 5,000. .
  • the polyisocyanate compound (b) to be reacted with the polyether polyol is a compound having two or more isocyanate groups in one molecule, and is not particularly limited.
  • the polyisocyanate compound (b) include toluene diisocyanate (hereinafter referred to as "TDI"), xylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. , dicyclohexylmethane diisocyanate, and the like.
  • the polyisocyanate compound (b) may be used singly or in combination of two or more.
  • the polyisocyanate compound (b) when the polyisocyanate compound (b) is a compound having isomers, it may be one type of each isomer or a mixture of two or more isomers.
  • TDI has two isomers, toluene-2,4-diisocyanate (2,4-TDI) and toluene-2,6-diisocyanate (2,6-TDI). ,6-TDI alone or a mixture of the two may be used.
  • the polyisocyanate compound (a) is not particularly limited, and specific examples thereof include the same as those exemplified for the polyisocyanate compound (b), which is the starting material for synthesizing the urethane prepolymer.
  • the polyisocyanate compound (a) may be used alone or in combination of two or more.
  • the polyisocyanate compound (a) may be the same as or different from the polyisocyanate compound (b) used as the starting material for synthesizing the urethane prepolymer.
  • the content of the polyisocyanate compound (a) is set in consideration of the viscosity of the flexible polyurethane foam composition, the hydrophilicity of the flexible polyurethane foam, etc., and is preferably 35 parts by mass with respect to 100 parts by mass of the urethane prepolymer. Below, it is more preferably 1 to 30 parts by mass, still more preferably 2 to 25 parts by mass.
  • the curing agent is a compounding component for cross-linking and curing the urethane prepolymer and the polyisocyanate compound (a), and is also called a cross-linking agent.
  • curing agents include water; polyhydric alcohols such as glycerin, 1,4-butanediol and diethylene glycol; amine compounds such as ethanolamines and polyethylenepolyamines. Polyols obtained by ring-opening polymerization of polyhydric alcohol with ethylene oxide, propylene oxide, etc., and those obtained by adding a small amount of propylene oxide to the above-mentioned amine compounds may also be used. These may be used individually by 1 type, or may use 2 or more types together.
  • water is preferably used from the viewpoint of reactivity, ease of handling, cost, and the like.
  • the content of the curing agent in the flexible polyurethane foam composition can be appropriately set in consideration of the flexibility, elasticity, strength, etc. of the flexible polyurethane foam obtained from the composition.
  • a blowing agent is a formulation ingredient for the foam formation of flexible polyurethane foams.
  • the foaming agent generates carbon dioxide gas by reacting with an isocyanate group during a reaction to produce polyurethane, or evaporates itself during an exothermic reaction to foam polyurethane.
  • foaming agents include water, hydrofluorocarbons (HFC), hydrofluoroolefins (HFO), hydrochlorofluoroolefins (HCFO), carbon dioxide, and hydrocarbons such as cyclopentane. These may be used individually by 1 type, or may be used in combination of 2 or more types.
  • water is preferably used alone from the viewpoint of ease of handling, cost, environmental protection, and the like.
  • the content of the foaming agent in the flexible polyurethane foam composition is appropriately set in consideration of the foaming speed (foam generation speed) of the flexible polyurethane foam produced using the composition, the mixing state of the composition, and the like. can do.
  • water works both as a curing agent and as a foaming agent, and is suitable as a compounding component of a flexible polyurethane foam composition.
  • the content of water when used as a curing agent and a foaming agent in the flexible polyurethane foam composition is preferably 20 to 90 parts by mass with respect to a total of 100 parts by mass of the urethane prepolymer and the polyisocyanate compound (a). More preferably 25 to 85 parts by mass, still more preferably 30 to 80 parts by mass.
  • the flexible polyurethane foam composition may optionally contain other ingredients such as foam stabilizers, catalysts, inorganic fillers, colorants, and solvents.
  • the content of the other compounding components in 100 parts by mass of the flexible polyurethane foam composition is preferably 15 parts by mass or less, from the viewpoint of production efficiency of flexible polyurethane foams using the composition. It is more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.
  • a foam stabilizer is a compounding component for adjusting the foam state of a flexible polyurethane foam, and examples thereof include surfactants and silicone oils. These may be used individually by 1 type, or may use 2 or more types together.
  • the content of the foam stabilizer in 100 parts by mass of the flexible polyurethane foam composition is such that excess foam stabilizer remains in the flexible polyurethane foam, and from the viewpoint of suppressing foaming when the carrier is used. , preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.
  • catalysts include known catalysts used in the production of flexible polyurethane foams, such as triethylamine, triethylenediamine, diethanolamine, N,N-dimethylaminoethoxyethanol, N-methylmorpholine, N-ethylmorpholine, tetramethylguanidine.
  • tin catalysts such as stannous octoate and dibutyltin dilaurate; and other metal catalysts such as phenylmercuric propionate and lead octenate.
  • the inorganic filler is a compounding component for adjusting the specific gravity for the purpose of, for example, allowing the flexible polyurethane foam to quickly settle in water.
  • Examples thereof include barium sulfate, calcium carbonate, talc, silica, alumina, activated carbon, zeolite, and graphite. etc. These may be used individually by 1 type, or may use 2 or more types together.
  • the flexible polyurethane foam composition may be a one-component composition containing all of the ingredients, but is preferably a two-component composition of A and B components.
  • Liquid A preferably contains a urethane prepolymer and a polyisocyanate compound (a), and liquid B preferably contains a curing agent and a foaming agent.
  • a two-component composition in which two component liquids, A component and B component, are separately prepared and then mixed and foamed, is suitable for stable and efficient production of flexible polyurethane foam.
  • Liquid A contains the above-described urethane prepolymer and polyisocyanate compound (a), and may contain the other ingredients in the flexible polyurethane foam composition.
  • the total content of the urethane prepolymer and the polyisocyanate compound (a) in liquid A is preferably 30 parts by mass or more, more preferably 35 to 100 parts by mass in 100 parts by mass of liquid A, from the viewpoint of production efficiency of flexible polyurethane foam. parts by mass, more preferably 40 to 100 parts by mass.
  • Liquid B contains a curing agent and a foaming agent, and may contain the above-mentioned other compounding ingredients in the flexible polyurethane foam composition. From the viewpoint of efficiently producing a flexible polyurethane foam having a good cell structure, the total content of the curing agent and foaming agent in liquid B is preferably 45 parts by mass or more, more preferably 60 to 100 parts by mass, more preferably 65 to 100 parts by mass.
  • a method for producing a flexible polyurethane foam using a two-component flexible polyurethane foam composition of liquids A and B a known production method for a two-component flexible polyurethane foam can be applied.
  • a flexible polyurethane foam can be obtained by a method such as mixing liquid A and liquid B using a mixing head and performing injection foaming.
  • the mass mixing ratio of liquid A and liquid B is preferably 45/55 to 80/20, more preferably 50/50 to 77/23, from the viewpoint of efficiently obtaining a homogeneous flexible polyurethane foam with a desired cell structure. , more preferably 55/45 to 75/25.
  • the flexible polyurethane foam is a columnar body from the viewpoint of production efficiency and cost in mass production of the carrier.
  • the columnar body include a columnar body, a prismatic body, and a columnar body having a star-shaped polygonal bottom surface.
  • cylindrical bodies are preferable from the viewpoint of homogeneity and strength of the carrier.
  • a flexible polyurethane foam and a hard member harder than the flexible polyurethane foam are integrated.
  • the rigid material which is harder than the flexible polyurethane foam, suppresses the deformation and damage of the flexible polyurethane foam against physical agitation by stirring blades, impact from water flow, and self-weight pressure in the fixed bed when using the carrier. be. Therefore, the flexible polyurethane foam integrated with the hard member is endowed with excellent durability by the hard member while maintaining the organic wastewater treatment performance.
  • the material of the hard member is not particularly limited as long as it is harder than the flexible polyurethane foam to be integrated. From the viewpoints of preventing damage to the water treatment tank, facilitating integration with the flexible polyurethane foam, versatility, etc., it is preferable that the resin contains a thermoplastic resin.
  • thermoplastic resins include polyvinyl chloride, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-(meth)acrylate copolymer, Polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), nylon, polycarbonate, polyethylene terephthalate, poly(meth)acrylate, polyvinyl alcohol and the like.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • the specific gravity of the flexible polyurethane foam when the specific gravity of the flexible polyurethane foam is small, the specific gravity of the carrier is increased so that when the carrier is put into the water treatment tank, it quickly settles in the water, and organic wastewater is discharged while promoting the adhesion of microorganisms. It may also have a specific gravity adjusting role, such as ensuring good fluidity of the carrier therein. Therefore, from the viewpoint of specific gravity adjustment, it is also preferable to select the material of the hard member.
  • the method of integrating the flexible polyurethane foam and the hard member is not particularly limited. It may be integrated by self-adhesion.
  • the shapes of the flexible polyurethane foam and the hard member are not particularly limited. It may be formed in
  • FIGS. 1 and 2 Preferred embodiments of the carrier of the present invention are those shown in FIGS. 1 and 2, for example.
  • the carrier shown in FIGS. 1 and 2 has a rigid member 2 having slits S covering the side peripheral surfaces of columnar bodies 1 of flexible polyurethane foam.
  • the columnar body 1 is a cylindrical body, and in FIG. 2, the columnar body 1 is a quadrangular prism.
  • the hard member 2 covering the side peripheral surface of the columnar body is a cylindrical body covering the side peripheral surface of the columnar body 1 made of flexible polyurethane foam, or as shown in FIGS. It is preferably a slitted tubular body having a slit S as shown, and more preferably a slitted tubular body.
  • the hard member 2 has a C-shaped cross section in the bottom direction.
  • the size of the carrier is not particularly limited, and can be set as appropriate in consideration of the shape and scale of the water treatment tank, water swelling, microbial adhesion, handling, manufacturing efficiency, and the like.
  • the diameter of the bottom surface and the height of the columnar body 1 are each preferably 3. It is about to 200 mm, more preferably 5 to 100 mm, still more preferably 6 to 80 mm, still more preferably 7 to 50 mm.
  • the thickness of the hard member 2 integrated with the columnar body 1 is not particularly limited. It can be appropriately set according to the material of the sheath hard member 2 and the like. For example, when the diameter and height of the bottom surface of the columnar body 1 are about 3 to 200 mm, the thickness of the hard member 2 is preferably 0.1 to 10 mm, more preferably 0.2 to 8 mm. , more preferably 0.3 to 5 mm.
  • the hard member 2 to be integrated with the columnar body 1 is formed integrally with itself from the viewpoint of manufacturing efficiency and cost during mass production of the carrier, and as described above, it is a tubular body with slits. Preferably. Since the hard member 2 is a single member, it is possible to reduce the labor and burden of forming the hard member compared to the case where a plurality of members are combined. is likely to be retained, and separation and detachment can also be suppressed.
  • the shape of the slit S is not particularly limited. 1 and 2, one of S is a communication slit extending from one bottom end of the columnar body 1 of the hard member 2 to the other bottom end. is preferred. If one of the slits S is a communicating slit, while maintaining the integrity of the hard member 2, it is easy to secure a contact surface between the flexible urethane foam columnar body 1 and the organic wastewater when using the carrier. It is also preferable from the viewpoint of manufacturing efficiency during mass production.
  • the hard member 2 is preferably a cylindrical body or a slitted cylindrical body that covers at least a part of the side peripheral surface of the columnar body 1. Both bottom surfaces of the body 1 are preferably uncoated. That is, it is preferable that the flexible polyurethane foam is exposed on both bottom surfaces of the columnar body 1 .
  • the method for producing the carrier described above is not particularly limited, but the carrier of the present invention is preferably produced by, for example, the following production method.
  • a hollow elongated member having a slit extending in the longitudinal direction is used as the hard member, and the slit or the longitudinal end of the elongated member is formed in the hollow portion of the elongated member.
  • the flexible polyurethane foam composition injected and foamed from the slit or the end of the long material has a uniform cell structure throughout the hollow part of the long material.
  • Polyurethane foams can be formed. Injection and foaming through a slit is more preferable from the viewpoint of performing more uniform injection and foaming in the length direction of the elongated material.
  • the slit or the end of the elongated material is used to obtain a rod-shaped object in which the flexible polyurethane foam columnar body and the hard member are integrated, and by cutting the rod-shaped object, the same shape is obtained,
  • the cell structure of the porous body soft polyurethane foam
  • the carrier in which the rigid member and the porous body are integrated can be mass-produced efficiently.
  • the manufacturing method can be performed, for example, by the following steps.
  • a single linear slit is processed in the length direction of a cylindrical pipe made of thermoplastic resin, and a cylindrical body having a C-shaped cross section in the radial direction (bottom direction) of the pipe (hereinafter referred to as “C-shaped ) is obtained.
  • a flexible polyurethane foam composition is injected and foamed into the hollow portion of the C-shaped tubular body through a slit or an end portion in the length direction of the tubular body, and the flexible polyurethane foam is injected into the hollow portion of the C-shaped tubular body. to obtain a bar having
  • a carrier in which a cylindrical body of flexible polyurethane foam is covered with a C-shaped cylindrical body can be produced. .
  • sample carrier [Preparation of sample carrier] ⁇ Sample carrier (1)> A cylindrical transparent resin pipe made of polycarbonate having an outer diameter of 22 mm and a wall thickness of 2 mm was slit in the longitudinal direction with a width of about 10 mm to obtain a C-shaped tubular body. A flexible polyurethane foam composition obtained by mixing the following liquid A and liquid B at a mass mixing ratio of 71/29 was injected into the hollow portion of the C-shaped cylindrical body through a slit and foamed. After removing the soft polyurethane foam protruding from the C-shaped cylindrical body, the carrier was cut into a length of 22 mm, and the cylindrical body of the flexible polyurethane foam was covered with the C-shaped cylindrical body (sample carrier (1)). manufactured.
  • TDI-modified EO-PO copolymer as urethane prepolymer ⁇ Liquid A ⁇ TDI-modified EO-PO copolymer as urethane prepolymer (EO/PO mass ratio: 24/76, number average molecular weight of EO-PO copolymer: 2700 (theoretical value), NCO (isocyanate group) content: 4. 5% by mass)) and 88.3 g of TDI ("Coronate (registered trademark) T-80" manufactured by Tosoh Corporation; 2,4-TDI/2,6-TDI molar ratio 80/20) were stirred and mixed. was prepared.
  • a comparison sample carrier (1) was obtained by cutting the C-shaped tubular body of the sample carrier (1) as it was into a length of 22 mm.
  • sample carrier (2) In the manufacture of the above sample carrier (1), instead of the cylindrical transparent resin pipe made of polycarbonate, a cylindrical resin pipe made of ABS resin having the same shape is used, and the rest is the same as the sample carrier (1). , to prepare the sample carrier (2).
  • sample carrier (3) In the manufacture of the sample carrier (2), the cylindrical resin pipe made of ABS resin was not subjected to slit processing, but in the same manner as the sample carrier (2), the peripheral surface of the cylindrical body of flexible polyurethane foam was prepared. A carrier (sample carrier (3)) entirely covered with a cylindrical body (without slits) was produced.
  • Comparison sample carrier (2) was obtained by cutting the C-shaped tubular body of the sample carrier (2) as it was into a length of 22 mm.
  • Comparative sample carrier (3) A flexible polyurethane foam (without hard members) hollowed out from the sample carrier (1) was used as a comparative sample carrier (3).
  • a test piece (approximately 5 mm ⁇ approximately 5 mm, thickness of approximately 5 mm when swollen with water) was weighed with an electronic balance, dried in a drier at 110° C., and the absolute dry mass M d was measured.
  • the length of each side of the test piece in the absolute dry state is measured with a vernier caliper (resolution 0.05 mm; hereinafter the same), and the product of the length of each side is the volume of the test piece in the absolute dry state V d and The value of M d /V d was taken as the absolute dry density.
  • the volume swelling ratio is the ratio (V w /V d ) of the volume V w when swollen with water and the volume V d in the absolute dry state (V w /V d ).
  • ⁇ Average pore diameter> After measuring the volume Vw when swollen with water, an arbitrary point near the center of the surface of the test piece was observed with a microscope, and the major axis and minor axis of one pore in the observed image were measured.
  • the pore shape was regarded as a perfect circle whose diameter was the average value of the major and minor axes, and the diameters of 50 pores were obtained in the same manner. The average value of these diameters was taken as the average pore diameter when swollen with water.
  • ⁇ Underwater sedimentation time> One test piece (a cube with a length of 5 mm on each side) is placed in a 1 L polypropylene disposable cup and placed on the water surface of 600 mL of distilled water at 25 ° C. After dropping and putting it, the entire test piece is on the water surface. The time until it settled down (under water) was measured. Ten test pieces were measured. If the time until sedimentation (sedimentation time in water) was 1 hour or less, it was determined that the hydrophilicity was good.
  • sample carriers (1) to (3) were adhered to a tensile breaking strength tester (manufactured by Shimadzu Corporation), and tensile strength was measured . It was confirmed that the flexible polyurethane foam and the C-shaped cylindrical body covering it did not separate and maintained their integrated state. The same tensile strength measurement was performed on the flexible polyurethane foams having the same shape and size as the sample carriers (1) to (3) and the comparative sample carrier (3) (both flexible polyurethane foams only). All of them had a tensile breaking strength of about 3 N/cm 2 . From these evaluation results, sample carriers (1) to (3) maintained the state of integration between the flexible polyurethane foam and the hard member even when used for water treatment, and had greater strength than the case without the hard member. It can be said that it is high and has excellent durability.
  • test (1) sample carrier (1) and comparative sample carrier (1) were used, and in test (2), sample carriers (2) and (3), and comparative sample carriers (2) and (3) were used. .
  • test raw water mainly containing sodium nitrate was passed through the tank, and treated water was appropriately sampled from the tank to measure the residual NO 3 —N concentration (N 1 ).
  • the NO 3 —N concentration (N 0 ) of the test raw water passing through was also measured.
  • the ratio of the NO 3 -N concentration decrease (N 0 -N 1 ) to the NO 3 -N concentration (N 0 ) of the test raw water was calculated as the NO 3 -N removal rate [%].
  • the NO 3 —N concentration and raw water flow rate of the test raw water were adjusted, and the nitrogen volume load was changed to a high state, and the treatment effect was confirmed.
  • Table 2 shows the test results for sample carrier (1) and comparative sample carrier (1).
  • No. 4 the NO 3 —N removal rate decreased. After 5 trials were discontinued.
  • COD source glucose; COD 400 mg/L
  • the ratio of the decrease in COD value (C 0 ⁇ C 1 ) to the COD value (C 0 ) of test raw water was calculated as the COD removal rate [%].
  • the glucose concentration and raw water flow rate of test raw water were adjusted, and the treatment effect was confirmed assuming a state of high COD volume load.
  • Table 3 shows the test results for sample carriers (2) and (3) and comparative sample carriers (2) and (3).
  • the comparative sample carrier (2) No. Since the COD removal rate in No. 5 decreased, After 6 trials were discontinued.
  • the sample carriers (1)-(3) integrated with the hard member have a sufficiently high NO 3 —N, comparable to the comparative sample carrier (3) without the hard member. It was confirmed that the removal rate and the COD removal rate were exhibited. In addition, it was confirmed that all of the sample carriers (1) to (3) maintained the integrated state of the flexible polyurethane foam and the hard member even after the test, and were excellent in durability.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Microbiology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

L'invention concerne un véhicule de microorganismes immobilisés pour le traitement des eaux, qui présente une excellente durabilité tout en maintenant les performances de traitement des eaux usées organiques. Le véhicule de microorganismes immobilisés pour le traitement des eaux selon la présente invention comprend une forme intégrale d'une mousse de polyuréthane flexible et un élément rigide qui est plus dur que la mousse de polyuréthane flexible, la mousse de polyuréthane flexible ayant une densité de gonflement de 20-70 kg/m3 lorsqu'elle est gorgée d'eau, un nombre moyen de pores de 2 à 8 pores/5 mm lorsqu'elle est gorgée d'eau, et un rapport de gonflement en volume de plus de 100 % et de 1000 % ou moins lorsqu'elle est gorgée d'eau.
PCT/JP2022/034514 2021-09-28 2022-09-15 Véhicule de microorganismes immobilisés pour le traitement des eaux WO2023053985A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023551305A JPWO2023053985A1 (fr) 2021-09-28 2022-09-15

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021158236 2021-09-28
JP2021-158236 2021-09-28

Publications (1)

Publication Number Publication Date
WO2023053985A1 true WO2023053985A1 (fr) 2023-04-06

Family

ID=85782467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/034514 WO2023053985A1 (fr) 2021-09-28 2022-09-15 Véhicule de microorganismes immobilisés pour le traitement des eaux

Country Status (2)

Country Link
JP (1) JPWO2023053985A1 (fr)
WO (1) WO2023053985A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009220075A (ja) * 2008-03-18 2009-10-01 Chugoku Electric Power Co Inc:The 微生物固定化担体、生物学的硝化脱窒装置及びその使用方法
JP2013154298A (ja) * 2012-01-30 2013-08-15 Kubota Corp 水処理用濾材及び浄化槽
JP2016123957A (ja) * 2015-01-07 2016-07-11 三機工業株式会社 溶存性物質及び揮発性物質を含む廃水の処理装置及び同廃水の処理方法
WO2021045103A1 (fr) * 2019-09-02 2021-03-11 日清紡ケミカル株式会社 Procédé de production de mousse de polyuréthane souple
WO2021045102A1 (fr) * 2019-09-02 2021-03-11 日清紡ケミカル株式会社 Procédé de production de mousse de polyuréthane souple
WO2021131934A1 (fr) * 2019-12-23 2021-07-01 日清紡ケミカル株式会社 Support d'immobilisation de micro-organismes pour traitement des eaux, corps en mousse de résine et composition de matière de départ de celui-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009220075A (ja) * 2008-03-18 2009-10-01 Chugoku Electric Power Co Inc:The 微生物固定化担体、生物学的硝化脱窒装置及びその使用方法
JP2013154298A (ja) * 2012-01-30 2013-08-15 Kubota Corp 水処理用濾材及び浄化槽
JP2016123957A (ja) * 2015-01-07 2016-07-11 三機工業株式会社 溶存性物質及び揮発性物質を含む廃水の処理装置及び同廃水の処理方法
WO2021045103A1 (fr) * 2019-09-02 2021-03-11 日清紡ケミカル株式会社 Procédé de production de mousse de polyuréthane souple
WO2021045102A1 (fr) * 2019-09-02 2021-03-11 日清紡ケミカル株式会社 Procédé de production de mousse de polyuréthane souple
WO2021131934A1 (fr) * 2019-12-23 2021-07-01 日清紡ケミカル株式会社 Support d'immobilisation de micro-organismes pour traitement des eaux, corps en mousse de résine et composition de matière de départ de celui-ci

Also Published As

Publication number Publication date
JPWO2023053985A1 (fr) 2023-04-06

Similar Documents

Publication Publication Date Title
US6610205B2 (en) Process for nitrifying denitrifying organic waste water
ES2302205T3 (es) Espumas de poliuretano de baja densidad y su empleo en suelas de zapatos.
JP6917535B1 (ja) 軟質ポリウレタンフォームの製造方法
JPH02289608A (ja) 吸水性ポリウレタンフォーム成形品の製造方法
JP5490426B2 (ja) 微生物固定化担体用ポリウレタンフォーム
JP4123003B2 (ja) 微生物固定化担体、汚水浄化方法及び汚水浄化装置
WO2023053985A1 (fr) Véhicule de microorganismes immobilisés pour le traitement des eaux
WO2023053984A1 (fr) Véhicule fixé de microorganismes pour le traitement des eaux et son procédé de fabrication
US6565751B2 (en) Bioreactor carrier, process for producing the carrier and method for using the same
WO2005074583A2 (fr) Composite mousse pour l'absorption d'hydrocarbures et procede d'elaboration
WO2021131934A1 (fr) Support d'immobilisation de micro-organismes pour traitement des eaux, corps en mousse de résine et composition de matière de départ de celui-ci
CN114269804B (zh) 软质聚氨酯泡沫的制备方法
JP2004359950A (ja) 薬剤耐性を付与した水膨潤性ポリウレタンフォームとその製造方法及びそれを用いたバイオリアクター用担体
CN117120381A (zh) 水处理用微生物固定化载体、软质聚氨酯泡沫组合物以及软质聚氨酯泡沫的制备方法
JP2020028867A (ja) 水処理用の微生物固定化担体
JP4828370B2 (ja) 水処理用微生物担体の製造方法
CN111072909B (zh) 亲水性聚氨酯预聚物及其制备方法和在软质泡沫塑料中的应用
JP2024089252A (ja) 水処理用微生物固定化担体
JP4275815B2 (ja) 吸水性ポリウレタン発泡体の製造方法
WO2021045104A1 (fr) Procédé de production d'un support immobilisant des microorganismes pour le traitement des eaux
JP2002052394A (ja) バイオリアクター用担体、その製造方法及び該担体の使用方法
JPH11207380A (ja) 微生物担体
JP2021181538A (ja) 低膨潤親水性ウレタンフォーム
JP2004217708A (ja) 薬剤耐性を付与した水膨潤性ポリウレタンフォーム及びそれを用いたバイオリアクター用担体
JP2001314184A (ja) 流動床用微生物固定化担体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22875856

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023551305

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE