WO2010029911A1 - 供給側流路材、及びスパイラル型分離膜エレメント - Google Patents
供給側流路材、及びスパイラル型分離膜エレメント Download PDFInfo
- Publication number
- WO2010029911A1 WO2010029911A1 PCT/JP2009/065640 JP2009065640W WO2010029911A1 WO 2010029911 A1 WO2010029911 A1 WO 2010029911A1 JP 2009065640 W JP2009065640 W JP 2009065640W WO 2010029911 A1 WO2010029911 A1 WO 2010029911A1
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- WIPO (PCT)
- Prior art keywords
- supply
- separation membrane
- antibacterial agent
- flow path
- antibacterial
- Prior art date
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- 230000009422 growth inhibiting effect Effects 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229960004068 hexachlorophene Drugs 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- IDUWTCGPAPTSFB-UHFFFAOYSA-N hexyl hydrogen sulfate Chemical compound CCCCCCOS(O)(=O)=O IDUWTCGPAPTSFB-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- LSHSZIMRIAJWRM-UHFFFAOYSA-N oxolane-2,3-dicarbonyl chloride Chemical compound ClC(=O)C1CCOC1C(Cl)=O LSHSZIMRIAJWRM-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MTAAPVANJNSBGV-UHFFFAOYSA-N pentane-1,1,1-tricarbonyl chloride Chemical compound CCCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O MTAAPVANJNSBGV-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- VLRIRAGKJXODNO-UHFFFAOYSA-N propane-1,1,1-tricarbonyl chloride Chemical compound CCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O VLRIRAGKJXODNO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
- A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
- B01D63/101—Spiral winding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/14—Specific spacers
- B01D2313/143—Specific spacers on the feed side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/10—Use of feed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/42—Details of membrane preparation apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
- C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a supply-side channel material used for a spiral-type separation membrane element that separates components present in a liquid, and a spiral-type separation membrane element using the supply-side channel material, more specifically, The present invention relates to a technique for imparting antibacterial properties to a spiral separation membrane element.
- a spiral separation membrane element one in which one or more of a separation membrane, a supply-side flow path material, and a permeate-side flow path material are wound around a perforated central tube is known.
- the supply-side fluid raw water
- the permeation-side fluid permeate
- the supply side channel material a net made of resin such as polypropylene has been mainly used.
- the separation membrane element feed solution contains bacteria and microorganisms, so in long-term operation, microorganisms grow around the raw water-side channel material and form a biofilm, which is called biofouling. It becomes.
- biofouling since the flow resistance of the raw water-side channel material is increased, the load of the supply pump is increased, and the biofilm attached to the membrane surface becomes a resistance and the membrane performance is deteriorated. Therefore, when biofouling progresses, the user needs to perform chemical cleaning, which is a great burden in terms of cost and labor.
- an antibacterial agent is introduced into the separation membrane by a manufacturing method in which a triclosan-based antibacterial agent is added to the dope (film forming solution) when forming the support membrane layer of the separation membrane.
- Separation membrane elements are known.
- the treated water permeates through the membrane in one direction, which is effective in controlling microorganisms in the permeated water. Antibacterial effect is difficult to occur. For this reason, there has been no direct effect of preventing bacteria and microorganisms from growing on the surface of the separation membrane or the supply-side flow path material, on which bacteria and the like are particularly likely to deposit.
- the volume per unit area (volume) of the flow channel material on the supply side is larger, and the antibacterial agent is retained in the method of introducing the antibacterial agent into the separation membrane. Since the amount cannot be increased, it was difficult to maintain the antibacterial effect for a long time.
- Patent Document 3 a separation membrane element formed by dispersing or coating an antibacterial agent on a supply side channel material is known.
- the antibacterial agent include silver zeolite, a compound having an amidine group or a guanidine group, or a quaternary ammonium salt.
- an object of the present invention is to provide a supply-side flow path material and a supply-side flow path material that can effectively prevent biofouling because sufficient antibacterial action is obtained even in a gap region between constituent yarns. It is to provide a spiral separation membrane element used.
- the present inventors have found that the above object can be achieved by including a chlorophenol-based antibacterial agent in the net constituting yarn, and have completed the present invention.
- the supply-side flow path material of the present invention is a supply-side flow path material used for a spiral separation membrane element, and the net constituting yarn constituting the net-shaped supply-side flow path material is made of a chlorophenol-based antibacterial agent. It is characterized by containing.
- the supply-side flow path material of the present invention as shown in the results of the examples, by including the chlorophenol antibacterial agent in the net constituting yarn, sufficient antibacterial action is obtained even in the gap region between the constituting yarns. Therefore, it is possible to provide a supply-side channel material that can effectively prevent biofouling.
- a sufficient antibacterial action can be obtained in the gap region between the constituent yarns even when the distance between the intersections of the net constituent yarns is 4 to 15 mm.
- the chlorophenol antibacterial agent is preferably triclosan (2,4,4'-trichloro-2'-hydroxy diphenyl ether) or a derivative thereof.
- the content of the chlorophenol antibacterial agent is preferably 0.005 to 10% by weight in the total weight.
- the content of the antibacterial agent is such, a sufficient antibacterial action can be obtained even in the gap region between the constituent yarns, and the strength and the like of the flow path material can be sufficiently maintained.
- the chlorophenol-based antibacterial agent is dispersed in the resin forming the net constituting yarn.
- coatings are subject to deterioration over time, so that they can be dispersed in the resin that forms the net yarn in terms of durability of antibacterial effects.
- it is.
- the spiral type separation membrane element of the present invention is a spiral type separation element in which one or more of a separation membrane, a supply side flow channel material and a permeate side flow channel material are wound around a perforated hollow central tube.
- the supply side flow path material is the supply side flow path material described above.
- the spiral separation membrane element of the present invention since the supply-side flow path material of the present invention is used, sufficient antibacterial action can be obtained even in a gap region between constituent yarns, thereby effectively preventing biofouling. It is possible to provide a spiral-type separation membrane element that can be used.
- the separation membrane preferably contains an inorganic antibacterial agent.
- inorganic antibacterial agents have high safety and sustainability with respect to toxicity and the like, and have a wide range of applicable bacterial species, but their antibacterial and bactericidal powers are weak, for example, the antibacterial area is extremely narrow.
- organic systems have high sustained release and diffusivity, they have high antibacterial and bactericidal activities, but have problems such as low persistence and a narrow range of applicable bacterial species.
- triclosan an organic antibacterial agent
- an inorganic antibacterial agent for the separation membrane through which water permeates and an organic antibacterial agent having a wide antibacterial range for the supply-side channel material through which the water passes the accumulation of bacteria is effectively suppressed. be able to.
- the antibacterial range (antibacterial spectrum) affected by the use of a plurality of types of antibacterial agents is widened, and the growth of more bacteria than in the case of one type can be suppressed.
- production of the resistant microbe by denaturation of microbe can also be suppressed.
- the separation membrane is a composite semipermeable membrane in which a skin layer containing a polyamide-based resin obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component is formed on the surface of the porous support, It is preferable that the antibacterial layer containing a silver type antibacterial agent and a polymer component is formed on the skin layer directly or via another layer.
- this composite semipermeable membrane When this composite semipermeable membrane is used, it has an antibacterial layer containing a silver-based antibacterial agent and a polymer component, and the antibacterial contamination property can be maintained for a long time by the antibacterial layer.
- the weight ratio of the silver antibacterial agent to the polymer component in the antibacterial layer is adjusted to 55:45 to 95: 5 (silver antibacterial agent: polymer component), and the silver antibacterial agent is excessive compared to the polymer component.
- the antibacterial layer is formed on the skin layer directly or via another layer and the antibacterial agent is not dispersed in the skin layer, the denseness of the skin layer is maintained. Thereby, the fall of the performance of a skin layer can be suppressed and not only a contamination
- the partially broken perspective view which shows an example of the nozzle used for the manufacturing method of the supply side flow-path material of this invention Explanatory drawing explaining operation of a nozzle hole
- the figure which shows an example of the supply side channel material of this invention Photograph showing results obtained in Antibacterial Evaluation Test 1
- the graph which shows the result obtained in antibacterial evaluation test 3 The partially broken perspective view which shows an example of the spiral type separation membrane element of this invention
- the supply-side flow path material of the present invention is a supply-side flow path material used for a spiral separation membrane element, and is a net-constituting yarn 1, 2 constituting a net-shaped supply-side flow path material. Is characterized by containing a chlorophenol antibacterial agent.
- the net-shaped supply-side flow path material may not have the net-constituting yarns 1 and 2 joined together, but the net-constituting yarns 1 and 2 are preferably joined together.
- a chlorophenol antibacterial agent refers to an antibacterial agent which is a phenol compound and has a chlorine group.
- Chlorophenol antibacterial agents include triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether), o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,4-dichlorophenol pentachlorophenol O-cresol, m-cresol, p-cresol, 4-chloro-m-cresol, 2,3,6-trichlorophenol, 2,3-dichlorophenol, 2,4,5-trichlorophenol, 2,4, 6-trichlorophenol, 2,3,4,6-tetrachlorophenol, 4-chloro-3,5-xylenol, 2,4-dichloro-3,5-xylenol, 4-chloro-3-methyl-6-isophenol Propylbenzene, P-chloro-o, n-amylphenol, P-chloro-o,
- triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether) represented by the chemical formula (Chemical Formula 1) or a derivative thereof can be preferably used.
- Triclosan derivatives include those in which the chlorine group of triclosan is substituted with a hydrogen atom or other halogen group, homologues having different substitution positions, or phosphoric acid esters, phosphonic acid esters, sulfuric acid esters, glucuronic acid esters of triclosan. Succinic acid ester or glutamic acid ester.
- a method of containing the chlorophenol-based antibacterial agent in the supply side channel material a method of mixing in advance in the raw material pellets when performing extrusion molding of the channel material, or after the extrusion molding, There is a method of post-processing the surface with a coating material containing an antibacterial agent.
- the antibacterial agent is mixed and kneaded with the material for forming the supply-side channel material and dispersed in the resin forming the net constituting yarn. It is possible to achieve the purpose of this application by applying an antibacterial agent solution to the surface and fixing it by heat drying, etc. However, in applications where a water flow at high pressure is used, such as a spiral separation membrane element, deterioration with time is likely to occur. From the viewpoint of durability of the effect, it is preferable to disperse in the resin forming the net constituting yarn.
- the content of the antibacterial agent is preferably 0.005 to 10% by weight in the total weight from the viewpoint of obtaining a sufficient antibacterial action even in the gap region between the constituent yarns and maintaining the strength of the flow path material and the like. .
- the content is preferably 1% by weight or less, and more preferably 0.75% by weight or less.
- the concentration is too low, it is difficult to obtain a sufficient antibacterial effect. Therefore, when used for a supply-side channel material for water treatment membrane applications, the antibacterial property is 0.020% by weight over the entire region of the supply-side channel material. The above is preferably used.
- the amount is preferably 0.005 to 1% by weight, more preferably 0.01 to 0.1% by weight, based on the total weight of the coating material.
- Examples of the resin constituting the net-like supply-side channel material or the base material before coating include resins such as polypropylene, polyethylene, nylon, and polyester, and polyolefin resins such as polypropylene and polyethylene are particularly preferable.
- the supply-side flow path material or the base material before coating of the present invention can be produced by, for example, shear method molding or fusion method molding, and as shown in FIG. A net-like material joined with C can be obtained.
- shear molding as an example.
- the MFR of a resin such as polypropylene according to JIS K7210: 1999 is preferably 1.5 g / 10 min or more, and more preferably 1.7 to 4.0 g / 10 min. If the MFR is too low, a web-like deformation tends to occur at the intersection. On the other hand, if the MFR is too high, it becomes difficult to form the net.
- the resin MFR can generally be adjusted by the weight average molecular weight, molecular weight distribution, type and amount of additives added to the resin, and the like.
- the total thickness of the net obtained is preferably 0.3 to 2 mm
- the diameter (width) of the constituent yarn is preferably 0.08 to 1 mm
- the crossing angle is preferably 30 to 150 °. .
- the thickness of the net is reduced, the linear velocity of the membrane surface increases and concentration polarization can be suppressed.
- the thickness of the net is too small, the problem of floating components in the supply liquid blocking the flow path and the pump for feeding the supply liquid There is a problem that the required power of becomes large.
- the thread spacing and diameter ratio of each of the net constituting threads 1 and 2 can be freely changed.
- the intersection distance (thread spacing) is 4 to 15 mm, and the diameter ratio is 1 /. It is preferably 2 to 2/1, more preferably the intersection distance (thread distance) is 5 to 7 mm, and the diameter ratio is more preferably 2/3 to 3/2.
- each net structure is formed from a large number of nozzle holes 14 and 10 arranged on two circumferences of the die of the extruder. While extruding the yarns 1 and 2, the nozzle holes 14 and 10 are rotated relative to each other so that the nozzle holes 14 and 10 overlap each other at the intersecting portion of the net constituting yarn to form one nozzle, and the net constituting yarn 1 and 1 are intersected at the intersecting portion. A net is formed while 2 are fused together.
- FIG. 1 is a partially broken perspective view showing an example of a nozzle used in the method for manufacturing a supply-side flow path material of the present invention, and (b) is arranged on the inner circumference. It is the enlarged view of a nozzle hole.
- 2A is a bottom view showing the rotation operation of the nozzle hole
- FIGS. 2B to 2C are main part views showing the rotation operation of the nozzle hole
- FIG. 2D is obtained by this rotation operation. It is a top view of a net.
- the nozzle includes an inner rotary die 12 having nozzle holes 14 arranged on the inner circumference, and an outer rotary die 6 having nozzle holes 10 arranged on the outer circumference.
- the outer peripheral surface 13 of 12 and the inner peripheral surface 9 of the outer rotating die 6 are in contact with each other and can rotate in the reverse direction.
- the inner rotating die 12 is driven by the rotating shaft 4, and the outer rotating die 6 is driven by a gear 11 connected thereto.
- the outer rotating die 6 is rotatably held by the die housings 5 and 7.
- the resin extruded from the extruder is extruded from the nozzle holes 14 and 10 through a gap between the inner surface 5a of the die housing 5 and the outer surface 12a of the inner rotary die 12, and each net constituting yarn 1 and 2 is extruded. It becomes.
- the nozzle holes 14 and 10 are relatively rotated (see FIG. 2B), and the position where both the nozzle holes 14 and 10 are overlapped to form one nozzle (see FIG. 2C) is the net. And the net constituting yarns 1 and 2 are fused to each other.
- the MFR of the resin is low, the water scraping portion 3 is likely to be generated as shown in FIG.
- the temperature at which the resin is extruded from the nozzle holes 14 and 10 is preferably 230 to 300 ° C, more preferably 250 to 270 ° C. If the temperature at the time of extrusion is less than 230 ° C., the fluidity of the resin is insufficient and it becomes difficult to form a net, and water web deformation tends to occur. Moreover, when the temperature at the time of extrusion exceeds 300 degreeC, there exists a tendency for fluidity
- the extruded net is generally cooled in water or the like, wound up, and then cut into an appropriate size.
- the antibacterial agent can be uniformly dispersed throughout the flow path material by previously mixing the antibacterial agent into the raw material pellets.
- a method in which an antibacterial agent is mixed only in part of the raw material pellet master batch method
- an antibacterial agent is previously supported on porous fine particles, and this support is mixed with the raw material pellet.
- the porous fine particles include inorganic fine particles such as silica and zeolite, or porous polymer particles.
- the coating method is a solution or melt of a mixture of a coating material such as a resin and an antibacterial agent.
- a method of coating by coating, spray coating or the like is preferable.
- the coating material a material having good adhesion to the base material of the flow path material is preferable.
- a polyolefin resin is used as the base resin, it is preferable to use a polyvinyl alcohol (PVA) resin as the coating material.
- PVA polyvinyl alcohol
- the spiral separation membrane element of the present invention has a structure in which one or more of a separation membrane, a supply-side channel material, and a permeation-side channel material are wound around a perforated hollow central tube.
- a separation membrane a separation membrane
- a supply-side channel material a supply-side channel material
- a permeation-side channel material a permeation-side channel material
- the supply-side channel material conventionally known separation membranes, permeation-side channel materials, hollow central tubes, etc. Either can be adopted.
- a plurality of supply-side channel materials and permeation-side channel materials are used, a plurality of membrane leaves are wound around a hollow central tube.
- FIG. 7 is a partially broken perspective view showing an example of a conventional (invention) spiral separation membrane element.
- a cylindrical wound body R wound in a spiral shape around a perforated center tube 25 in a state where the separation membrane 21, the supply-side channel material 22, and the permeation-side channel material 23 are laminated.
- a sealing portion for preventing mixing of the supply-side fluid and the permeation-side fluid.
- the sealing portion includes, for example, a both-end sealing portion 31 and an outer peripheral side sealing portion 32, and a sealing portion 33 may be formed for sealing around the central tube 25.
- the separation membrane 21, the supply-side channel material 22, and the permeation-side channel material 23 are spirally wound around the perforated central tube 25 in a laminated state. It can be manufactured by a method including a step of forming the circular body R and a step of forming the sealing portions 31 and 32 for preventing the supply side fluid and the permeation side fluid from being mixed.
- the spiral separation membrane element of the present invention is not intended to limit the application, but has a particularly large antibacterial action against Escherichia coli, so that the separation membrane used for separation treatment such as wastewater treatment, brine desalination, seawater desalination, etc. The effect is particularly exerted when used in an element.
- the separation membrane used contains an inorganic antibacterial agent.
- the inorganic antibacterial agent include an antibacterial glass, a quaternary ammonium salt, a quaternary phosphonium salt and the like in addition to a silver antibacterial agent described in detail later.
- an ultrafiltration membrane, a loose reverse osmosis membrane, a reverse osmosis membrane or the like is preferably used.
- a method of containing an inorganic antibacterial agent a method of containing an inorganic antibacterial agent in the separation membrane itself (for example, a skin layer of a reverse osmosis membrane), an antibacterial agent directly on the surface of the separation membrane or via another layer, and Examples thereof include a method for forming an antibacterial layer containing a polymer component.
- the method of forming an antibacterial layer directly on the surface of the separation membrane or via another layer allows the antibacterial layer to maintain the microbial contamination resistance for a long period of time and to reduce the performance of the skin layer. This is preferable because not only the anti-contamination property but also the water permeation performance and the salt rejection can be kept high.
- the separation membrane is a composite semipermeable membrane in which a skin layer containing a polyamide-based resin obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component is formed on the surface of a porous support.
- the antibacterial layer containing the silver antibacterial agent and the polymer component is preferably formed on the skin layer directly or via another layer.
- a polyamide resin and a silver salt compound obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component are used as a method of adding an inorganic antibacterial agent to the separation membrane itself (for example, a skin layer of a reverse osmosis membrane).
- a method including a step of forming a skin layer including the surface of the porous support and a step of reducing the silver salt compound to deposit metallic silver in and / or on the skin layer is preferable.
- the silver salt compound is preferably reduced with active energy rays, and silver nitrate is preferably used as the silver salt compound.
- the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic and alicyclic polyfunctional amines.
- aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
- aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
- examples include benzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
- Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
- Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine, and the like.
- the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
- Examples of the polyfunctional acid halide include aromatic, aliphatic and alicyclic polyfunctional acid halides.
- aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonylbenzene dicarboxylic acid.
- An acid dichloride etc. are mentioned.
- Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoid Examples include luhalides.
- Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, and tetrahydrofuran.
- Examples thereof include tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
- the porous support for supporting the skin layer is not particularly limited as long as it can support the skin layer, and usually an ultrafiltration membrane having micropores with an average pore diameter of about 10 to 500 mm is preferably used.
- the material for forming the porous support include various materials such as polysulfone and polyarylethersulfone such as polyethersulfone, polyimide, and vinylidene fluoride.
- the thickness of such a porous support is usually about 25 to 125 ⁇ m, preferably about 40 to 75 ⁇ m, but is not necessarily limited thereto.
- the porous support is reinforced by backing with a base material such as woven fabric or nonwoven fabric.
- the method for forming the skin layer containing the polyamide resin on the surface of the porous support is not particularly limited, and any known method can be used.
- an interfacial condensation method is a method in which a skin layer is formed by bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization.
- a polyamide resin skin layer is directly formed on a porous support by interfacial polymerization on the porous support. Details of the conditions of the interfacial condensation method are described in JP-A-58-24303 and JP-A-1-180208, and those known techniques can be appropriately employed.
- the thickness of the skin layer formed on the porous support is not particularly limited, but is usually about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
- an antibacterial layer containing a silver antibacterial agent and a polymer component is formed on the skin layer directly or via another layer.
- the weight ratio of the silver antibacterial agent and the polymer component in the antibacterial layer is preferably 55:45 to 95: 5 (silver antibacterial agent: polymer component), more preferably 60:40 to 90:10. is there.
- the silver antibacterial agent used in the present invention is not particularly limited as long as it is a compound containing a silver component, and examples thereof include metallic silver, silver oxide, silver halide, and a carrier containing silver ions. Of these, it is particularly preferable to use a support containing silver ions. Examples of the support include zeolite, silica gel, calcium phosphate, and zirconium phosphate. Of these, it is preferable to use zirconium phosphate. Zirconium phosphate is more hydrophobic than other carriers and can maintain the antibacterial effect of silver ions for a long period of time during water treatment.
- the average particle size of the silver antibacterial agent is preferably 1.5 ⁇ m or less, more preferably 1 ⁇ m or less.
- the measuring method of an average particle diameter is based on description of an Example.
- the polymer component is not particularly limited as long as it does not dissolve the skin layer and the porous support and does not elute during the water treatment operation.
- polyvinyl alcohol polyvinyl pyrrole, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyethylene glycol, And saponified polyethylene-vinyl acetate copolymer.
- polyvinyl alcohol it is preferable to use polyvinyl alcohol, and it is particularly preferable to use polyvinyl alcohol having a saponification degree of 99% or more.
- the antibacterial layer is obtained by applying an aqueous solution containing the silver antibacterial agent and the polymer component directly on the skin layer or through another layer (for example, a protective layer containing a hydrophilic resin) and then drying. To form.
- a coating method spraying, application
- the solvent in addition to water, an organic solvent such as a skin layer that does not deteriorate the performance may be used in combination.
- the concentration of the silver antibacterial agent in the aqueous solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
- the concentration of the polymer component in the aqueous solution is preferably 0.01 to 1% by weight, more preferably 0.1 to 0.7% by weight.
- the thickness of the antibacterial layer is not particularly limited, but is usually 0.05 to 5 ⁇ m, preferably 0.1 to 3 ⁇ m, more preferably 0.1 to 2 ⁇ m. If the thickness of the antibacterial layer is too thin, the antibacterial property is not sufficiently exhibited, and when the spiral element is wound, the film is likely to be scratched by rubbing, and the salt inhibition rate may be lowered. On the other hand, if the thickness of the antibacterial layer is too thick, the water permeation flux may be lowered to a practical range or less.
- the silver content in the antibacterial layer is preferably 30 mg / m 2 or more, and more preferably 35 mg / m 2 or more. When the silver content is less than 30 mg / m 2 , it becomes difficult to maintain excellent antibacterial properties for a long period of time.
- the silver content in the antibacterial layer is preferably 1000 mg / m 2 or less, more preferably 500 mg / m 2 or less, from the viewpoint of cost and prevention of film damage.
- the produced flat membrane-like composite semipermeable membrane is cut into a predetermined shape and size and set in a cell for flat membrane evaluation.
- An aqueous solution containing about 1500 mg / L NaCl and adjusted to pH 6.5 to 7.5 with NaOH is brought into contact with the membrane at 25 ° C. by applying a differential pressure of 1.5 MPa between the supply side and the permeation side of the membrane.
- the permeation rate and conductivity of the permeated water obtained by this operation were measured, and the permeation flux (m 3 / m 2 ⁇ d) and the salt rejection (%) were calculated.
- Salt rejection was calculated in advance using a correlation (calibration curve) between NaCl concentration and aqueous solution conductivity in advance.
- Salt rejection (%) ⁇ 1 ⁇ (NaCl concentration in the permeate [mg / L]) / (NaCl concentration in the feed liquid [mg / L]) ⁇ ⁇ 100
- Example 1 Using an extruder equipped with the nozzle shown in FIG. 1, by introducing pellets containing 0.025% by weight of triclosan as an antibacterial agent into polypropylene resin (F122G, manufactured by Mitsui Chemicals), melt extrusion at 260 ° C. A net-like supply-side channel material was formed by shearing molding.
- the nozzle shape and the extrusion conditions were adjusted so that the net obtained had a total thickness of 0.79 mm, a constituent yarn diameter (width) of 0.3 mm, a yarn interval of 5 mm, and an intersection angle of 90 °.
- Example 1 a flow path material was produced under the same conditions as in Example 1 except that pellets containing no antibacterial agent were used.
- Example 2 the flow channel material was used under the same conditions as in Example 1 except that pellets containing 2% by weight of silver zeolite (manufactured by Kanebo Kasei Co., Ltd., bactekiller, silver content: 30% by weight) were used as the antibacterial agent. Was made.
- pellets containing 2% by weight of silver zeolite manufactured by Kanebo Kasei Co., Ltd., bactekiller, silver content: 30% by weight
- Antibacterial evaluation test 1 E. coli K-12 was inoculated into LB medium and cultured at 35 ° C. for 24 hours.
- In order to attach Escherichia coli to the channel material prepare 10 3 to 10 4 cfu / ml physiological saline solution of Escherichia coli, put 20 ml of the bacterial solution in the centrifuge tube, put each channel material one by one, and shake for 1 hour did. The channel material was taken out, washed with 10 ml of physiological saline three times, placed on an SCDA medium, and cultured at 35 ° C. for 2 to 5 days.
- Example 1 did not show bacterial growth.
- the bacteria containing no antibacterial agent of Comparative Example 1 showed growth of many bacteria.
- the growth of bacteria was less when the silver antibacterial agent of Comparative Example 2 was added than when there was no antibacterial agent, the growth of bacteria was observed.
- Antibacterial evaluation test 2 E. coli K-12 was inoculated into LB medium and cultured at 35 ° C. for 24 hours.
- As an inhibition circle formation test an Escherichia coli 10 6 to 10 7 cfu / ml physiological saline solution was prepared and smeared on an SCDA medium. Each channel material was placed thereon and cultured at 35 ° C. for 2 days.
- the channel material containing triclosan of Example 1 had a region that prevented colony formation inside and around the channel material (a gap region between constituent yarns). On the other hand, in the case where the antibacterial agent of Comparative Example 1 was not contained, bacterial growth was observed around and inside the flow path material.
- Antibacterial evaluation test 3 E. coli K-12 was inoculated into LB medium and cultured at 35 ° C. for 24 hours.
- the prepared channel material is placed on a sterile petri dish, 400 ⁇ l of the prepared Escherichia coli 10 5 cfu / ml (500-fold diluted LB medium) bacterial solution is dropped and covered with a polyethylene film so that the liquid does not dry. I made it.
- Example 2 An aqueous solution containing 1.0% by weight of a silver antibacterial agent having an average particle size of 0.9 ⁇ m (manufactured by Toagosei Co., Ltd., Novalon AG1100) and 0.5% by weight of polyvinyl alcohol (degree of saponification: 99%) Penetration composite membrane (manufactured by Nitto Denko Corporation, model: ES20, skin layer: polyamide resin, performance: permeation flux 1.2 (m 3 / m 2 ⁇ d), salt rejection 99.6 (% )) And then dried in an oven at 130 ° C. for 3 minutes to form an antibacterial layer to produce a composite semipermeable membrane. A spiral-type separation membrane element shown in FIG. 7 using this composite semipermeable membrane, the supply-side channel material obtained in Example 1, and the transmission-side channel material (PET resin, thickness 0.3 mm) was made.
- water treated with activated sludge and MF membrane (SDI value 3 to 6) from industrial wastewater at the Hakozaki site in Fukuoka Prefecture has a permeation flux of 0.3 to 0.4 (m 3 / m 2 ⁇ d). Then, before and after flowing for about 1 month at a recovery rate of 15 to 20%, an evaluation test was performed by applying a pressure of 1.5 MPa using an evaluation water containing 1500 ppm of NaCl and pH 6.5 to 7.0. The permeation flux retention was 90% or more.
- Example 3 18% by weight of polysulfone (P-3500, manufactured by Solvay Co., Ltd.) was dissolved in N, N monodimethylformamide (DMF) on a non-woven fabric substrate, and uniformly applied with a wet thickness of 200 ⁇ m, and then placed in a 40-50 ° C. water bath.
- the porous support was produced by solidifying and washing by immersion. On this porous support, 3% by weight of m-phenylenediamine, 0.15% by weight of sodium lauryl sulfate, 3% by weight of triethylamine, 6% by weight of camphorsulfonic acid, 5% by weight of isopropyl alcohol, and 0.5% by weight of silver nitrate.
- An aqueous solution coating layer was formed by applying the aqueous amine solution and then removing the excess aqueous amine solution.
- an organic solution containing 0.2% by weight of trimesic acid chloride and naphthenic hydrocarbon (manufactured by Shin Nippon Oil Co., Ltd., naphthesol 160) was applied to the surface of the aqueous solution coating layer. Then, it hold
- UV-A 320 ⁇ 390nm
- UV-B 280 ⁇ 320nm
- UV-C 250 ⁇ 260nm
- the composite semipermeable membrane was produced by irradiating / cm 2 , UV-V: 70 mJ / cm 2 , reducing silver nitrate and precipitating metallic silver in the skin layer and / or on the surface.
- the permeation flux of the membrane was 1.2 (m 3 / m 2 ⁇ d), and the salt rejection was 99 (%), and the produced composite semipermeable membrane had antibacterial properties.
- Example 2 Using this composite semipermeable membrane, the supply-side channel material obtained in Example 1, and the transmission-side channel material (PET resin, thickness 0.3 mm), the spiral type separation membrane shown in FIG. An element was produced. When this element was evaluated in the same manner as in Example 2, the permeation flux retention was 80% or more.
- Example 4 A supply-side channel material prepared in Example 1, a composite semipermeable membrane prepared in Example 2 without using a silver-based antibacterial agent, and a transmission-side channel material (made of PET resin, thickness 0.3 mm) The spiral separation membrane element was used to make it. When this element was evaluated in the same manner as in Example 2, the permeation flux retention was 75% or more.
- Comparative Example 3 Using the supply-side channel material of Comparative Example 1, the composite semipermeable membrane prepared in Example 2 without using the silver-based antibacterial agent, and the transmission-side channel material (PET resin, thickness 0.3 mm) A spiral separation membrane element was produced. When this element was evaluated in the same manner as in Example 2, the permeation flux retention was about 60%.
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Abstract
Description
水溶液中の銀系抗菌剤の濃度は、0.1~10重量%であることが好ましく、より好ましくは0.5~5重量%である。また、水溶液中のポリマー成分の濃度は、0.01~1重量%であることが好ましく、より好ましくは0.1~0.7重量%である。
作製した平膜状の複合半透膜を所定の形状、サイズに切断し、平膜評価用のセルにセットする。約1500mg/LのNaClを含みかつNaOHを用いてpH6.5~7.5に調整した水溶液を25℃で膜の供給側と透過側に1.5MPaの差圧を与えて膜に接触させる。この操作によって得られた透過水の透過速度および電導度を測定し、透過流束(m3/m2・d)および塩阻止率(%)を算出した。塩阻止率は、NaCl濃度と水溶液電導度の相関(検量線)を事前に作成し、それらを用いて下式により算出した。
塩阻止率(%)={1-(透過液中のNaCl濃度[mg/L])/(供給液中のNaCl濃度[mg/L])}×100
実施例1
図1に示すノズルを備えた押出機を用いて、ポリプロピレン樹脂(三井化学製、F122G)に抗菌剤としてトリクロサンを0.025重量%含有するペレットを導入し、260℃で溶融押出しすることで、剪断法成形にてネット状の供給側流路材を形成した。このとき、得られるネットが、全厚み0.79mm、構成糸の径(幅)0.3mm、糸間隔5mm、交差角度90°になるようにノズル形状と押出条件を調整した。
実施例1において、抗菌剤を含有しないペレットを用いたこと以外は、実施例1と同じ条件で流路材を作製した。
実施例1において、抗菌剤として銀ゼオライト(カネボウ化成(株)製、バクテキラー、銀含有量30重量%)2重量%含有するペレットを用いたこと以外は、実施例1と同じ条件で流路材を作製した。
大腸菌K-12をLB培地に植菌し35℃×24時間培養した。流路材への大腸菌を付着させるために、大腸菌103~104cfu/ml生理食塩水溶液を調製し、菌液20mlを遠沈管に入れ、各流路材を1枚ずつ入れ、1時間振盪した。流路材を取り出し生理食塩水10mlで3回洗浄後、SCDA培地上に置き、35℃で2~5日培養した。
大腸菌K-12をLB培地に植菌し35℃×24時間培養した。阻止円形成試験として、大腸菌106~107cfu/ml生理食塩水溶液を調製し、SCDA培地上に塗沫した。各流路材をその上に置き、35℃で2日間培養した。
大腸菌K-12をLB培地に植菌し35℃×24時間培養した。抗菌力試験として、準備した流路材を滅菌シャーレ上に置き、調整した大腸菌105cfu/ml(500倍希釈LB培地)菌液を400μl滴下し、ポリエチレンフィルムをかぶせて、液体が乾かないようにした。35℃(湿度90%以上)24H培養する。培養後菌液を回収し、その菌数をSCDA培地にて計数した。
平均粒子径0.9μmの銀系抗菌剤(東亜合成社製、ノバロンAG1100)1.0重量%、及びポリビニルアルコール(ケン化度:99%)0.5重量%を含む水溶液を、超低圧逆浸透複合膜(日東電工社製、型式:ES20、スキン層:ポリアミド系樹脂、性能:前記測定方法で透過流束1.2(m3/m2・d)、塩阻止率99.6(%))のスキン層上に塗布し、その後オーブンにて130℃で3分間乾燥させて抗菌層を形成して複合半透膜を作製した。この複合半透膜と、実施例1で得られた供給側流路材と、透過側流路材(PET樹脂製、厚み0.3mm)とを用いて図7に示したスパイラル型分離膜エレメントを作製した。
不織布基材上にポリスルホン(Solvay社製、P-3500)18重量%をN,N一ジメチルホルムアミド(DMF)に溶解し、Wet厚み200μmで均一に塗布した後、40~50℃の水浴中に浸漬させることで凝固、洗浄して多孔性支持体を作製した。この多孔性支持体上にm-フェニレンジアミン3重量%、ラウリル硫酸ナトリウム0.15重量%、トリエチルアミン3重量%、カンファースルホン酸6重量%、イソプロピルアルコール5重量%、及び硝酸銀0.5重量%を含有するアミン水溶液を塗布し、その後余分なアミン水溶液を除去することにより水溶液被覆層を形成した。次に、前記水溶液被覆層の表面にトリメシン酸クロライド0.2重量%及びナフテン系炭化水素(新日本石油株式会社製、ナフテゾール160)を含有する有機溶液を塗布した。その後、120℃の熱風乾燥機中で3分間保持して、多孔性支持体上にポリアミド系樹脂及び硝酸銀を含むスキン層を形成した。その後さらにスキン層表面に高圧水銀ランプの紫外線(UV-A(320~390nm):280mJ/cm2、UV-B(280~320nm):200mJ/cm2、UV-C(250~260nm):150mJ/cm2、UV-V:70mJ/cm2、を照射して、硝酸銀を還元してスキン層中及び/又は表面に金属銀を析出させて複合半透膜を作製した。作製した複合半透膜の透過流束は1.2(m3/m2・d)、塩阻止率は99(%)であった。また、作製した複合半透膜は抗菌性を有していた。
実施例1で作製した供給側流路材と、実施例2において銀系抗菌剤を用いずに作製した複合半透膜と、透過側流路材(PET樹脂製、厚み0.3mm)とを用いてスパイラル型分離膜エレメントを作製した。このエレメントに対して実施例2と同様の評価を行ったところ、透過流束の保持率は75%以上であった。
比較例1の供給側流路材と、実施例2において銀系抗菌剤を用いずに作製した複合半透膜と、透過側流路材(PET樹脂製、厚み0.3mm)とを用いてスパイラル型分離膜エレメントを作製した。このエレメントに対して実施例2と同様の評価を行ったところ、透過流束の保持率は約60%程度であった。
2 ネット構成糸
3 水掻き部
10 ノズル孔(外側)
14 ノズル孔(内側)
C 交差部
21 分離膜
22 供給側流路材
23 透過側流路材
25 中空状中心管
Claims (8)
- スパイラル型分離膜エレメントに用いる供給側流路材であって、ネット状の供給側流路材を構成するネット構成糸が、クロロフェノール系抗菌剤を含有する供給側流路材。
- 前記ネット構成糸の交点間隔が4~15mmである請求項1記載の供給側流路材。
- 前記クロロフェノール系抗菌剤が、トリクロサン(2,4,4’‐trichloro-2’-hydroxy diphenyl ether)又はその誘導体である請求項1又は2に記載の供給側流路材。
- 前記クロロフェノール系抗菌剤の含有量が、全重量中0.005~10重量%である請求項1~3いずれかに記載の供給側流路材。
- 前記クロロフェノール系抗菌剤が、ネット構成糸を形成する樹脂中に分散している請求項1~4いずれかに記載の供給側流路材。
- 分離膜、供給側流路材及び透過側流路材の単数又は複数が、有孔の中空状中心管の周りに巻きつけられているスパイラル型分離膜エレメントにおいて、前記供給側流路材は、請求項1~5いずれかに記載の供給側流路材であることを特徴とするスパイラル型分離膜エレメント。
- 前記分離膜は無機系抗菌剤を含有する請求項6に記載のスパイラル型分離膜エレメント。
- 前記分離膜は、多官能アミン成分と多官能酸ハライド成分とを反応させてなるポリアミド系樹脂を含むスキン層が多孔性支持体の表面に形成されている複合半透膜であって、スキン層上に直接又は他の層を介して銀系抗菌剤及びポリマー成分を含有する抗菌層が形成されている請求項7に記載のスパイラル型分離膜エレメント。
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CN2009801328307A CN102131565A (zh) | 2008-09-09 | 2009-09-08 | 供给侧流路材料和螺旋型分离膜元件 |
US13/062,759 US20110168623A1 (en) | 2008-09-09 | 2009-09-08 | Feed side passage material and spiral separation membrane element |
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JP (1) | JP5231362B2 (ja) |
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EP2447397A1 (de) * | 2010-10-29 | 2012-05-02 | Carl Freudenberg KG | Vliesstoffe aus synthetischen Polymeren sowie Rotationsspinnverfahren zur Herstellung derselben |
CN104411385A (zh) * | 2012-06-26 | 2015-03-11 | 康韦德塑料制品有限公司 | 使用低能量进料间隔件的膜过滤 |
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CN102791363A (zh) * | 2010-01-15 | 2012-11-21 | 海德拉罗迪克斯公司 | 用于过滤装置的盐水密封件 |
CN105120973A (zh) * | 2012-12-25 | 2015-12-02 | 墨尔本大学 | 材料和方法 |
KR101647966B1 (ko) * | 2013-03-29 | 2016-08-12 | 충남대학교산학협력단 | 미량 유해가스 탈취 및 제거용 복합섬유필터의 제조방법 |
USD800747S1 (en) | 2015-03-17 | 2017-10-24 | Samsung Electronics Co., Ltd. | Display screen or portion thereof with animated graphical user interface |
JP6135721B2 (ja) * | 2015-08-10 | 2017-05-31 | 大日本印刷株式会社 | 樹脂付リードフレームおよびその製造方法、ならびに半導体装置およびその製造方法 |
CN106474945A (zh) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | 一种抗菌聚酰胺高分子膜及其制备方法和应用 |
JP6719291B2 (ja) * | 2016-06-24 | 2020-07-08 | オルガノ株式会社 | 水処理装置の有機分離膜の洗浄方法 |
US11673095B2 (en) | 2018-04-19 | 2023-06-13 | Crosstek Membrane Technology | Helical separation membranes and technologies utilizing the same |
CN109632678A (zh) * | 2018-11-16 | 2019-04-16 | 蓝星(杭州)膜工业有限公司 | 一种聚酰胺复合膜片残留胺含量的检测方法 |
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US20110168623A1 (en) | 2011-07-14 |
JP5231362B2 (ja) | 2013-07-10 |
CN102131565A (zh) | 2011-07-20 |
KR20110052748A (ko) | 2011-05-18 |
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