WO2000052252A1 - Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber - Google Patents
Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber Download PDFInfo
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- WO2000052252A1 WO2000052252A1 PCT/JP2000/001043 JP0001043W WO0052252A1 WO 2000052252 A1 WO2000052252 A1 WO 2000052252A1 JP 0001043 W JP0001043 W JP 0001043W WO 0052252 A1 WO0052252 A1 WO 0052252A1
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- fiber
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- chelate
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- forming
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2303/16—Regeneration of sorbents, filters
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
Definitions
- the present invention relates to a novel metal chelate-forming fiber and a metal chelate-forming fiber and a method for producing the metal chelate fiber.
- the metal ion trapping method using this fiber, and the metal chelate fiber, the chelate-forming fiber is, for example, a metal ion present in a very small amount in water, particularly copper, zinc, It is capable of selectively and efficiently adsorbing harmful heavy metal ions such as nickel and cobalt even in the low pH range, and is widely used for purification of industrial wastewater, drinking water and oil.
- the metal chelate fiber which can be used effectively and chelate-bonded to the metal, can be used as a catalyst for various catalysts, antibacterial and bactericidal agents, Electromagnetic shielding material, light shielding material, colored clothing It can be effectively used as an ornament, a fertilizer, a metal protective agent, etc., and can be easily disposed of or incinerated.
- BACKGROUND ART Various kinds of harmful heavy metal ions may be contained in industrial wastewater, etc., and from the viewpoint of environmental pollution prevention, these harmful heavy metal ions are reduced as much as possible by wastewater treatment. Need to be removed. In addition, many of these harmful heavy metal ions can be effectively used as useful metals, etc., which are separated and recovered and used as secondary resources. If it can be used effectively, it is two birds with one stone.
- ion-exchange resins are widely used to remove harmful heavy metal ions contained in wastewater and capture valuable metal ions, but selectively use low-concentration metal ions.
- the effect of adsorbing on water is not always satisfactory.
- the chelate resin which has the property of forming chelates with metal ions and selectively capturing them, is an excellent selective capture for metal ions, especially heavy metal ions. It is used in the water treatment field to remove and trap heavy metals.However, many of the chelate resins are based on crosslinking agents such as divinylbenzene. Bead shape with a rigid three-dimensional structure and high hydrophobicity, and the diffusion and penetration rate of metal ions and regenerant into the resin is slow, so there is also a problem with processing efficiency. . In addition, even in the case of disposable use without recycling, it is difficult to incinerate, and the problem of how to reduce the volume of used resin becomes a major problem.
- a fibrous chelating resin As a measure to improve the properties, a fibrous chelating resin has been proposed (for example, Patent No. 277201).
- the fibrous chelating resin has a large specific surface area and exhibits high absorption / desorption properties because a chelate-forming functional group serving as a metal ion absorption / desorption point is present on the surface.
- this fibrous chelating resin is a polymer of olefin or halogenated olefin, dioxin or the like is used during incineration. causes the problem of harmful gas generation.
- the production method of the fibrous chelating resin that is, the modification treatment for imparting metal chelating activity is complicated, and a special method using ionizing radiation or the like must be adopted. Points to be improved in terms of equipment, safety, manufacturing costs, etc. There are many.
- the present invention has been made in view of the above circumstances.
- the first object of the present invention is to have excellent trapping performance against harmful heavy metal ions, etc.
- the second object of the present invention is to provide a metal chelate-forming fiber which can be easily incinerated, etc., and can be manufactured at a low cost by a simple and safe method.
- An object of the present invention is to provide a method capable of easily, safely and efficiently producing such a metal chelate forming fiber.
- a third object of the present invention is to use the above-mentioned metal chelate-forming fibers to reduce metal ions contained in a small amount in an aqueous liquid, an oily liquid, or a gas such as exhaust gas. It is an object of the present invention to provide a method that can be efficiently captured by a simple method. Further, a fourth object of the present invention is to provide a metal chelate in which various metals are chelate-bonded to the surface of the chelate-forming fiber so that the catalytic activity and antibacterial activity of the metal can be effectively utilized. Provide fiber.
- the metal-chelate-forming fiber of the present invention which can solve the above-mentioned problems, includes a reactive double bond and a glycidyl group in a fiber molecule of a natural fiber or a regenerated fiber. At least one selected from the group consisting of amino dicarboxylic acid, thiocarboxylic acid, and phosphoric acid having reactivity with an epoxy group via a crosslinking reactive compound in the molecule.
- the gist is where the metal chelate-forming compounds are bound.
- cross-linking reactive compound is Glycidyl acrylate, glycidyl acrylate, and arginoleglycidyl ether, which may be used alone or in combination of two or more as necessary be able to.
- Preferred specific examples of the chelate-forming compound include iminodiacetic acid, ethylenediamine diacetate, ethylenediamine triacetic acid, thioglycolic acid, and the like. Examples thereof include thiolingic acid and phosphoric acid, which can be used alone or in combination of two or more.
- these metal chelate-forming compounds particularly preferred are iminodiacetic acid, ethylenediamine triacetic acid, and thioglycolic acid.
- Examples of the above natural fibers or regenerated fibers include vegetable fibers such as cellulosic fibers including regenerated fibers such as biscoice, and animal fibers such as wool and silk.
- the fibers can be used as a powder material in the form of short fibers, or as a filter material such as a sheet, mat, or non-woven fabric.
- the production method of the present invention is positioned as a method capable of industrially and efficiently producing the above-mentioned metal chelate-forming fiber, and the composition is a natural fiber or a regenerated fiber.
- a cross-linking reactive compound having a reactive double bond and a glycidyl group in the molecule is subjected to a graph-polymerization reaction using a redox catalyst. Characterized by the addition reaction of at least one chelate-forming compound selected from the group consisting of amino dicarboxylic acid, thiocarboxylic acid and phosphoric acid having the following reactivity: have.
- Preferred examples of the crosslinking reactive compound used here include glycidyl methacrylate, glycidyl acrylate, and aryl glycidyl ether. Can be used alone If necessary, two or more types can be used in combination.
- Preferred specific examples of chelate-forming compounds include iminodiacetate, ethylendiamine diacetate, ethylendiamine triacetic acid, thioglycolic acid, and thiolin. Goic acid, phosphoric acid and the like can be mentioned, and these can be used alone or in combination of two or more.
- the preferred redox catalyst used in carrying out this production method is a combination of a ferrous salt, hydrogen peroxide and thiourea dioxide. If a method is used in which the fiber is pre-treated with a ferrous salt and hydrogen peroxide and thiourea dioxide are allowed to act on the pre-treated fiber to perform a graph polymerization reaction, natural fibers and recycled fibers can be used. Can react the cross-linking reactive compound more efficiently, and the amount of the metal chelate-forming compound introduced thereafter can be increased, so that a higher chelating activity can be imparted. I like it.
- the metal chelate-forming fiber is brought into contact with a gas such as an aqueous liquid or an oily liquid containing metal ions, or an exhaust gas, and is contained therein.
- a gas such as an aqueous liquid or an oily liquid containing metal ions, or an exhaust gas, and is contained therein.
- FIG. 1 is a graph showing the relationship between the treatment liquid pH and the adsorption amounts of various metal ions when using the chelate fiber A obtained in Example 1.
- FIG. 2 is a graph showing the relationship between the treatment solution pH and the adsorption amounts of various metal ions when the commercial chelating resin used as a control in Example 1 was used. Fig.
- the metal chelate-forming fiber of the present invention has a base material of a natural fiber or a regenerated fiber, specifically, a plant fiber such as a cellulosic fiber, or an animal such as silk or wool. These are hydrophilic fibers, which have a polar group such as a hydroxyl group or a amino group in the fiber molecule, are hydrophilic, and exhibit excellent wettability to aqueous liquids and the like.
- the fiber molecule is reacted with a double bond and a cross-linking reactive compound having a glycidyl group in the molecule in the presence of a redox catalyst, whereby the cross-linking reactivity is increased.
- a cross-linking reactive compound having a glycidyl group in the molecule in the presence of a redox catalyst, whereby the cross-linking reactivity is increased.
- Compounds can be easily introduced into fiber molecules.
- a chelate-forming compound reactive with a glycidyl group preferably iminodiacetic acid, ethylenediamine, or the like is used.
- acetic acid, ethylenediamine triacetic acid, thioglycolic acid, thiolingoic acid, phosphoric acid, etc. it is possible to easily impart metal chelate forming ability to fiber molecules. .
- innumerable metal keys are attached to the molecular surface of natural and regenerated fibers.
- a chelate-forming functional group is introduced, and nitrogen, sulfur, carboxyl groups, etc., present in the chelate-forming functional group are replaced with copper, zinc, nickel, Demonstrates excellent selective adsorption to heavy metal ions such as cobalt.
- these chelate-forming functional groups are exposed on the surface in a state of being graphed on the fiber molecules, the metal chelate-forming fibers are present in the chelate existing in the fiber molecules. It exhibits excellent metal ion selective adsorption activity due to the forming functional group.
- the base material is natural fiber or regenerated fiber, biodegradation can be expected even when disposed, and no harmful gas is generated even if incinerated.
- the types of natural fibers and regenerated fibers used as the base material of the metal chelate-forming fibers according to the present invention are not particularly limited, and various vegetable fibers such as cotton, hemp, and wood; Regenerated fibers such as cotton, polynosic, and acetate; all animal fibers such as silk and wool are included.
- the base fiber either, long filament monofilament, multifilament, short fiber spun yarn, or woven fabric of these. It may be a woven or knitted fabric or a non-woven fabric, or a fiber or woven or knitted fabric obtained by compounding or blending two or more kinds of fibers. It is also possible to use wood pulp and paper that can be used, as well as pieces of wood, wood chips and sheets.
- the base fiber In order to increase the contact efficiency with the fluid to be treated, it is also effective to use the base fiber as a short fiber powder or a filter material.
- the preferred shape of the short fiber powder used here is 0.01 to 5 mm in length, preferably 0.03 to 3 mm, and the single fiber diameter is l to 50 ⁇ m, preferably 5 to 30 ⁇ m, and the aspect ratio is about 1 to 600, preferably about 1 to 100 1. It is.
- the short fiber powder metal chelate-forming fiber is added to an aqueous or oily liquid containing a metal ion, and the mixture is stirred.
- the metal ions contained in the fluid to be treated can be efficiently captured and purified in a very simple manner of performing the treatment and in a short time.
- the metal chelate-forming fibers in the form of short fiber powder are filled in a column or the like, and the fluid to be treated is passed through the column or the like. Thus, a similar metal ion trapping effect can be obtained.
- a filter material having a metal chelate trapping ability can be easily obtained. Can be obtained.
- the metal chelate fiber obtained by trapping a metal having a bactericidal action such as copper or silver in the short fiber powder-like chelate trapping material obtained in this way is kneaded into a resin or the like.
- antibacterial properties can be imparted, and metal chelate fibers in which a metal ion having a redox effect is captured can be useful as a catalyst.
- chelate fibers trapping copper, nickel, and the like are useful as electromagnetic wave shielding materials.
- the material of the file is not special, but depending on the application,
- a single-layer or multi-layer mat consisting of a woven or knitted or non-woven fabric with an arbitrary fiber gap and assembled into an appropriate support.
- a metal is added to the glycidyl group of the cross-linking reactive compound graphitically bonded to the fiber molecule.
- a method of introducing a metal chelate-forming functional group into a fiber material afterwards by subjecting it to a graphite polymerization reaction and then contacting it with a metal chelate-forming compound
- a metal chelate-forming functional group into a filter-like fiber material, it is possible to obtain a filter that has both the ability to capture chelate and the ability to capture insoluble contaminants.
- a fiber material whose fiber density is adjusted so as to have a mesh size corresponding to the size of the insoluble contaminants contained in the liquid to be treated and the gas to be treated is used, the liquid to be treated and the gas to be treated are When passing through the filter, the metal ions contained in the liquid to be treated and the gas to be treated are chelate-forming.
- insoluble contaminants are prevented from passing by the mesh of the filter, and the metal ions and the insoluble contaminants can be removed simultaneously. It becomes possible.
- the thickness, weaving and knitting density, the number of laminations and the lamination density of the fiber material to be used are adjusted, and the string-shaped chelating fibers are wound into a plurality of layers to form a filter.
- the gap between fibers can be arbitrarily adjusted by adjusting the winding density, layer thickness, winding tension, etc., it is mixed in the fluid to be treated. By adjusting the gap between the fibers according to the particle size of the insoluble contaminants, it is possible to obtain a file having a required cleaning performance.
- the crosslinking reactive compound for immobilizing the metal chelate-forming functional group on the fiber base material includes, A compound having a reactive double bond and a glycidyl group is used. Then, when the cross-linking reactive compound is brought into contact with a fiber base material in the presence of a redox catalyst as described later, a reactive double bond reacts with a fiber molecule to form a reactive functional group. Thus, a group having a glycidyl group is pendantly graphitized in the fiber molecule.
- a metal chelate-forming compound having a reactive functional group with a glycidyl group is reacted with the graphitic adduct. Reacts with the glycidyl group of the compound to introduce a metal chelate-forming functional group into the fiber molecule.
- the cross-linking reactive compound used here has not only a graphite addition reactivity to the fiber molecule but also a molecule in order to realize a reaction with the metal chelate forming compound. Yes, as long as the compound has both a reactive double bond and a glycidyl group. Although it can be used effectively, it can be more efficiently graphitized with natural fibers and recycled fiber base materials, and can also efficiently carry out the subsequent introduction reaction of metal chelate forming compounds. Particularly preferred are glycidyl methacrylate, glycidyl acrylate, and aryl glycidyl ether, and particularly, the ease of introduction into fiber molecules. Glycidyl methacrylate is the most preferred in view of the availability of raw materials and raw materials.
- an aminodicarboxylic acid, a thiocarboxylic acid and a phosphoric acid having reactivity with a glycidyl group are selected. These compounds have high reactivity with glycidyl groups, and react almost equimolarly with the glycidyl groups of the bridge reactive compound introduced into the fiber molecule. You. Moreover, since they have a high chelating ability with respect to metal ions, the use of these compounds allows the formation of metal chelating functional groups in fiber molecules. It can be introduced efficiently with a high reaction rate.
- imino diacetic acid is preferred in consideration of the reaction efficiency, the ability to capture the chelate, the availability of raw materials, the cost, etc.
- the method for producing a metal chelate-forming fiber according to the present invention comprises, as described above, a metal chelate-forming compound in a molecule of a natural fiber or a regenerated fiber via a crosslinking reactive compound. It is positioned as a method that can be efficiently and easily introduced, and the above-mentioned cross-linking reactive compound is grouped into fiber molecules using a redox catalyst. After the raft reaction, a method is employed in which the chelate-forming compound is subjected to an addition reaction.
- redox catalysts examples include hydrogen peroxide, benzoyl peroxide, barium oxide at the mouth of the methane oxide as an oxidizing agent, and ferrous salt, dioxide as a reducing agent.
- Thiourea, chromion, sulfite, hydroxylamine, hydrazine and the like can be mentioned.
- the combination of hydrogen peroxide, ferrous salt and thiourea dioxide is most preferred.
- the fiber is pre-treated with a ferrous salt, and then treated with hydrogen peroxide and thiourea dioxide.
- This method is preferable because a high graph reaction rate can be obtained in a short time even under relatively mild conditions.
- the reaction at the time of introducing the metal chelate-forming functional group into the natural fiber molecule using the cross-linking reactive compound is not particularly limited, but a preferred method is as follows.
- the natural or regenerated fiber is immersed in an aqueous solution of ferrous salt in advance for about 1 to 30 minutes at room temperature, washed, and then washed with hydrogen peroxide, thiourea dioxide and a crosslinking reactive compound (as required)
- This method involves immersion in an aqueous solution containing a homogeneous reaction accelerator such as an emulsifier, and reaction at 40 to 100 ° C for about 10 minutes to 5 hours.
- the cross-linking reactive compound efficiently reacts with the hydroxyl group in the fiber molecule by the graphitic reaction, and easily reacts with the metal chelate-forming compound. Groups can be efficiently introduced into fiber molecules.
- the fiber into which the glycidyl group is introduced by the above reaction and the above-mentioned chelate-forming compound are dissolved in water or a polar solvent such as N, N'-dimethylformamide or dimethylsulfoxide. If necessary, the reaction is carried out at 50 to 100 ° C. for 10 minutes to several tens of hours using a reaction solvent, whereby the amino group in the metal chelate-forming compound is converted to the above group. Reacts with lysidyl groups and introduces metal chelate-forming functional groups into fiber molecules.
- the amount of the metal chelate-forming compound introduced into the natural or regenerated fiber is determined in consideration of the amount of the reactive functional group in the fiber molecule, and the amount of the crosslinking reactive compound used in the introduction reaction, or Can be arbitrarily adjusted according to the amount of the metal chelate-forming compound and the reaction conditions.
- the substituent means all the substituents introduced from the cross-linking reactive compound and the metal chelate forming compound.
- the above substitution rate is high in order to enhance the metal ion capturing ability. Therefore, the upper limit of the substitution rate is not particularly specified, but if the substitution rate is too high, the crystallinity of the substituent-introduced fiber tends to be high, and the fiber tends to be brittle.
- the pressure drop when using the filter media as a filter for capturing metal ions tends to increase, so that the filter material becomes practically useful as a metal ion capture material. In consideration of the economic efficiency and the like, it is desirable to keep the substitution rate at about 200% by mass or less, more preferably at about 100% by mass or less.
- the metal chelate-forming fiber obtained as described above may be monofilament-like multifilament-like depending on the properties of the base fiber used as described above. It can be obtained in any form such as spun yarn, non-woven fabric, fiber woven / knitted, powdery, filter-like, etc. Substantially all of the metal chelate-forming functional groups introduced on the molecular surface effectively exhibit the metal ion capturing performance, and therefore, are extremely inferior to, for example, a granular or film-like capturing material. Demonstrates excellent metal ion trapping ability.
- this fiber has a very good metal ion selective adsorption performance, the pH of the fluid to be treated and other conditions must be changed. Thereby, it is also possible to selectively capture only the target metal.
- the fibers are brought into contact with a liquid or gas containing a metal ion, and specifically, the fibers are laminated to an arbitrary thickness or filled into a column to form a liquid or gas to be treated.
- the metal ion components contained in the water to be treated, the oil to be treated, and the exhaust gas to be treated are efficiently captured and removed, or specific metal ions can be selectively captured. Wear.
- the fibers capturing the metal ions as described above are treated with a strong acid aqueous solution such as hydrochloric acid or sulfuric acid, the metal ions captured by forming a chelate are easily separated. Therefore, if these properties are used, it is possible to recover the metal component as a beneficial component from the regenerating solution.
- a strong acid aqueous solution such as hydrochloric acid or sulfuric acid
- a metal having a specific activity can be captured by the chelate-forming fiber so that the properties of the metal can be utilized. It is used as a metal chelate fiber, and can be used in the following forms, for example.
- Metals with catalytic activity such as iron, are chelated and used as redox reagents (such as catalysts for removing NOx and SOx).
- An antibacterial metal such as copper, nickel, silver, etc. is captured on a sheet-like or mat-like fiber base material, and the antibacterial or sterilizing sheet or mat (specifically, shoes) Use as insoles, medical bedding, toilets, 'one-mat', hand-washing etc.) Use as a filter, (3) Powdered fiber in which antibacterial or bactericidal metal is chelated and kneaded into a resin, for example, and used as a material for obtaining antibacterial and bactericidal plastic.
- 0.5 g of the above chelate fiber AO.5 was diluted with an aqueous sulfuric acid solution containing about lmmol / liter of copper, zinc, nickel, and copper, and the pH was adjusted to 0-10. After adding to m 1 and stirring at 20 ° C. for 20 hours, the adsorption amount of each metal ion was examined and compared with the adsorption amount of a commercially available chelate resin.
- Fig. 1 shows the results of adsorption using chelate fiber A, which shows excellent capture of any metal ion of copper, zinc, nickel, and cobalt. It can be seen that the compound exhibits an effect and exhibits a high adsorption activity in the vicinity of neutrality even in a lower pH region.
- the results for the sales chelate resin (Mitsubishi Chemical Corporation's product name “Diaion CR11”) are shown in Fig. 2, and the pH 2 Below, it can be seen that the adsorption performance is very poor and the pH dependence is high.
- the chelate fiber A or the commercially available chelate fiber Each lg of the beaded chelating resin was added to 1 liter of an aqueous copper sulfate solution having a copper ion concentration of 10 O ppm, and the change over time in the copper ion concentration in the solution was examined.
- Example 1 In Example 1 described above, 20 g of powdered cellulose (trade name “KC Block W-100” manufactured by Nippon Paper Industries) was used in place of the cotton cloth (unbleached cotton knit). Except for the above, the procedure was the same as that of Example 1 to obtain 30.0 g of metal chelate-forming fiber (chelate fiber B) (substitution ratio: 50% by mass). When a similar adsorption test was performed using the obtained chelate fiber B, it was confirmed that the chelate fiber B exhibited a copper capturing ability of 1.2 mmo 1 per 1 g of the chelate fiber B. Was.
- Example 3 Example 3
- a commercially available cartridge filter (Advantech Toyo Co., Ltd., product name “TCW-1”) in which a cotton spun yarn is wound in a twill form on a stainless steel core material.
- — CSS Nominal pore diameter of 1 m
- a housing made of Polypropylene Adno, manufactured by TEC Toyo Co., Ltd., trade name“ 1 PP — 1 — FS — 0 0 0 ”).
- 2.5 g of ammonium ferrous sulfate was dissolved in 10 liters of distilled water. The solution is circulated using a circulation pump at a flow rate of 15 liters / min at 20 ° C for 15 minutes, then drained, and washed by circulating 5 liters of distilled water in the same manner. did.
- This metal chelate-forming filter was mounted on the polypropylene housing described above, and copper sulfate was dissolved in distilled water to adjust the copper ion concentration to 10 ppm.
- a test solution obtained by dispersing 3.05 g of fine powder of silicon dioxide having an average particle diameter of 10 zm as insoluble contaminants in 10 liters of the solution obtained above was dissolved at a flow rate of 15 liters Z, 2 Circulated at 5 ° C for 1 hour.
- Example 1 was repeated except that 800 g of a 30% aqueous solution of ethylenediamine triacetic acid / 3 sodium salt was used in place of the aqueous solution of iminodiacetic acid. As a result, 27.3 g (substitution rate: 36.5% by mass) of a metal chelate-forming fiber (chelate fiber D) was obtained. When an adsorption test similar to that of Example 1 was performed using this chelate fiber D, it was confirmed that the chelate fiber D exhibited a copper capturing ability of 1.O mmo 1 per lg of the chelate fiber D. Was.
- Example 1 a metal cloth was prepared in the same manner as in Example 1 except that 2 Og of rayon cloth (rayon tough) was used instead of cotton cloth (unbleached cotton knit). 30.9 g (replacement ratio: 54.5% by mass) was obtained. A similar adsorption test was carried out using this chelate fiber F. It was confirmed that the protein F had a capacity of capturing 1.3 mmol of copper per lg of lg. INDUSTRIAL APPLICABILITY
- the metal chelate-forming fiber of the present invention is constituted as described above, and not only has to have a high trapping capacity for metal ions, but also has a high trapping speed. It is extremely excellent, and captures and removes metal ions in wastewater, oil, and gas (including various exhaust gases, etc.) extremely efficiently compared to conventional ion exchange resins and chelating resins. It is possible to clean them very efficiently.
- the metal chelate-forming fiber of the present invention which has captured metal ions, easily releases the metal ions by treatment with an aqueous acid solution such as a mineral acid or an organic acid, so that the regeneration is easy and repeated. Not only can it be returned and used, but it can also be used to concentrate metal components.
- powdered fibers are used as the fiber base material, it is possible to combine the performance of removing metal ions and the performance as a filter aid, and use a filter-like fiber material. By doing so, it is possible to provide a cleaning operation having both a metal ion trapping performance and an insoluble contaminant removal performance.
- biodegradation can be expected because the base material is natural fiber or regenerated fiber, and harmful gas hardly occurs even if incinerated.
- metal ions to be chelate-trapped are positively selected, the properties of the metal itself, such as catalytic action, antibacterial action and bactericidal action, can be imparted to the metal chelate fiber. It can be widely and effectively used as a filter-like exhaust gas treatment catalyst, an antibacterial / sterilizing sheet material, and a filter material for air conditioning equipment.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Zoology (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Separation Of Gases By Adsorption (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00905299A EP1179627B1 (en) | 1999-02-26 | 2000-02-24 | Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
DE60008097T DE60008097T2 (de) | 1999-02-26 | 2000-02-24 | Zur Metallchelatbildung fähige Faser, Verfahren zum Herstellen derselben, Verfahren zum Metallion-Komplexieren mit der Faser und Metallchelatfaser |
US09/914,356 US6875508B1 (en) | 1999-02-26 | 2000-02-24 | Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/50897 | 1999-02-26 | ||
JP05089799A JP3940236B2 (ja) | 1999-02-26 | 1999-02-26 | 金属キレート形成性繊維及びその製法、並びに該繊維を用いた金属イオン捕捉法及び金属キレート繊維 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000052252A1 true WO2000052252A1 (en) | 2000-09-08 |
Family
ID=12871544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/001043 WO2000052252A1 (en) | 1999-02-26 | 2000-02-24 | Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
Country Status (6)
Country | Link |
---|---|
US (1) | US6875508B1 (ja) |
EP (1) | EP1179627B1 (ja) |
JP (1) | JP3940236B2 (ja) |
CN (1) | CN1136354C (ja) |
DE (1) | DE60008097T2 (ja) |
WO (1) | WO2000052252A1 (ja) |
Cited By (3)
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WO2003106757A1 (ja) * | 2002-06-13 | 2003-12-24 | 中部キレスト株式会社 | キレート形成性繊維及びこれを用いた金属イオン含有水の処理法 |
US6875508B1 (en) * | 1999-02-26 | 2005-04-05 | Chelest Corporation | Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
EP3125335A4 (en) * | 2014-03-25 | 2017-09-06 | Kuraray Co., Ltd. | Separator for alkaline batteries, and alkaline battery using same |
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WO1998016680A1 (fr) * | 1996-10-15 | 1998-04-23 | Chelest Corporation | Fibre de formation de chelate metallique, procede de preparation de cette fibre, et procede de sequestration d'ions metalliques au moyen de cette derniere |
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DE69819321T2 (de) * | 1997-04-22 | 2004-07-22 | Chelest Corp. | Metallchelatbildende fasern, verfahren zu deren herstellung und verfahren zum binden von metallen und daraus hergestellte filter |
JP3940236B2 (ja) * | 1999-02-26 | 2007-07-04 | キレスト株式会社 | 金属キレート形成性繊維及びその製法、並びに該繊維を用いた金属イオン捕捉法及び金属キレート繊維 |
JP3964573B2 (ja) * | 1999-05-25 | 2007-08-22 | 中部キレスト株式会社 | 金属キレート形成性繊維の製法、並びに該繊維を用いた金属イオン捕捉法及び金属キレート繊維 |
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1999
- 1999-02-26 JP JP05089799A patent/JP3940236B2/ja not_active Expired - Lifetime
-
2000
- 2000-02-24 EP EP00905299A patent/EP1179627B1/en not_active Expired - Lifetime
- 2000-02-24 CN CNB008039798A patent/CN1136354C/zh not_active Expired - Lifetime
- 2000-02-24 DE DE60008097T patent/DE60008097T2/de not_active Expired - Lifetime
- 2000-02-24 WO PCT/JP2000/001043 patent/WO2000052252A1/ja active IP Right Grant
- 2000-02-24 US US09/914,356 patent/US6875508B1/en not_active Expired - Lifetime
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JPS55112386A (en) * | 1979-02-22 | 1980-08-29 | Dainippon Printing Co Ltd | Dry transfer printing |
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WO1998016680A1 (fr) * | 1996-10-15 | 1998-04-23 | Chelest Corporation | Fibre de formation de chelate metallique, procede de preparation de cette fibre, et procede de sequestration d'ions metalliques au moyen de cette derniere |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6875508B1 (en) * | 1999-02-26 | 2005-04-05 | Chelest Corporation | Fiber capable of forming metal chelate, process for producing the same, method of trapping metal ion with the fiber, and metal chelate fiber |
WO2003106757A1 (ja) * | 2002-06-13 | 2003-12-24 | 中部キレスト株式会社 | キレート形成性繊維及びこれを用いた金属イオン含有水の処理法 |
EP3125335A4 (en) * | 2014-03-25 | 2017-09-06 | Kuraray Co., Ltd. | Separator for alkaline batteries, and alkaline battery using same |
US10461294B2 (en) | 2014-03-25 | 2019-10-29 | Kuraray Co., Ltd. | Separator for alkaline batteries, and alkaline battery using same |
Also Published As
Publication number | Publication date |
---|---|
US6875508B1 (en) | 2005-04-05 |
EP1179627B1 (en) | 2004-02-04 |
DE60008097T2 (de) | 2004-12-23 |
EP1179627A4 (en) | 2002-05-02 |
CN1136354C (zh) | 2004-01-28 |
EP1179627A1 (en) | 2002-02-13 |
DE60008097D1 (de) | 2004-03-11 |
JP3940236B2 (ja) | 2007-07-04 |
JP2000248467A (ja) | 2000-09-12 |
CN1341176A (zh) | 2002-03-20 |
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