JP2001123381A - Chelate-forming fiber, method for producing the same, and method of using the same - Google Patents

Abstract

(57) [Problem] A chelate that has excellent trapping performance for metals or similar metals, is easy to incinerate, etc., and can be manufactured at a low cost by a simple and safe method. To provide formable fibers and develop their manufacturing and use. SOLUTION: Polyethyleneimine having preferably an average molecular weight of 300 to 70,000 is introduced into fiber molecules, and a chelate-forming fiber provided with a chelate-forming ability with a metal or a class of metal elements, a method for producing the same, and A method for capturing a metal or a class of metal elements using the fiber is disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fiber capable of forming a chelate with a metal or a similar metal and a method for producing the same.
In addition, regarding its use, this fiber is, for example, metal ions present in trace amounts in water, oil or gas, particularly harmful heavy metal ions such as copper, zinc, nickel and cobalt, or compounds thereof, or similar metals, especially boron or germanium or It has the ability to selectively and efficiently adsorb those compounds, etc., and purifies industrial water, agricultural water, edible oils and food processing oils, purifies air, and valuable resources including the above metals and related metals. The fibers can be widely used for recovery and the like, and the chelate fibers in which the fibers are chelated with a metal or a similar metal can be used as various catalysts, fungicides, antibacterial·
Disinfectant, antistatic agent, electromagnetic wave shielding material, light shielding material,
It can be effectively used as colored clothing / decorative goods, fertilizer, metal rust inhibitor, etc.

[0002]

2. Description of the Related Art Various kinds of harmful ions may be contained in industrial wastewater. From the viewpoint of preventing environmental pollution, these metal ions must be sufficiently removed by wastewater treatment. In addition, heavy metal components contained in rivers and groundwater adversely affect the human body. Therefore, careful consideration must be given to the effective use of these components. Furthermore, when producing edible oils or food processing oils, metals that may be mixed in as a hydrogenation catalyst or the like need to be removed as much as possible because they adversely affect storage stability and the human body. is there.

[0003] Metals and metal compounds such as boron and germanium are widely distributed in the natural world. For example, boron is newly set as an environmental standard substance in February 1999, and its harmfulness is noticed. Have been.

[0004] On the other hand, boron and its compounds are extremely useful components for the development of new materials that support the current advanced industry, such as superconducting materials, semiconductor materials, and neutron absorbing materials, and the development of boron resources is being actively promoted in various countries. Have been.

[0005] Under the circumstances described above, the present invention efficiently captures and removes these metal ions and metal ions and their compounds from a liquid to be treated such as water or edible oil to purify or recover them. In order to provide a chelate-forming fiber that can be used for the treatment of liquids to be treated, such as water and oil, the chelate-forming fiber has been used for further research. Was.

Conventionally, ion-exchange resins have been widely used for removing harmful metal ions contained in wastewater or capturing useful metal ions, but selectively adsorb and separate low-concentration metal ions. The effect of doing this is not always satisfactory.

Further, a chelate resin having a property of forming a chelate with a metal ion or a class of metal ions and selectively trapping the chelate has an excellent selective capturing property for the metal ion or the class of metal ions. It is used in water treatment fields. However, most of the chelate resins simply have a chelate-forming functional group introduced therein and do not always show satisfactory chelate-forming ability.

A conventional ion exchange resin or chelate resin is a rigid bead having a three-dimensional structure given by a cross-linking agent such as divinylbenzene, and the diffusion rate of metal ions and a regenerant into the resin is low. Therefore, there is also a problem in processing efficiency. Furthermore, since it is difficult to dispose in a disposable type without regenerating, it is also a big problem how to reduce the volume of used resin.

As a solution to the problem of the bead-like chelating resin, a fibrous or sheet-like chelating material has been proposed (JP-A-7-10925). The fibrous or sheet-like chelating material has a large specific surface area, and a chelating functional group serving as a trapping point for metal ions or metal ions exists on the surface, so that the trapping efficiency is enhanced, and furthermore, incineration disposal and the like are also possible. Easy to do,
It has many advantages. However, the production method of the fibrous or sheet-like chelating material is complicated, and a special method using ionizing radiation must be adopted. Point out many problems.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a metal or a class of metals having excellent trapping performance. Another object of the present invention is to provide a chelate-forming fiber which can be easily incinerated and can be produced at a low cost by a simple and safe method. A second object is to provide such a chelate-forming fiber. Another object of the present invention is to provide a method that can be manufactured simply, safely, and efficiently. A third object of the present invention is to provide a method capable of efficiently capturing a trace amount of metal or similar metal contained in water, oil, exhaust gas, or the like by a simple method. Further, a fourth object of the present invention is to provide a metal having a chelate-bonding of various metals or similar metals to the surface of the chelate-forming fiber, thereby making it possible to effectively utilize the catalytic activity and antibacterial activity of the metal or similar metals. Another object of the present invention is to provide a chelate fiber which is chelate-bound to a metal like metal.

[0011]

Means for Solving the Problems The chelate-forming fiber according to the present invention, which can solve the above-mentioned problems, has polyethyleneimine introduced into fiber molecules and has a chelate-forming ability with a metal or a class of metals. There is a gist where you are.

Among the above-mentioned polyethylene imines to be introduced into the fiber molecule, particularly preferred is a polyethylene imine having an average molecular weight of 300 to 70,000.

[0013] The above-mentioned polyethyleneimine has a reactive functional group (hydroxyl group, amino group, imino group,
Aldehyde group, carboxyl group, thiol group, etc.), or may be indirectly linked via a crosslinking agent. As the base fiber, any of natural fibers, regenerated fibers, and synthetic fibers can be used, and natural fibers or regenerated fibers are particularly preferable for efficient introduction of polyethyleneimine. The most preferable is a cellulosic fiber in consideration of the stability and the like.

Further, the method for producing a chelate-forming fiber according to the present invention means that polyethyleneimine is directly reacted with a reactive functional group in a fiber molecule, or a reactive functional group in the fiber molecule is reacted with a polyethyleneimine. Epoxy group, reactive double bond,
It is characterized in that, after reacting a compound having two or more functional groups selected from a halogen group and an acid anhydride, polyethyleneimine is reacted. The polyethyleneimine used here is most preferably an average molecular weight of 300 to 7 in consideration of the ability to form a chelate with a metal or a similar metal, the reactivity with a fiber molecule and the cost.
0000 polyethyleneimine.

Still another configuration of the present invention is characterized in that the chelate-forming fiber is used to capture a metal such as copper, zinc, nickel and cobalt, or a similar metal such as boron and germanium. In this case, the chelate-forming fiber is brought into contact with a liquid containing a metal or a similar metal to thereby capture the metal or the like metal in the liquid, or the chelate-forming fiber is brought into contact with a gas containing a metal or a similar metal. A method of capturing the metal or similar metal in the gas by bringing the gas into contact can be adopted. In addition, the chelate fibers in which the chelate-forming fibers are chelated to a metal and / or a class of metals exhibit catalytic activity and antibacterial activity depending on the type of the metal or the class of the metal. Metal chelate fibers are also included in the scope of the present invention.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The chelate-forming fiber of the present invention comprises
As described above, by introducing polyethyleneimine into the fiber molecule, more preferably, polyethyleneimine having an average molecular weight of 300 to 70,000, the ability to form a chelate with a metal or a similar metal is given. are doing.

That is, in the present invention, by introducing polyethyleneimine, particularly preferably polyethyleneimine having an average molecular weight of 300 to 70,000, excellent chelate-forming ability can be imparted to metals or similar metals. This makes it possible to effectively capture metals or similar metals.

The type of the base fiber into which the polyethyleneimine is introduced in the present invention is not particularly limited, for example, various plant fibers including cotton, hemp, etc .; various animal fibers including silk, wool, etc .; Various recycled fibers such as viscose rayon; various synthetic fibers such as polyamide, acrylic, and polyester can be used. These fibers are variously modified as necessary. It does not matter.

Among these base fibers, particularly preferred are vegetable fibers, animal fibers, and regenerated fibers having a functional group reactive with polyethyleneimine such as a hydroxyl group or an amino group in the fiber molecule. In view of the stability and strength of the fibers, the most preferable are cellulosic fibers. These fibers are preferable because polyethyleneimine can be easily introduced by reacting polyethyleneimine with a reactive functional group in the fiber molecule. However, even when the raw fiber itself does not have a reactive functional group, it is modified by any means such as oxidation to introduce a functional group having reactivity with polyethyleneimine, and this functional group is It is also possible to introduce polyethyleneimine into the fiber molecule by utilizing.

There is no particular limitation on the shape of the base fiber, and long filament monofilaments, multifilaments,
It may be a spun yarn of short fibers, a fabric obtained by weaving or knitting them in a woven or knitted shape, or a nonwoven fabric. In addition, a fiber or a woven or knitted material obtained by compounding or blending two or more kinds of fibers can also be used.

In order to further increase the contact efficiency with the fluid to be treated, it is effective to use the base fiber as a short fiber powder or a filter material.

The preferred shape of the short fibrous powder used here is 0.01 to 5 mm in length, preferably 0.03 to 5 mm.
3 mm and a single fiber diameter of about 1 to 50 μm, preferably 5
The aspect ratio is about 1 to 600, preferably about 1 to 100.

If such a short fiber powder material is used, the short fiber powder chelate-forming fiber is added to an aqueous or oily liquid containing metal ions or similar metal ions, and the mixture is agitated. It is possible to efficiently capture and clean metal ions or metal-like ions contained in the fluid to be treated by a very simple method of performing the treatment and in a short time. In some cases, a similar effect of capturing metal ions or similar metal ions can be obtained by filling the column or the like with the chelate-forming fibers in the form of short fiber powder and passing the fluid to be treated. Further, if a process such as molding is performed after introducing a chelate-forming functional group into the short fiber powder material by the above-described method, a filter material having a chelate capturing ability can be easily obtained.

Further, the metal chelate fiber obtained by trapping a metal having a bactericidal action such as copper, silver or zinc in the chelate-forming fiber in the form of short fiber powder obtained in this way is kneaded into a resin or the like to deodorize. A metal chelate fiber that can impart deodorizing / antifungal properties, antibacterial properties, and bactericidal properties, and that captures metal ions having an oxidation-reduction action can also be used as a catalyst for various reactions.

The form and structure when the fibers are used as a filter are not particularly special, and a single-layer or multi-layer mat made of a woven, knitted or non-woven fabric having an arbitrary fiber gap according to the application. A structure in which the fibers are formed into a shape and assembled to an appropriate support, a structure in which a plurality of layers of cord-like fibers are wound around the outer periphery of a liquid-permeable support tube in a twill, or a woven / knitted or nonwoven fabric made of the same fibers All known forms can be used, such as a structure in which a sheet is folded into a pleated shape and attached to a support member, a woven / knitted fabric made using the same fiber, or a bag filter type in which a nonwoven fabric is formed into a bag shape.

In the case where the chelate-forming fiber is used as a filter as described above, polyethyleneimine is introduced into the filter-like fiber material directly or through a cross-linking agent and processed into the above-mentioned filter shape. In addition, the above-mentioned fiber material is processed into a filter shape and incorporated into a filter device, and the fiber filter incorporated in the device is reacted directly or with a cross-linking agent. It is also possible to introduce polyethyleneimine into the fiber filter after the fact by contacting with a treatment solution containing the same.

As described above, by introducing a chelate-forming functional group into a filter-like fiber material, a filter having both a chelate-capturing ability and an insoluble contaminant-capturing ability can be obtained. If a fiber material whose fiber density is adjusted so as to have a mesh size corresponding to the size of 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 filtered by the filter. When passing through, the metal ions and metal ions contained in the liquid to be treated and the gas to be treated are captured by the chelate-forming functional group, and the insoluble impurities are blocked from passing by the mesh of the filter, It is possible to simultaneously remove metal ions or metal-like ions and insoluble inclusions.

At this time, the thickness and weave of the fiber material used
When adjusting the knitting density, the number of laminations, the lamination density, etc., and when winding a string-like chelating fiber into multiple layers to make a filter, adjust the winding density, layer thickness, winding tension, etc. By adjusting the inter-fiber gap according to the particle size of the insoluble contaminants mixed in the fluid to be treated, the inter-fiber gap can be adjusted as desired. Obtainable.

In the present invention, the polyethyleneimine to be introduced into the base fiber refers to a product obtained by ring-opening polymerization of ethyleneimine, a product obtained by polycondensing ethylene chloride and ethylenediamine, or a product obtained by subjecting 2-oxazolidone to a heat reaction. Collectively. These raw materials of polyethyleneimine have extremely high reaction activity. In the polymerization, for example, primary, secondary and tertiary amino groups of linear structural units or branched structural units are mixed as shown in the following formula. The ratio of the structural units and the primary to tertiary amines may be any, and in the present invention, they are collectively referred to as polyethyleneimine.

[0030]

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These polyethyleneimines have chelating ability with metals or similar metals, reactivity with fiber molecules,
Considering the cost etc. comprehensively, the average molecular weight is 300 to 7
The most practical ones are in the range of 0000, more preferably 600 to 10,000.

The polyethyleneimine introduced into the fiber molecule to provide the metal or similar metal chelate-forming ability has a reactive functional group (eg, a hydroxyl group, an amino group, an imino group, a carboxyl group, an aldehyde group) in the fiber molecule. , Thiol group, etc.), or indirectly via a cross-linking agent. However, considering the ease of introduction into fiber molecules, crosslinking such as described below Those introduced indirectly through the agent are recommended as those having high practicality.

The method for producing the chelate-forming fiber according to the present invention includes a method in which polyethyleneimine is directly added to the above-mentioned reactive functional group originally possessed by the fiber molecule or the reactive functional group introduced by modification. After reacting or reacting the reactive functional group with a crosslinking agent having two or more functional groups selected from an epoxy group, a reactive double bond, a halogen group, and an acid anhydride group in the molecule. And a method of reacting polyethyleneimine.

For example, when a fiber molecule has a carboxyl group, a carboxyl group, or the like, polyethyleneimine can be directly reacted with the carboxyl group, and the polyethyleneimine can be introduced into the fiber molecule in a pendant manner. The following is an example of a typical reaction.

[0035]

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If the reactivity between the reactive functional group in the fiber molecule and the polyethyleneimine is poor, the fiber is first reacted with a crosslinking agent to convert the functional group having a high reactivity with the polyethyleneimine into a pendant form. Polyethyleneimine can be introduced in a pendant manner by introducing and then reacting the functional group with polyethyleneimine. In particular, if the latter method is employed, the amount of the cross-linking agent and polyethyleneimine used for the fiber is adjusted, so that the ability to capture metals or similar metals (ie, the amount of polyethyleneimine introduced) can be arbitrarily controlled according to the purpose of use. It is preferable because it can be used.

Preferred crosslinking agents used herein include two or more, preferably two or more, epoxy groups, reactive double bonds, halogen groups, acid anhydride groups, aldehyde groups, carboxyl groups, and isocyanate groups in the molecule. Specific examples of preferred crosslinking agents include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl sorbate, epichlorohydrin, epibromohydrin, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Glycerin diglycidyl ether, polypropylene glycol diglycidyl ether,
Maleic anhydride, itaconic anhydride, aconitic anhydride,
Citraconic anhydride, maleated methylcyclohexene tetrabasic anhydride, endmethylenetetrahydrophthalic anhydride, chlorendic anhydride, crotonic anhydride, acrylic acid anhydride, methacrylic anhydride, maleic acid, succinic acid, adipic acid, glyoxal, glyoxylic acid , Tolylene diisocyanate, hexamethylene diisocyanate, and the like.Examples are particularly preferable in consideration of reaction efficiency, cost, and the like when introduced into fiber molecules, and among them, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, epichlorohydrin, and ethylene are particularly preferable. Glycol diglycidyl ether, maleic anhydride, itaconic anhydride and the like.

A specific reaction when introducing a polyethyleneimine into a fiber molecule using the above-described crosslinking agent is as follows.

[0039]

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The reaction when introducing polyethyleneimine into the fiber using these crosslinking agents is not particularly limited, but preferred methods include, for example, a method in which the base fiber and the crosslinking agent are mixed with water or N, N'-dimethylformamide or dimethyl. In a polar solvent such as sulfoxide, a reaction catalyst or an emulsifier is used in combination, if necessary, and the reaction is carried out at about 60 to 100 ° C. for about 30 minutes to several tens of hours. A functional group that reacts with a reactive functional group (for example, a hydroxyl group or an amino group) to bind to the fiber and easily react with polyethyleneimine can be introduced into the fiber molecule. Next, the fiber into which the functional group has been introduced and polyethyleneimine are mixed in a polar solvent such as water or N, N'-dimethylformamide or dimethylsulfoxide at 60 to 100 ° C for 30 minutes to several tens of minutes using a reaction catalyst if necessary. After reacting for about an hour, the amino group of the polyethyleneimine reacts with the reactive functional group (for example, an epoxy group or a halogen group) of the crosslinking agent, and the polyethyleneimine is introduced into the fiber molecule in a pendant manner.

This reaction is usually carried out successively as described above. However, depending on the reaction system, it is also possible to allow the crosslinking agent and polyethyleneimine to coexist at the same time and to react the fibers simultaneously and in parallel. As the base fiber used in this reaction, a long fiber monofilament, multifilament, short fiber spun yarn, or a woven or knitted or woven or knitted fabric thereof, or a nonwoven fabric is optionally selected and used. As described above, it is possible to use a fiber or a woven or knitted fabric obtained by compounding or blending two or more kinds of fibers.

The amount of the polyethyleneimine introduced into the base fiber is determined in consideration of the amount of the reactive functional group in the base fiber molecule, the amount of the polyethyleneimine used for the introduction reaction, the amount of the crosslinking agent and the polyethyleneimine, and the reaction conditions. Although it can be arbitrarily adjusted by, for example, in order to impart sufficient chelate capturing ability to the fiber, the polyethyleneimine (PEI) substitution rate calculated by the following formula is about 10% by mass or more, more preferably about 20% by mass or more. It is desirable to adjust as follows. PEI substitution ratio (% by mass) = [(fiber mass after PEI introduction−fiber mass before PEI introduction) / fiber mass before PEI introduction] × 100 (where PEI represents polyethyleneimine)

In order to enhance the ability to capture metals or similar metals, the above-mentioned PEI substitution ratio is preferably as high as possible. Therefore, the upper limit of the substitution ratio is not particularly limited. Fibers tend to be brittle, and when used as a filter material or a filter for a metal or similar metal capturing material, the pressure loss tends to increase. In consideration of such factors as a whole, the PEI replacement ratio is desirably suppressed to about 130% by mass or less, more preferably to about 100% by mass or less. However, depending on the type of the functional group and the cross-linking agent in the fiber molecule, or the use, etc., 150 to 2
By setting the PEI substitution rate to a high level such as 00% by mass, it is possible to enhance the ability to capture metals or similar metals.

The chelate-forming fiber obtained as described above can be obtained in any form such as a monofilament, a multifilament, a spun yarn, a nonwoven fabric, a fiber woven or a knitted fabric, depending on the properties of the base fiber used. In any case, in any case, substantially all of the polyethyleneimine introduced on the molecular surface of the small-diameter fiber effectively exerts a metal or metal-class-capturing performance, so that, for example, a granular or film-like Demonstrates very excellent trapping ability as compared to the trapping material.

Therefore, this fiber is brought into contact with a liquid or a gas containing metal ions or metal ions, and specifically, the fiber is laminated at an arbitrary thickness or filled in a column to form a liquid to be treated, When the gas to be treated is passed, metal ions, metal ions or compounds thereof contained in the liquid to be treated or the gas to be treated can be efficiently captured.

Further, when the fiber capturing the metal or the like metal as described above is treated with a strong acid aqueous solution such as hydrochloric acid or sulfuric acid, the chelate is formed and the captured component is easily separated. By utilizing such characteristics, it becomes possible to effectively recover a metal or a similar metal as a valuable component from the regenerating solution.

[0047]

EXAMPLES Next, examples of the present invention will be described. However, the present invention is not limited by the following examples, and the present invention can be practiced with appropriate modifications within a range that can conform to the spirit of the preceding and following examples. Of course, it is possible, and all of them are included in the technical scope of the present invention.

Example 1 0.025 g of ammonium ferrous sulfate hexahydrate was dissolved in 1000 ml of distilled water, and 50 g of cotton yarn (40/1 cotton single yarn bleached product made by Dyeing & Sampling Materials Co., Ltd.) was added thereto. 30 at room temperature
Stir for minutes. Then glycidyl methacrylate 5
0g, nonionic surfactant (Nonion O manufactured by NOF Corporation)
T-221), 1 g of a 31% H ₂ O ₂ aqueous solution and 0.81 g of thiourea dioxide are added, and the mixture is stirred at 60 ° C. for 1 hour. The treated cotton yarn is washed with distilled water, drained, and then drained.
After drying at 0 ° C. for 15 hours, 68.5 g of graft fibers obtained by grafting glycidyl methacrylate in cotton yarn molecules are obtained.

Then, polyethyleneimine (average molecular weight 6 manufactured by Wako Pure Chemical Industries, Ltd.) was added to 700 g of dimethyl sulfoxide.
00) The above graft fiber is immersed in a solution in which 300 g is dissolved, and heat-treated at 80 ° C. for 2 hours. Thereafter, the resultant was sufficiently washed with water, drained, and dried at 50 ° C. for 15 hours to obtain 90.3 g of a chelate-forming fiber (chelate fiber A) grafted with polyethyleneimine (PEI substitution rate: 8).
0.6% by mass).

1 g of the obtained chelate fiber A was
ol / liter of copper sulfate aqueous solution,
After stirring at 0 ° C. for 20 hours, the amount of copper ions remaining in the solution was quantified to examine the copper trapping ability. As a result, it was confirmed that 1.0 mmol of copper trapping ability was exhibited per 1 g of the chelate fiber A. Was done.

On the other hand, for comparison, a commercially available beaded styrene iminodiacetic acid-based chelate resin (trade name “Diaion CR11” manufactured by Mitsubishi Chemical Corporation) was used in place of the chelate fiber A.
When the copper capturing ability was examined in the same manner as described above, except that was used, it was confirmed that the copper capturing ability per 1 g (in terms of solid content) of the chelate resin was 0.7 mmol.

Further, 1 g of the above chelate fiber A was
mol / liter of boric acid aqueous solution
After stirring at 0 ° C. for 20 hours, the amount of boron remaining in the solution was quantified to examine the boron trapping ability. As a result, it was confirmed that the chelating fiber A exhibited 0.1 mmol of boron trapping ability per gram. Was.

Further, 1 g of the above chelate fiber A was added to 1.4 g
It is added to 500 ml of a germanium aqueous solution (a solution of germanium dioxide dissolved in an aqueous solution of sodium hydroxide and neutralized with hydrochloric acid) at 500 mmol / liter, stirred at 20 ° C. for 20 hours, and quantified by determining the amount of germanium remaining in the solution. When the germanium trapping ability was examined, it was confirmed that 0.6 mmol of germanium trapping ability was exhibited per 1 g of the chelate fiber A.

(Copper ion trapping rate test) In order to confirm the copper ion trapping rate of the chelate fiber A, 1 g of the chelate fiber A was treated with an aqueous copper sulfate solution having a copper ion concentration of 200 ppm.
Liter, and the change with time of the copper ion concentration in the solution was examined.

The results are as shown in FIG. 1. In the case of a commercially available beaded chelate resin, it takes about 4 hours for the copper-capturing ability to be saturated, whereas the chelate fiber A of the present invention into which polyethyleneimine has been introduced is used. The time required for the copper-capturing ability to be saturated when using is only 1 hour, and the chelating fiber of the present invention has about four times the copper-capturing ability at a speed as compared with the conventional chelating resin. You can see that it is.

(Breakthrough Curve Measurement Test) The Chelate Fiber A
Was charged into a glass column having a diameter of 5 mm, and an aqueous solution of copper sulfate having a copper ion concentration of 20 ppm was SV = 100 hr ^-1.
And the breakthrough curve was determined by measuring the copper ion concentration in the distillate.

The results are as shown in FIG. 2. When a commercially available chelating resin was used, copper ions flowed out before being sufficiently captured, whereas the chelating fiber A into which polyethyleneimine had been introduced was used. When used, the chelate fiber A exhibits almost complete metal capturing ability until the metal capturing ability is saturated. From these results, it can be confirmed that the chelate-forming fiber of the present invention has excellent metal ion capturing ability.

Example 2 In the same manner as in Example 1 except that polyethyleneimine having an average molecular weight of 10,000 was used instead of polyethyleneimine having an average molecular weight of 600 (manufactured by Wako Pure Chemical Industries, Ltd.). As a result, 79.6 g of a chelate-forming fiber (chelate fiber B) (PEI substitution ratio: 55.2% by mass) was obtained. When a capture test similar to that of Example 1 was performed using this chelate fiber B, it was confirmed that 0.8 g of copper, 0.07 mmol of boron, and 0.45 mmol of germanium exhibited a capture ability per 1 g of the chelate fiber B. Was done.

Example 3 10 g of cotton yarn was immersed in a solution of 500 g of maleic anhydride in 1,000 ml of N, N'-dimethylformamide, and heat-treated at 80 ° C. for 10 hours. Next, the treated cotton yarn was washed with acetone and distilled water, drained, and dried at 40 ° C. for 15 hours to obtain 12.3 g of a fiber having a reactive double bond introduced into the cotton yarn molecule. .

Next, an average molecular weight of 60 ml was added to 800 ml of distilled water.
The cotton yarn into which the reactive double bond has been introduced is immersed in a solution in which 200 g of polyethyleneimine is dissolved, and heated at 25 ° C. for 20 hours. Next, after sufficiently washing with water and dewatering, 15.5 g of a chelate-forming fiber (chelate fiber C) introduced with polyethyleneimine (PEI substitution ratio: 55.5% by mass) was dried at 50 ° C. for 15 hours. Obtained. When a capture test similar to that of Example 1 was performed using this chelate fiber C, per 1 g of the chelate fiber C,
It was confirmed that 0.8 mmol of copper, 0.05 mmol of boron, and 0.4 mmol of germanium exhibited a capturing ability.

Example 4 After adding 10 g of silk cloth (silk feather double with 6 momme) and 6 g of epichlorohydrin to 500 ml of isopropyl alcohol,
Heat treatment was performed at 50 ° C. for 5 hours. Next, the treated silk cloth was washed with methanol and distilled water, drained, and dried at 40 ° C. for 15 hours to obtain 12.1 g of a fiber having halogen introduced into the silk cloth molecules.

Then, an average molecular weight of 60 ml was added to 350 ml of distilled water.
The above-described silk cloth into which the halogen has been introduced is immersed in a solution in which 150 g of polyethyleneimine is dissolved, and heat-treated at 80 ° C. for 5 hours. Then, after thoroughly washing with water and draining, 50 ° C
For 15 hours, the chelate-forming fiber (chelate fiber D) into which polyethyleneimine has been introduced.
4.3 g (PEI substitution ratio: 43.0% by mass) were obtained. When a capture test similar to that of Example 1 was performed using the chelate fiber D, copper was used in an amount of 0.6 g / g of the chelate fiber D.
mmol, boron 0.03 mmol, germanium 0.3
It was confirmed that it exhibited the ability to capture mmol.

Example 5 To 400 ml of distilled water, 10 g of silk cloth (silk feather double with 6 momme) and 2 g of ethylene glycol diglycidyl ether were added.
After heating to 0 ° C., a solution prepared by dissolving 30 g of polyethyleneimine having an average molecular weight of 600 in 70 g of distilled water is added dropwise over 1 hour, and further heated at 70 ° C. for 2 hours. Next, after thoroughly washing with distilled water and methanol and removing the liquid, 50 ° C.
By heating for 15 hours at room temperature to obtain a chelate-forming fiber (chelate fiber E) into which polyethyleneimine has been introduced.
13.5 g (PEI substitution ratio 35% by mass) were obtained. When the same adsorption test as in Example 1 was performed using this chelate fiber E, copper 0.5 mm / g of the chelate fiber E was used.
ol, boron 0.03 mmol, germanium 0.3 mm
It was confirmed that it exhibited the ability to capture ol.

[0064]

The present invention is constituted as described above, and has not only a high trapping ability for not only metal ions but also metal ions, and also a remarkably excellent trapping speed. Compared to conventional ion-exchange resins and chelate resins, they can capture and remove wastewater, oil, and metals or similar metals in air (including various exhaust gases, etc.) very efficiently. It can be done effectively. Moreover, the chelate-forming fiber of the present invention in which the component has been captured is easily separated from the component by treating it with an aqueous acid solution or the like. Can also be used. In addition, if chelate-forming fibers such as a nonwoven fabric or a fabric are used, it is easy to use them as a cartridge system to enhance exchangeability and other workability. It can be easily incinerated by an incinerator.

Further, if the production method of the present invention is adopted, the method can be carried out safely and easily by a simple method such as heat treatment in water or a general-purpose polar solvent without special equipment or treatment such as ionizing radiation. High performance chelating fibers can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing a comparison between a chelate fiber A obtained in Example 1 and a capture rate of copper ions using a commercially available beaded chelate resin.

FIG. 2 is a graph showing a comparison between a chelate fiber A obtained in Example 1 and a breakthrough curve of copper ions using a commercially available beaded chelate resin.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 3/00 108 C09K 3/00 108A D06M 14/04 D06M 14/04 15/273 15/273 // C02F 1/28 C02F 1 / 28Z (72) Inventor Osamu Ito Osamu 3-3-3 Hinagahigashi, Yokkaichi City, Mie Prefecture Inside the Yokkaichi Plant, Central Kyrest Co., Ltd. (72) Inventor Takao Doi 3-3, Hinagahigashi, Yokkaichi City, Mie Prefecture F-term in Yokkaichi Plant of Chubu Kyrest Co., Ltd. (reference)

Claims (16)

[Claims] 1. A chelate-forming fiber characterized in that polyethyleneimine is introduced into a fiber molecule and has a chelate-forming ability with a metal or a metal-like element. 2. The chelating fiber according to claim 1, wherein the polyethyleneimine has an average molecular weight of 300 to 70,000. 3. The chelating fiber according to claim 1, wherein the polyethyleneimine is directly bonded to a reactive functional group in the fiber molecule. 4. The chelate-forming fiber according to claim 1, wherein the polyethyleneimine is introduced into a reactive functional group in a fiber molecule via a crosslinking agent. 5. The chelate-forming agent according to claim 4, wherein the crosslinking agent is a compound having two or more functional groups selected from an epoxy group, a reactive double bond, a halogen group, and an acid anhydride in the molecule. fiber. 6. The cross-linking agent is at least one selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, epichlorohydrin, ethylene glycol diglycidyl ether, maleic anhydride, and itaconic anhydride. Item 6. A chelate-forming fiber according to Item 5. 7. The chelating fiber according to claim 1, wherein the fiber is a natural fiber or a regenerated fiber. 8. The chelating fiber according to claim 7, wherein the natural fiber or the regenerated fiber is a cellulosic fiber. 9. The chelating fiber according to claim 1, wherein the fiber is a synthetic fiber. 10. A method for producing chelate-forming fibers, wherein polyethyleneimine is directly reacted with a reactive functional group in a fiber molecule. 11. A compound having two or more functional groups selected from an epoxy group, a reactive double bond, a halogen group, and an acid anhydride as a cross-linking agent is reacted with a reactive functional group in a fiber molecule. A method for producing chelate-forming fibers, comprising reacting polyethyleneimine after the reaction. 12. The cross-linking agent is at least one selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, epichlorohydrin, ethylene glycol diglycidyl ether, maleic anhydride, and itaconic anhydride. Item 12. The production method according to Item 11. 13. A method for capturing a metal or a metal-like element, comprising using the chelate-forming fiber according to claim 1 and capturing a metal or a metal-like element. 14. The capturing method according to claim 13, wherein the chelate-forming fiber is brought into contact with an aqueous liquid or an oily liquid containing a metal or a metal-like element, and the metal or metal-like element in the liquid is captured. 15. The capturing method according to claim 13, wherein the chelate-forming fiber is brought into contact with a gas containing a metal or a metal-like element to capture the metal or the metal-like element in the gas. 16. A metal- and / or metal-like chelate fiber, wherein the chelate-forming fiber according to any one of claims 1 to 8 is a metal and / or a metal-like metal chelate-bonded.