JP2000169828A - Powdery chelate-catching material and its production, and ion-catching using the catching material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a powdery chelate-catching material capable of exhibiting excellent catching performances for metal ions and the like and capable of being used in the present form as such or in an existing device by introducing chelate-forming functional groups to the molecules of a powdery material. SOLUTION: This powdery chelate-catching material is obtained by introducing chelate-forming functional groups, preferably acyl groups of the formula [R1-R3 are each a lower alkylene; (n) is 1-4], to the molecules of a powdery raw material (preferably the powder of natural fibers or regenerated fibers, the powder of synthetic fibers, or the like). A method for introducing the chelate-forming functional groups to the powdery raw material includes a method for directly reacting the functional groups with a chelate-forming compound having a reactive functional group (preferably nitrilotriacetic acid anhydride, ethylenediamine tetraacetic acid dianhydride, or the like). For example, ethylenediaminetetraacetic acid dianhydride is heated and dissolved in N,N- dimethylformamide and then powdery cellulose is added.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery chelate trapping material capable of efficiently removing and purifying metal ions and metal ions in a non-treatment fluid, a method for producing the same, and an ion using the trapping material. It relates to a trapping method, and this powdery chelate trapping material is a metal ion contained in a liquid such as an aqueous liquid or an oily liquid, or a gas such as various exhaust gases, and in particular, harmful heavy metal ions such as copper, zinc, nickel and cobalt. Or toxic or valuable metal ions such as boron, germanium, arsenic, antimony, antimony, selenium, tellurium and the like can be efficiently removed, for example, water such as industrial wastewater, drinking water, food processing water, etc. Alternatively, it is effective in purifying various liquids such as edible oil and food processing oil, exhaust gas, and the like.

[0002]

2. Description of the Related Art Industrial wastewater may contain various harmful ions, and it is necessary to sufficiently remove such metal ions by wastewater treatment from the viewpoint of preventing environmental pollution. 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. Further, metals that may be mixed as a hydrogenation catalyst when producing edible oils or food processing oils, etc., also need to be removed as much as possible because they adversely affect storage stability and the human body. .
Further, various harmful metals may be mixed in exhaust gas from a plating factory, a clean room, or the like, and it is desired to remove these as much as possible.

[0003] Boron and boron compounds, which are a kind of a class of metals, are widely distributed in nature and are indispensable elements for the human body. On the other hand, it has also been confirmed that excessive intake leads to adverse effects. Have been. In addition, there are reported cases of human contamination due to boron components contained in rivers and groundwater, and there is a concern about adverse effects when water is reused. In addition to boron, for example, arsenic and arsenic compounds are harmful to the human body and must be removed as much as possible from drinking water or the like, which may be mixed.

In the present invention, under the above-described circumstances, these metal ions and metal ions and their compounds are efficiently captured and removed from a liquid to be treated such as water or edible oil, an exhaust gas, and the like to purify them. The present invention provides a powdery chelate scavenger which can be used, and further studies on the technology for purifying a fluid to be treated using the powdery chelate scavenger.

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

Further, a chelate resin having a property of forming a chelate with a metal ion and selectively trapping the chelate has an excellent selective trapping property for a metal ion, particularly a heavy metal ion. It is used for removing and capturing heavy metals in the field of water treatment. However, most of the chelate resins simply have a chelate-forming functional group such as iminodiacetic acid introduced therein, and do not necessarily show satisfactory chelate-forming ability.

A conventional ion exchange resin or chelate forming resin is a bead having a rigid 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. Because it is slow, there is a problem with processing efficiency, and because it contains tens of percent water,
As it is, it cannot be used for non-aqueous liquids such as oil. Furthermore,
Since it is difficult to incinerate by using the disposable type without recycling, there is a big problem how to reduce the volume of the used resin.

[0008] As a solution to the problem of the bead-like chelate-forming resin, a fibrous or sheet-like chelating agent has been proposed (JP-A-7-10925, etc.). The fibrous or sheet-like chelating agent has a large specific surface area, and a chelating functional group serving as a metal ion absorption / desorption point is present on the surface, so that absorption / desorption efficiency is enhanced, and furthermore, incineration disposal, etc. Has many advantages, such as easy operation. However, since the production method of the fibrous or sheet-form chelating agent is complicated, and a method using ionizing radiation must be adopted, it is practical in terms of facilities, safety, production cost, and the like. Many problems are pointed out above.

The fibrous or sheet-like chelating agent has a higher ion adsorption rate than the bead-like chelating resin, but is greatly affected by the fiber shape.

Further, when a fluid is treated using a fibrous or sheet-like chelating agent, it is necessary to devise, for example, processing the adsorbent into a filter in order to bring the fluid into contact with the adsorbent efficiently. In addition, a fibrous or sheet-like chelating agent cannot be used in a simple form using existing equipment.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object to provide metal ions or similar metal ions in an aqueous liquid, an oily liquid, or various kinds of exhaust gas, and the like. In addition to having excellent trapping performance for compounds, it does not require special processing at the time of use, it can be trapped in the same form and using existing equipment, and it is easy to incinerate etc. In addition, we have developed a powdery chelate trapping material that can be manufactured at a low cost with a simple and safe method, and established a method that can efficiently purify fluids by making good use of the specialty of the chelate trapping material. Is to do.

[0012]

The powdery chelate trapping material of the present invention which can solve the above-mentioned problems is selected from the group consisting of the following general formulas [1] to [4] in the molecule of the powdery material. It is characterized in that at least one type of chelating functional group is introduced.

[0013]

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Wherein R ₁ , R ₂ and R ₃ are lower alkylene groups, and n is an integer of 1 to 4.

[0015]

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Wherein G is a sugar alcohol residue or a polyhydric alcohol residue, R is a hydrogen atom, a (lower) alkyl group or -G (G has the same meaning as described above, and is the same as or different from G above. May be a group)

[0017]

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[Wherein, X is a residue obtained by removing one carboxyl group from a monocarboxylic acid or dicarboxylic acid, V is a hydrogen or carboxyl group, M is a hydrogen or a carboxyl group.

[0019]

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(R ₄ is a residue obtained by removing one hydrogen from a carbon chain in an alkylene group, R ₅ is a direct bond or an alkylene group, Y ₁ and Y ₂ are the same or different and are hydrogen, carboxyl group, amino group, hydroxyl group Group, phosphone group or thiol group, n is an integer of 1-4, M ′ is hydrogen or

[0021]

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(R ₆ is a residue obtained by removing one hydrogen from a carbon chain in an alkylene group, R ₇ is a direct bond or an alkylene group, Y ₃ and Y ₄ are the same or different and are hydrogen, carboxyl group, amino group, hydroxyl group Group or thiol group), Z represents hydrogen or the same meaning as the above M, but may be the same as or different from the above M]

[0023]

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[Wherein, V, X, Z and M 'have the same meanings as above]

As a method for introducing a chelate-forming functional group into the powdery material, a reactive functional group (hydroxyl group, carboxyl group, aldehyde group, amino group, etc.) in a molecule constituting the powdery material may be used. In addition to a method of directly reacting a chelate-forming compound having a reactive functional group with a group of the above, the introduction of a chelate-forming group by reacting the chelate-forming compound via a more reactive crosslinking agent Increasing efficiency is also effective.

The preferred chelate-forming compound used in carrying out the production method of the present invention includes a polycarboxylic acid represented by the aforementioned general formula [5] and used for producing a chelate fiber previously developed by the present inventors. Acid anhydrides of acids, specifically, nitrilotriacetic anhydride, ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaacetic dianhydride, or the like, or an amine compound represented by the general formula [6], specifically, D-glucamine, N-methyl-D-glucamine,
Dihydroxypropylamine and the like are preferably used.

As another preferred method, a powdery material having a functional group reactive with an acid anhydride in a molecule is used,
It is also effective to react the material with an acid anhydride having a reactive double bond as a cross-linking agent, and then react the compound with a chelate-forming compound. A compound having at least one group selected from the group consisting of an amino group, an imino group and a thiol group and a carboxyl group, specifically, amino acids, iminodiacetic acid, iminodisuccinic acid, ethylenediaminediacetic acid, ethylenediamine Acetic acid, ethylenediamine disuccinic acid, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptopropionic acid and the like are preferably used.

The amount of the chelate-forming functional group introduced into the fiber molecule by these methods is 5% by weight or more in terms of the amount obtained by the following formula, so that a powder having a high chelate-capturing ability can be obtained. A chelate scavenger in a state can be obtained. Introduced amount (% by weight) = [(weight of powdery material after introduction of chelate-forming functional group−weight of powdery material before introduction of chelate-forming functional group) / weight of powdery material before introduction of chelate-forming functional group] × 100

The type of the powdery material into which the chelate-forming functional group is introduced is not particularly limited, and various natural fibers typified by vegetable fibers such as cotton and hemp and animal fibers such as silk and wool. Fibers or regenerated fibers, and further powders composed of various synthetic fibers such as polyester fibers and polyamide fibers can be arbitrarily selected and used. Among them, particularly preferred are hydroxyl groups and carboxyl groups in the molecules constituting the powdery material, It is a natural fiber or a regenerated fiber having a reactive functional group such as an aldehyde group and an amino group.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The powdery chelate trapping material of the present invention is a powdery material in which a chelate-forming functional group represented by the above general formulas [1] to [4] is introduced into the molecule. ,
The general formulas [1], [3] and [4] show that nitrogen, sulfur and carboxylic acid present therein exhibit excellent selective adsorption to heavy metal ions such as copper, zinc, nickel and cobalt, In the general formula [2], nitrogen and hydroxyl groups present therein exhibit excellent selective adsorption to metal ions such as boron, germanium, arsenic, antimony, selenium, and tellurium.

In the chelate trapping material of the present invention, since the functional group having the selective adsorption activity is exposed on the surface of the molecule constituting the powdery material, excellent selective adsorption activity is exhibited.

Hereinafter, the features of the present invention will be further clarified while explaining a typical method of introducing a chelating functional group into a powdery material.

The first method is a method in which the powdery material is reacted with the chelate-forming compound represented by the general formula [5]. The acyl group represented by the general formula [1] introduced by this method is used. The nitrogen and carboxylic acid present therein exhibit excellent chelate trapping ability for heavy metal ions such as copper, zinc, nickel and cobalt.

In the general formula (1), R₁ ~ R_Two Low indicated by
As the lower alkylene group, C₁ ~ C ₆ Is an alkylene group
Among them, methylene and ethyl are particularly preferable.
Ren and propylene. In particular, as the number of repetitions n
Preferred is 1 or 2.

Preferred specific examples of the acid anhydride of the polycarboxylic acid represented by the general formula [5] include nitrilotriacetic acid anhydride (NTA anhydride), ethylenediaminetetraacetic acid dianhydride (EDTA dianhydride). ), Ethylenediaminetetraacetic acid monoanhydride (EDTA monoanhydride), diethylenetriaminepentaacetic acid dianhydride (DTPA dianhydride),
Examples include diethylenetriaminepentaacetic acid / monoanhydride (DTPA / monoanhydride), and particularly preferred are:
NTA anhydride, EDTA dianhydride, DTPA dianhydride.

Then, these acid anhydrides are dissolved in a polar solvent such as N, N'-dimethylformamide or dimethylsulfoxide, and reacted with the powdery material at about 60 to 100 ° C. for about 30 minutes to several hours. The acid anhydride group reacts with and binds to a reactive functional group (for example, a hydroxyl group or an amino group) in a molecule constituting the powdery material, and the chelate-forming functional group comprising the acyl group is introduced in a pendant form, A powdery chelate scavenger excellent in selective adsorption to metal ions can be obtained.

When there is no reactive functional group in the molecules constituting the powdery material, the reactive functional group is first introduced into the powdery material by any means such as oxidation, graft polymerization, and the like.
The polycarboxylic acid anhydride may be reacted, and even when a reactive functional group is present, if the reactivity with the polycarboxylic acid anhydride is low, a highly reactive reactive functional group is used. It is also effective to react with the polycarboxylic anhydride after the introduction.

The introduction reaction of the acyl group is schematically shown below, taking the reaction of cotton or silk with ethylenediaminetetraacetic acid / dianhydride as an example.

(Cotton)

[0040]

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(In the case of silk)

[0042]

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In the above description, the case where the above-mentioned polycarboxylic anhydride is reacted with the hydroxyl group or the amino group in the molecule constituting the powdery material is typically shown. However, = NH, -SH or other reactive functional groups In the case where the above-mentioned acyl group is introduced by utilizing the above, the same can be considered.

Thus, by introducing the acyl group represented by the general formula [1] into the molecules constituting the powdery material, the material to be treated having a low metal ion concentration can be obtained not only in the vicinity of neutrality but also in a low pH range. Even when applied to water, it is possible to obtain a powdery chelate trapping material which exhibits excellent heavy metal ion selective adsorption activity and has an excellent adsorption rate.

The metal to be captured by the powdery chelate capturing material having the chelate-forming functional group introduced therein is copper,
Lanthanum belonging to the nickel, cobalt, zinc, calcium, magnesium, iron and the like or the rare earth elements scandium, yttrium, and lanthanoids,
Cerium, praseodymium, neodymium, samarium, eurobium, gadolinium, dysprosium, holmium,
Examples include radioactive elements such as erbium and ytterbium, and technetium, promethium, francium, radium, uranium, plutonium, and cesium.

The following method for introducing a chelate-forming functional group into a powdery material is carried out by converting a powdery material having a reactive functional group, such as a hydroxyl group or an amino group, into an amine compound represented by the above formula [6]. Is added to a treatment liquid containing the compound (1) to introduce a chelate-forming functional group represented by the formula [2] into the molecule.

The powdery chelate scavenger having a chelate-forming functional group represented by the above formula [2] has an excellent chelate scavenging ability for metal ions, and one example is N-methyl. Taking boron ions as an example with a powdery chelate trapping agent into which a -D-glucamine residue has been introduced, the following formula is obtained.

[0048]

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That is, this powdery chelate trapping material has a group having an amino group and two or more hydroxyl groups in the molecule,
In particular, groups with at least two hydroxyl groups attached to adjacent carbons have been introduced, exhibiting excellent chelating ability for similar metals such as boron, thereby effectively trapping similar metals .

Preferred groups satisfying such requirements are as shown in the above formula [2], wherein G represents a sugar alcohol residue or a polyhydric alcohol residue,
Represents a hydrogen atom, a (lower) alkyl group or -G (G has the same meaning as described above, and may be the same as or different from -G); (Lower) alkyl group. In the above, examples of the (lower) alkyl group include C ₁ -C ₆ alkyl groups, and particularly preferred are a methyl group and an ethyl group.

Among the groups represented by the general formula [2], particularly preferred are groups in which G is a sugar alcohol residue or a polyhydric alcohol residue, and R is a hydrogen atom or a (lower) alkyl group. Examples include D-glucamine, D-
Galactamine, D-mannosamine, D-arabicylamine, N-methyl-D-glucamine, N-ethyl-D-glucamine, N-methyl-D-galactamine, N-ethyl-D-galactamine, N-methyl -D-mannosamine,
Examples thereof include a sugar alcohol residue obtained by removing an amino group from N-ethyl-D-arabitylamine and the like, and a dihydroxyalkyl group, in consideration of easy introduction into a molecule, availability of raw materials, and the like. Most preferred are residues other than the amino group of D-glucamine or N-methyl-D-glucamine or a dihydroxypropyl group.

The groups introduced to impart the metal-chelate-forming ability include reactive functional groups (eg, hydroxyl group, amino group, imino group, carboxyl group, aldehyde group, Thiol group)
And the like, or may be indirectly linked via a cross-linking bond as described below.

As a method for introducing the above-mentioned metal chelate-forming functional group into the molecule of the powdery material, the reactive functional group originally possessed by the powdery material or the reactive functional group introduced by modification is used. The functional group has the general formula [6]
Or reacting the reactive functional group with two or more functional groups such as an epoxy group, a reactive double bond, a halogen group, an aldehyde group, a carboxyl group, and an isocyanate group in the molecule. A method of reacting the compound having the compound with the amine compound represented by the formula [2] is employed.

That is, when the powdery material has a hydroxyl group, a carboxyl group, or the like, these groups are directly reacted with the amine compound represented by the general formula [6], and this is pendantly formed into fiber molecules. A typical reaction in this case is as follows.

[0055]

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When the reactivity between the reactive functional group in the powdery material and the amine compound is poor, the material is first reacted with a crosslinking agent to pendant the functional group having high reactivity with the amine compound. Then, by reacting this functional group with the above-mentioned amine compound, a group having the ability to form a metal-like chelate can be introduced in a pendant manner. In particular, if the latter method is adopted, by adjusting the amount of the cross-linking agent or the amine compound used for the powdery material, the like metal trapping ability according to the purpose of use (ie,
It is preferable because the amount of the group having the ability to form a metal-like chelate can be arbitrarily controlled.

Preferred examples of the crosslinking agent used herein include compounds having two or more, preferably two, epoxy groups, reactive double bonds, halogen groups, aldehyde groups, carboxyl groups, isocyanate groups and the like. Specific examples of the crosslinking agent 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 acid, succinic acid,
Examples thereof include adipic acid, glyoxal, glyoxylic acid, tolylene diisocyanate, and hexamethylene diisocyanate, and particularly preferred are glycidyl methacrylate, epichlorohydrin, and ethylene glycol diglycidyl ether.

A specific reaction when introducing an amine compound using the above-mentioned cross-linking agent is as follows.

[0059]

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The reaction when introducing a group having the ability to form a metal-like chelate into a powdery material by using these cross-linking agents is not particularly limited. However, in a preferred method, the cross-linking agent is added to the powdery material. Dissolve in water or a polar solvent such as N, N'-dimethylformamide or dimethylsulfoxide, and optionally use a reaction catalyst, an emulsifier, etc.
This is a method in which the reaction is carried out by contacting at about 00 ° C. for about 30 minutes to several tens of hours, and by this reaction, a cross-linking agent causes a reactive functional group (for example, a hydroxyl group, an amino group, etc.) in a molecule constituting the powdery material. ) Can be introduced into the fiber molecule by binding to the fiber by reacting with the amine compound as shown in the above formula [6]. Next, a solution prepared by dissolving the powdered material having the functional group introduced therein and the amine compound in a polar solvent such as water or N, N'-dimethylformamide or dimethylsulfoxide is used, if necessary, in a group of 60 to 60 with a combined use of a reaction catalyst. When the reaction is carried out by contacting at 100 ° C. for about 30 minutes to several tens of hours, the amino group of the amine compound reacts with a reactive functional group (for example, an epoxy group or a halogen group) of the cross-linking agent. A powdery chelate trapping material in which the indicated group having the ability to form a metal-like chelate is introduced in the molecule in a pendant manner is obtained.

This reaction is usually carried out sequentially as described above. However, depending on the reaction system, a crosslinking agent and an amine compound are simultaneously brought into contact with a powdery material, and the molecules constituting the powdery material are simultaneously reacted. It is also possible to react in parallel.

Examples of the similar metals to be captured by the powdery chelate capturing material into which these chelate-forming functional groups are introduced include boron, arsenic, antimony, selenium, tellurium, silicon and the like.

Another method for obtaining a powdery chelate trapping material is to use a powdery material having a reactive functional group with an acid anhydride in the molecule,
This is a method in which an acid anhydride having a reactive double bond is reacted as a crosslinking agent, and then a chelate-forming compound is reacted.

According to this method, the acid anhydride having a reactive double bond is reacted with the reactive functional group in the molecule constituting the powdery material as described above, thereby forming the molecule constituting the powdery material. By introducing a reactive double bond therein and reacting the reactive double bond with a metal chelating compound, the powdery material is given a metal chelating ability.

The acid anhydride having a reactive double bond used herein is not particularly limited as long as it is a compound having both an acid anhydride group and a reactive double bond in the molecule. Specific examples include maleic anhydride, itaconic anhydride, aconitic anhydride, citraconic anhydride, maleated methylcyclohexene tetrabasic anhydride, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, crotonic anhydride, acrylic acid anhydride, Methacrylic anhydride and the like can be mentioned. Among these, particularly preferred are intramolecular anhydrides of dibasic acids, and particularly preferred are maleic anhydride and itaconic anhydride in view of the reaction efficiency and cost when introduced into the molecule.

The acid anhydride having a reactive double bond and the powdery material are mixed, for example, with a reaction catalyst in a polar solvent such as N, N'-dimethylformamide or dimethylsulfoxide, for example, for 60 to 60 hours. 30 at about 100 ° C
When contact is made for minutes to several hours, the reactive functional group in the molecule constituting the powdery material reacts with the acid anhydride group to bond, and a group having a reactive double bond is introduced into the fiber molecule.

When the chelate-forming compound is reacted with the powdery material into which the reactive double bond has been introduced, the chelate-forming compound is introduced in a pendant manner into the molecules of the powdery material, and Has a metal chelate forming ability.

Here, as the chelate-forming compound, a compound having a functional group having a reactivity with a reactive double bond in the molecule is used. Particularly preferred as the functional group having reactivity with the reactive double bond are an amino group, an imino group, and a thiol group. These groups easily react with the above-mentioned reactive double bond. N or S in
However, it exhibits a metal chelate forming ability together with a coexisting carboxyl group.

When the acid anhydride having a double bond is introduced into a molecule constituting the powdery material, one carboxyl group is generated by ring opening, and this exhibits a chelate-forming ability together with N and S. Therefore, the presence of a carboxyl group in the chelate-forming compound itself is not essential, but the chelate-forming ability is more effectively exerted by the interaction of N and S coexisting in the same molecule with the carboxyl group. Therefore, it is preferable to use a compound having at least one of an amino group, an imino group, and a thiol group and a carboxyl group in the molecule as the chelate-forming compound.

Specific examples of the chelating compound having at least one of an amino group, an imino group and a thiol group and a carboxyl group in the molecule include amino acids such as glycine, alanine, aspartic acid and glutamic acid; Diacetic acid, iminonisuccinic acid, ethylenediaminediacetic acid, ethylenediaminetriacetic acid, ethylenediaminedisuccinic acid, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptopropionic acid, and the like are exemplified. Thiomalic acid.

The method of reacting the above-mentioned chelate-forming compound with the above-mentioned powdery material into which the acid anhydride having a double bond is introduced is not particularly limited.
A metal chelate-forming compound is dissolved in water or a polar solvent such as N, N'-dimethylformamide or dimethylsulfoxide, and a processing solution to which a reaction catalyst is added if necessary, for example, at about 10 to 100 ° C for 30 minutes to several tens of hours. In this method, the amino group, imino group or thiol group reacts with the reactive double bond introduced into the molecules constituting the powdery material, whereby the above-mentioned general formula [3] The chelating functional group shown in [4] is introduced in a pendant manner into fiber molecules constituting the powdery material.

Typical examples of such a reaction include cotton as a fiber,
Maleic anhydride as an acid anhydride, iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminedisuccinic acid, iminonisuccinic acid, thioglycolic acid or thiomalic acid as a chelate-forming compound. As shown in FIG.

[0073]

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In the above formula, a case where an acid anhydride is reacted with a hydroxyl group in a fiber molecule is typically shown.
The same applies to the case where another reactive functional group such as an amino group, an imino group, a glycidyl group, an isocyanate group, an aridinyl group, and a thiol group is used.

That is, the types of the acyl groups represented by the general formulas [3] and [4] introduced into the powdery material molecule by the above method are different from those of the acid anhydride used for introducing the acyl groups. Various changes can be made depending on the combination with the metal chelating compound. Accordingly, the acyl group includes various acyl groups as shown below, in addition to those shown in the above formula.

[0076]

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[0077]

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The metal to be captured by the powdery chelate capturing material having the chelating functional group introduced via the acid anhydride group as described above is copper, nickel, cobalt, or the like.
Zinc, calcium, magnesium, iron and the like, or the rare earth elements scandium, yttrium, and lanthanum belonging to the lanthanoid series, cerium, praseodymium, neodymium, samarium, eurobium, gadolinium, dysprosium, holmium, erbium, ytterbium, and further radioactive elements Technetium, which is
Promethium, francium, radium, uranium, plutonium, cesium and the like are exemplified.

In the present invention, the amount of the chelate-forming functional group introduced into the powdery material is determined by the amount of the reactive functional group in the molecule constituting the base powdery material or the amount of the chelate-forming compound used. Alternatively, it can be arbitrarily adjusted depending on the amount of the cross-linking agent used, and furthermore, their introduction reaction conditions, etc.
The introduction amount calculated by the following formula is about 5% by weight or more,
More preferably, it is desirable to adjust so as to be about 10% by weight or more. Introduced amount (% by weight) = [(weight of powdery material after introduction of chelate-forming functional group−weight of powdery material before introduction of chelate-forming functional group) / weight of powdery material before introduction of chelate-forming functional group] × 100 (however, the introduced amount indicates the introduced amount of the chelate-forming functional group)

In order to enhance the ability to capture chelate, the higher the amount of introduction, the better. Therefore, the upper limit of the amount of introduction is not particularly limited. However, the crystallinity of the chelate-forming functional group-introduced molecule, which is too high, increases. Since the trapping material tends to be brittle, the amount of introduction can be suppressed to about 130% by weight or less, more preferably about 80% by weight or less, in consideration of the practicality and economy as a chelate-trapping material. desirable. However, depending on the application etc., 150 to 2
It is also possible to increase the chelate capturing ability by setting the introduced amount to a high level such as 00% by weight.

The type of the powdery material to which the chelate-forming ability is imparted is not particularly limited. For example, various plant fibers such as cotton and hemp; various animal fibers such as silk and wool; Various recycled fibers such as coarse rayon and acetate; various synthetic fibers such as polyamide, acrylic, and polyester; and those obtained by cutting or crushing these fibers into powder.

The powdery material is preferably a short fiber organic polymer powder. Among these powdery materials, particularly preferred are reactive functional groups such as hydroxyl groups and amino groups in the material molecules. It is a monofilamentary powdery material obtained by processing plant fibers, animal fibers, and regenerated fibers. These powdery materials are preferable because a metal chelate-forming functional group as described above can be easily introduced by using a reactive functional group in a molecule constituting the powdery material. However, even when the raw material powder itself does not have a reactive functional group, it may be modified by any means such as oxidation, or a more reactive functional group may be added via a crosslinking agent. It is also possible to introduce the above-mentioned groups using the functional groups.

The preferred shape of the powdery material used here is 0.01 to 5 mm in length, preferably 0.03 to 3 mm.
mm, the single fiber diameter is about 1 to 50 μm, preferably 5 to 50 μm.
It is a single fiber having an aspect ratio of about 1 to 600, preferably about 1 to 100.

If the powdery chelate trapping material of the present invention is used, the powdery chelate trapping material is added to an aqueous or oily liquid containing metal ions or metal ions and stirred, followed by ordinary filtration. With such a very simple method, it is possible to capture and clean metal ions and metal-like ions contained in the fluid to be treated in a short time. In some cases, the same effect can be obtained by packing the powdery chelate trapping material in a column or the like and passing the fluid to be treated.

Further, by introducing a chelate-forming functional group into the single-fibrous powdery material by the above-described method and then performing processing such as papermaking, a filter agent having chelate-forming ability can be easily obtained. it can.

Further, after a metal having a bactericidal action, such as copper or silver, is adsorbed on the powdery chelate trapping material of the present invention, it is kneaded into a resin or the like to impart antibacterial properties or a metal having an oxidation-reduction action. After adsorbing the ions, it can be used as a catalyst.

The present invention is constituted as described above, and the following advantages can be obtained by using the powdery chelate trapping material.

The conventional granular chelate resin has an outer peripheral surface and a fine pore as a part functioning to capture the chelate. However, the fine pore is slow in diffusion and substantially all functional groups cannot contribute to the chelate capture. Therefore, the effective utilization rate of the chelate resin as a whole is extremely low, and the absolute amount of the element that can be trapped must be insufficient.However, in the powdery chelate trapping material of the present invention, the chelate resin is introduced on the surface of the powdery material. Since all of the chelate-forming functional groups are effectively utilized for chelate trapping of the metal component and have a large effective specific surface area, an extremely high chelate trapping ability can be obtained with a small amount of use.

Since the chelating functional group is exposed on the surface of the molecule constituting the powdery material, the adsorption speed is high.

The particulate chelate resin generally becomes brittle and finely powdered when dried, making it impractical. However, the powdery chelate trapping material used in the present invention has a chelate-forming functional group introduced into the constituent molecules of the powdery material. Because
It does not become brittle even when dried, is easy to use repeatedly by regeneration, and can be used for oily liquids.

The form of use of the granular chelate resin is restricted by the shape of the filling container. However, since the present invention is in the form of powder, it can be filled into any shape or processed into any shape according to the purpose of use.

In the case of the granular chelate resin, the porosity is automatically determined depending on the particle size. However, in the case of the powdery chelate trapping material, the packing density can be arbitrarily changed, so that the degree of freedom in designing the processing equipment is high.

[0093] The powdery chelate trapping material of the present invention forms a chelate easily by trapping a metal ion or a similar metal ion and then treating it with a strong acid aqueous solution such as hydrochloric acid or sulfuric acid. The metal component can be recovered as a valuable component from the regenerating solution.

The above-mentioned powdery chelate trapping material used in the present invention has a property of selectively forming a chelate with a metal ion or a similar metal, and therefore, other metal ions such as Mg, Ca, Na, and the like. Even when a metal such as K or other anions such as halogen ions such as fluorine, chlorine and iodine coexist, it can be used very effectively as a selective trapping material for desired ions. Therefore, in various manufacturing processes, Mg, Ca, N
Remove only harmful heavy metals from the process liquid containing a, K, etc., or remove only harmful heavy metals, for example, leaving Mg, Ca, Na, K, etc. that may be contained in drinking water or food processing water. It is also possible to remove it.

Since the powdery chelate trapping material used in the present invention also has an effect as a filter aid, it can be added to a fluid containing both metal ions and insoluble contaminants, stirred and filtered. In addition, metal ions and insoluble contaminants can be efficiently removed simultaneously.

Thus, according to the powdery chelate scavenger of the present invention, metals or similar metals can be efficiently removed, and thus can be effectively used in the following applications, for example.

Purification of various liquid substances (for example, purification of drinking water and food processing water, purification of hydrogen peroxide water, purification of surfactant-containing substances, production of ultrapure water, quality of sake and soft drinks, etc. Stabilization, purification of water-soluble dye baths, purification of organic solvents and polymerizable monomers, etc.), removal or capture and recovery of metals from various liquids (eg, removal of hardness components from washing water,
Removal of harmful metals from textile refining wastewater, removal of similar metals and radioactive elements from wastewater at nuclear power plants, removal of selenium from wastewater at thermal power plants, wastewater and various reaction liquids,
Capture and recovery of valuable metals from seawater, etc., more specifically, recovery and purification of tin from chemical copper plating baths, removal or separation and recovery of heavy metals and similar metals from various wastewaters, rare metals from natural water, etc. Separation or capture, separation, recovery and purification of valuable metals from ore-treated water, removal and recovery of polymerization catalyst (such as germanium) mixed in raw material ethylene glycol distilled off during polyester production, engine oil and motor oil And the like, removal of heavy metals and similar metals contained in waste oils, removal of metal ions in edible oils and fats, and removal of harmful metals contained in various exhaust gases in plating plants and clean rooms.

[0098] In still another embodiment of the powdery chelate trapping material according to the present invention, a metal having catalytic activity, for example, iron, is trapped by the trapping material, and a redox reagent (N
Removal catalysts such as Ox and SOx)
Alternatively, it can be effectively used as an antibacterial or bactericidal powder in which an antibacterial metal such as copper, silver, nickel or the like is captured (for example, an antibacterial and bactericidal plastic can be obtained by kneading in a resin). Further, if the powdery chelate trapping material of the present invention is formed by a paper making method or the like, it can be used as a filter paper or a filter material having chelate forming ability.

[0099]

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 (Production of EDTA-type powdery chelate scavenger) 35.3 g of ethylenediaminetetraacetic acid dianhydride was added to N,
5 g of powdered cellulose ("KC Floc W-50 (S)" manufactured by Nippon Paper Industries Co., Ltd.) is added to a solution of N-dimethylformamide heated and dissolved in 200 ml at 80C, and the mixture is heated at 80C with stirring for 6 hours. Next, the unreacted ethylenediaminetetraacetic acid is dissolved and removed by adding the powdered cellulose to 500 ml of distilled water, adjusting the pH to about 10 using aqueous ammonia, and stirring for 3 hours.
Thereafter, the powdered cellulose was added to a 0.1N sulfuric acid aqueous solution 5
After stirring for 3 hours after adding to the water-based mixture, the washing was repeated with distilled water until the washing solution became neutral, and dried at 60 ° C. for 5 hours to obtain an EDTA type powdery chelate scavenger (powder chelate scavenger). A) 6.1 g (introduction rate: 22)
% By weight).

0.5 g of the obtained powdery chelate trapping material A
Was added to 500 ml of a dilute sulfuric acid aqueous solution containing 70 ppm of copper and adjusted to pH 5, and stirred at 20 ° C. for 20 hours. The copper ion trapping ability was determined by measuring the copper ion concentration of the solution. It was confirmed that 0.7 mmol / g of copper capturing ability was exhibited. Meanwhile, for comparison,
In place of the powdery chelate trapping material A, a copper bead trapping ability was examined in the same manner as described above except that a commercially available beaded styrene-IDA type chelate resin (trade name "Diaion CR11" manufactured by Mitsubishi Chemical Corporation) was used. However, 0.5 mmol / g
Only the ability to trap copper.

The above-mentioned powdery chelate trapping material A0.5
g was added to 500 ml of an aqueous solution having a copper concentration of 70 ppm, and the time-dependent change in the copper concentration in the solution was examined. Further, with respect to the commercially available beaded styrene-IDA type chelate resin (the same as above), the time-dependent change in the solution containing the same was also examined in the same manner as described above.

The results are as shown in FIG. 1. In the case of a commercially available bead-like chelating resin, the copper trapping performance was about 7
While it takes as long as 0 minutes, the time required to saturate the copper trapping performance when using the powdery chelate trapping material A of the present invention is only 7 minutes, and the powdery chelate trapping material A of the present invention is used.
It can be seen that the copper has about 10 times the copper capturing performance in terms of speed as compared with the conventional chelate resin.

Example 2 (Production of Glucamine-type Powdery Chelate Scavenger) In a solution prepared by dissolving 0.05 g of ammonium iron (II) sulfate hexahydrate in 200 ml of distilled water, powdered cellulose ("KC Floc" manufactured by Nippon Paper Industries) was added. W-50 (S) "), and stirred at 20 ° C for 15 minutes. Then, 1.5 g of glycidyl methacrylate and 0.1 g of a nonionic surfactant (" Nonion OT-221 "manufactured by NOF Corporation) were added. , 31% aqueous hydrogen peroxide and 0.06 g of thiourea dioxide, and heat-treated at 60 ° C. for 2 hours. Next, the treated powdered cellulose is washed and distilled with distilled water.
A solution prepared by dissolving 60 g of D-glucamine in 140 g of distilled water is added, and heat-treated at 80 ° C. for 2 hours. Then, after sufficiently washing with water and draining, the mixture was dried at 60 ° C. for 2 hours to obtain 7.2 g of a glucamine-type powdery chelate trapping material (powder-like chelate trapping material B) (substitution ratio: 44% by weight).

5 g of the obtained powdery chelate trapping material B
Was added to 500 ml of a boric acid aqueous solution containing 120 ppm of boron and adjusted to pH 8, and stirred at 20 ° C. for 20 hours. The boron concentration of the solution was measured to determine the boron capturing ability. It was confirmed that g exhibited the ability to capture boron. On the other hand, for comparison, a copper styrene-glucamine type chelate resin (trade name “Diaion CRB02” manufactured by Mitsubishi Chemical Corporation) was used in place of the powdery chelate trapping material B in the same manner as above except that When the capturing ability was examined, 0.6 mmol /
g of copper scavenging ability.

In addition, 5 g of the above-mentioned powdery chelate trapping material B was added to 500 ml of a boric acid aqueous solution having a boron concentration of 120 ppm, and the time-dependent change in the boron concentration in the solution was examined. Further, with respect to the commercially available beaded styrene-glucamine-type chelate resin (the same as above), the time-dependent change in the solution containing the same was also examined in the same manner as described above.

The results are as shown in FIG. 2. In the case of a commercially available beaded chelate resin, it took about 60 minutes to saturate the boron trapping performance, whereas the powdery chelate trapping material B of the present invention was used. The time required for the boron trapping performance to be saturated at that time is only 5 minutes, and the powdery chelate trapping material A of the present invention is about 12 times faster than the conventional chelate resin.
It can be seen that it has twice the copper capturing performance.

Example 3 (Production of IDA type powdery chelate trapping material) A solution of 50 g of maleic anhydride in 100 ml of N, N'-dimethylformamide was added to powdered cellulose ("KC Floc W-50 (Nippon Paper)"). S))), and after 5 hours of heat treatment at 80 ° C., wash and drain with acetone and distilled water. Then, the treated powdered cellulose was added to 100 ml of distilled water in 20.2 ml of iminodiacetic acid.
g, add to a solution adjusted to pH 10 with sodium hydroxide, treat at 25 ° C. for 15 hours, and wash and drain. Thereafter, the powdered cellulose was added to 500 ml of a 0.1 N sulfuric acid aqueous solution and stirred for 3 hours, and the washing was repeated with distilled water until the washing liquid became neutral.
By drying at 5 ° C. for 5 hours, 6.3 g (substitution ratio: 26% by weight) of an IDA-type powdery chelate trapping material (powder-like chelate trapping material C) was obtained.

The obtained powdery chelate trapping material C was examined for copper ion trapping ability in the same manner as in Example 1.
It was confirmed that 7 mmol / g of copper capturing ability was exhibited.

Further, the time-dependent change of the copper concentration in the copper solution was examined in the same manner as in Example 1. The results are as shown in FIG.
In the case of a commercially available beaded chelate resin, it takes about 70 minutes to saturate the copper capturing performance, whereas the time required for the copper capturing performance to be saturated when the powdery chelate capturing material C of the present invention is used is as follows. This is only 7 minutes, and it is understood that the powdery chelate trapping material C of the present invention has a copper trapping performance about 10 times as fast as the conventional chelate resin.

[0111]

The present invention is constituted as described above, and has an excellent trapping performance for metal ions or similar metal ions and their compounds in an aqueous or oily liquid due to the large surface area of the powdery material. Therefore, the fluid can be efficiently purified. In addition, it does not require special processing at the time of use, it can be captured in the same form as it is, and it can be captured with existing equipment, and it can be manufactured easily and inexpensively by an easy and safe method. is there.

[Brief description of the drawings]

FIG. 1 is a graph showing a comparison between a powdery chelate trapping material A obtained in Example 1 and a commercially available chelate resin in terms of the ability to trap chelate with copper ions.

FIG. 2 is a graph showing a comparison of the chelate-capturing ability with respect to boron for the powdery chelate-trapping material B obtained in Example 2 and a commercially available chelate resin.

FIG. 3 is a graph showing a comparison between a powdery chelate trapping material C obtained in Example 3 and a commercially available chelate resin in terms of the ability to trap chelate with respect to copper ions.

Continued on the front page. (72) Inventor Osamu Ito 3-3-3 Hinagahigashi, Yokkaichi-shi, Mie Central, inside of Yokkaichi Plant, Kyresta Co., Ltd. (72) Inventor Shiho Sato 3-3-3, Hinagahigashi, Yokkaichi-shi, Mie (72) Inventor Takao Doi 3- 3-3, Hinagahigashi, Yokkaichi, Mie Pref. Central F. Term in Yokkaichi, Mie Pref. 4D025 AA03 AA06 AA09 AA10 AB22 AB23 AB24 AB26 AB33 BA17 BA22 CA03 CA08 CA10

Claims (26)

[Claims] 1. A powdery chelate scavenger, wherein a chelate-forming functional group is introduced into a molecule of the powdery material. 2. The powdery chelate trapping material according to claim 1, wherein the chelate-forming functional group is an acyl group represented by the following general formula [1]. Embedded image (Wherein, R ₁ , R ₂ and R ₃ are lower alkylene groups, and n is 1
Represents an integer of ４4. ) 3. The chelating functional group is an amino group,
The powdery chelate trapping material according to claim 1, which is a group having at least two hydroxyl groups bonded to carbon. 4. The powdery chelate trapping material according to claim 3, wherein the chelate-forming functional group is a group represented by the following general formula [2]. Embedded image [Wherein, G is a sugar alcohol residue or polyhydric alcohol residue, R is a hydrogen atom, a (lower) alkyl group or -G (G
Represents the same meaning as described above, and may be the same as or different from the above G). 5. The powdery chelate trapping material according to claim 4, wherein G in the formula [2] is a residue obtained by removing an amino group from D-glucamine, and R is a hydrogen atom or a lower alkyl group. 6. The powdery chelate trapping material according to claim 4, wherein G in the formula [2] is a dihydroxypropyl group, and R is a hydrogen atom or a lower alkyl group. 7. The powdery chelate trapping material according to claim 1, wherein the chelate-forming functional group is a group represented by the following general formula [3] or [4]. Embedded image [Wherein X is a monocarboxylic acid or dicarboxylic acid
V is hydrogen or carboxyl group, M is hydrogen or (R ₄ is a residue obtained by removing one hydrogen from a carbon chain in an alkylene group; R ₅ is a direct bond or an alkylene group;
₁ and Y ₂ are the same or different and are hydrogen, carboxyl group, amino group, hydroxyl group, phosphone group or thiol group, n is an integer of 1 to 4, M ′ is hydrogen or (R ₆ is a residue obtained by removing one hydrogen from a carbon chain in an alkylene group, R ₇ is a direct bond or an alkylene group, Y ₃
, Y ₄ are the same or different and are hydrogen, a carboxyl group, an amino group, a hydroxyl group or a thiol group), Z is hydrogen or has the same meaning as that of M, provided that it may be the same as or different from M. Good] [Wherein, V, X, Z and M 'have the same meanings as described above] 8. The introduction amount of the chelate-forming functional group calculated by the following formula is 5% by weight or more.
8. The powdery chelate trapping material according to any one of 7. Introduced amount (% by weight) = [(weight of powdery material after introduction of chelate-forming functional group−weight of powdery material before introduction of chelate-forming functional group) / weight of powdery material before introduction of chelate-forming functional group] × 100 9. The powdery chelate trapping material according to claim 1, wherein the chelate-forming functional group is directly bonded to a reactive functional group in a molecule constituting the powdery material. 10. The powdery chelate trap according to claim 1, wherein the chelate-forming functional group is introduced into a reactive functional group in a molecule constituting the powdery material via a cross-linking bond. Wood. 11. The powdery chelate trapping material according to claim 1, wherein the powdery material is a powder of natural fiber or regenerated fiber. 12. The powdery chelate trap according to claim 1, wherein the powdery material is a synthetic fiber powder. 13. The powdery chelate trapping material according to claim 1, which has a function of chelating trapping a metal-class element or a compound thereof. 14. The powdery chelate scavenger according to claim 13, wherein the metal-class element or a compound thereof is boron or a boron compound. 15. A compound represented by the following general formula [5] directly into a reactive functional group in a molecule constituting a powdery material or after introducing another reactive functional group into a molecule constituting the material. A method for producing a powdery chelate scavenger comprising reacting an acid anhydride of a polycarboxylic acid represented by the formula: Embedded image (Wherein, R ₁ , R ₂ , R ₃ and n represent the above-mentioned general formula [2]
The same meaning as 16. The polycarboxylic acid anhydride represented by the general formula [5] is at least selected from the group consisting of nitrilotriacetic anhydride, ethylenediaminetetraacetic dianhydride, and diethylenetriaminepentaacetic dianhydride. The method for producing a powdery chelate trapping material according to claim 15, which is one kind. 17. A method of directly reacting a reactive functional group in a molecule constituting a powdery material with an amine compound represented by the following general formula [6] to give a chelate forming ability with a metal-like element or a compound thereof. A method for producing a powdery chelate trapping material, comprising: Embedded image [Wherein, G and R have the same meanings as in the general formula [2]] 18. After reacting a compound having two or more groups selected from an epoxy group, a reactive double bond and a halogen group in a molecule with a reactive functional group in a molecule constituting the powdery material. A method of producing a powdery chelate trapping material, which comprises reacting an amine compound represented by the above formula [6] to give a chelate forming ability with a metal-like element or a compound thereof. 19. The method according to claim 1, wherein D-glucamine or N-methyl-D-glucamine is used as the amine compound.
19. The method for producing a powdery chelate trapping material according to 7 or 18. 20. The method for producing a powdery chelate scavenger according to claim 17, wherein diamine is used as the amine compound. 21. A powdery material having a reactive functional group with an acid anhydride group in a molecule is reacted with an acid anhydride having a reactive double bond, and further reacted with a chelate-forming compound. For producing a powdery chelate trapping material. 22. Powder having at least one group selected from the group consisting of a hydroxyl group, an amino group, an imino group, a glycidyl group, an isocyanate group, an aziridinyl group, and a thiol group as a reactive functional group with an acid anhydride. 22. The method for producing a powdery chelate trapping material according to claim 21, wherein a powdery material is used. 23. The compound according to claim 21, wherein the chelate-forming compound is a compound having at least one group selected from the group consisting of an amino group, an imino group and a thiol group and a carboxyl group in the molecule. For producing a powdery chelate trapping material. 24. The powdery chelate trapping material according to claim 1, which is brought into contact with water containing metal ions and / or metal ions, and the metal ions and / or metal ions in the water. A method for capturing metal ions and / or metal-like ions, characterized in that: 25. The powdery chelate scavenger according to any one of claims 1 to 14, which is brought into contact with an oil containing metal ions and / or metal ions, and the metal ions and / or metal ions in the oil. A method for capturing metal ions and / or metal ions, which comprises capturing ions. 26. Contacting the powdery chelate trapping material according to any one of claims 1 to 14 with a gas containing metal ions and / or metal ions, and trapping the metal ions in the gas. A method for trapping a characteristic metal ion and / or metal ion.