TWI827592B - Method for removing metals in liquid, and anion exchange resin-mixed h-type chelating resin - Google Patents

Abstract

The invention provides a method of removing metals in a liquid by bringing an H-type chelating resin that has been mixed with an anion exchange resin into contact with a processing target liquid, thereby removing the metals in the processing target liquid, wherein the quantity of the anion exchange resin in the mixture is within a range from 0.10 to 100.0% by volume relative to the H-type chelating resin. According to the present invention, a method of removing metals in liquid that uses an H-type chelating resin can be provided in which the problem of leakage of mineral acids does not occur.

Description

Metal removal method from liquid and anion exchange resin mixed with H-type chelating resin

The present invention relates to a method for removing metals from liquids using chelating resins to remove metal impurities in liquids such as water, aqueous solutions or organic solvents.

Ester-based organic solvents such as PGMEA are used as photoresist dissolving solvents, strippers, etc. When used as a dissolving solvent or stripper for photoresist, impurities in the organic solvent, especially metal impurities, cause deterioration of semiconductor elements made of photoresist and shorten the life of the element, so it is better to keep them as small as possible.

As such a method for removing metal impurities in an ester-based organic solvent, there is a method of bringing a metal removal target liquid into contact with a chelating resin. For example, Patent Document 1 discloses an apparatus for manufacturing a processing liquid for electronic parts, which includes a step of charging and mixing two or more chemicals in a mixing tank, wherein at least one chemical is filled with an ion exchange resin. Or chelating resin ion exchange resin or chelating resin treatment tower.

The functional groups of the chelating resin include those with amine groups such as iminodiacetic acid group, aminomethyl phosphate group, and imine propionic acid group. Moreover, chelate resins having iminodiacetic acid groups, aminomethylphosphonic acid groups, iminopropionic acid groups, etc. are usually sold on the market as Na type and Ca type. Therefore, in applications where the leakage of Na and Ca is not desired, these chelating resins are prepared into H type after being adjusted with inorganic acid. [Prior technical literature] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2001-228635

[Problem to be solved by the invention]

H-type chelating resin with amine groups adjusted by inorganic acid. Since the inorganic acid will remain in the resin, if H-type chelating resin is used to remove metals from the liquid to be treated, the amount of residue remaining in the chelating resin will The inorganic acid will gradually leak out. In addition, acid such as hydrochloric acid leaks into the liquid to be processed, which may impair the quality depending on the use. Even if ultrapure water is used for cleaning after conditioning with mineral acid, it is difficult to quickly remove residual mineral acid from the resin. Cleaning after conditioning with mineral acid does not solve the problem of leakage of the mineral acid.

In addition, when metals in the liquid to be treated are removed, protons may be released due to exchange with the metals and acid may be generated. When the liquid to be treated is an ester-based organic solvent, etc., hydrolysis will occur.

Therefore, the object of the present invention is to provide a method for removing metals from liquid using H-type chelating resin, which is a method that does not cause the problem of leakage of inorganic acid. [Means used to solve problems]

Such above-mentioned problems can be solved by the following invention. That is, the present invention (1) provides a method for removing metals from a liquid, which removes metals from the liquid to be treated by bringing the liquid to be treated into contact with an H-type chelating resin mixed with an anion exchange resin, and is characterized by: The mixing amount of the anion exchange resin is 0.10 to 100.0% by volume relative to the H-type chelating resin.

Furthermore, the present invention (2) provides a method for removing metals from liquids as in (1), characterized in that the functional group of the H-type chelating resin has an amine group.

In addition, (3) of the present invention provides a method for removing metals from liquids as in (1) or (2), characterized in that the functional group of the aforementioned H-type chelating resin is an iminodiacetic acid group, an aminomethyl phosphate group or Imidopropionic acid group.

Furthermore, the present invention (4) provides a method for removing metals from a liquid according to any one of (1) to (3), characterized in that the liquid to be treated is an ester-based organic solvent or a solution containing an ester-based organic solvent. A ketone organic solvent, a solution containing a ketone organic solvent, an olefinic organic solvent, or a solution containing an olefinic organic solvent, and the aforementioned anion exchange resin is a free base type weakly basic anion exchange resin.

Furthermore, the present invention (5) provides a method for removing metals from a liquid as in (4), characterized in that the neutral salt decomposition capacity of the free base type weakly basic anion exchange resin is 0.25 eq/L-R or less.

Furthermore, the present invention (6) provides an H-type chelating resin mixed with an anion exchange resin, which is an H-type chelating resin mixed with an anion exchange resin. It is characterized in that the mixing amount of the anion exchange resin relative to the H-type chelating resin is 0.10 to 100.0 volume %.

Furthermore, (7) of the present invention provides an anion exchange resin mixed H-type chelating resin as in (6), which is characterized in that the functional group of the H-type chelating resin has an amine group.

In addition, (8) of the present invention provides an anion exchange resin mixed H-type chelating resin such as (6) or (7), characterized in that the functional groups of the aforementioned H-type chelating resin are iminodiacetic acid groups and aminomethyl groups. Phosphate group or iminopropionic acid group. [Effects of the invention]

According to the present invention, it is possible to provide a method for removing metals from liquid using H-type chelating resin, which method does not cause the problem of leakage of inorganic acid.

The method for removing metals from liquids of the present invention is characterized by removing metals from the liquid to be treated by bringing the liquid to be treated into contact with an H-type chelating resin mixed with an anion exchange resin.

In the metal removal method from a liquid of the present invention, the liquid to be processed to be treated for removing metals may include: water such as pure water, ultrapure water, PGMEA (propylene glycol monomethyl ether acetate), isopropyl acetate Ester-based organic solvents, cyclohexanone, methyl isobutyl ketone, acetone, methyl ethyl ketone and other ketone-based organic solvents, 2,4-diphenyl-4-methyl-1-pentene, 2- Ethylene-based organic solvents such as phenyl-1-propene, solutions containing these organic solvents, such as mixed solutions of ester-based organic solvents and aromatic organic solvents, solutions containing ester-based organic solvents, ketone-based organic solvents, and alcohol-based organic solvents Mixed solutions of solvents, such as solutions containing ketone organic solvents, mixed solutions of olefinic organic solvents and aromatic organic solvents, and solutions containing olefinic organic solvents, etc.

The metal removal method in the liquid of the present invention is because the liquid to be treated is in an ester-based organic solvent, a ketone-based organic solvent, an olefin-based organic solvent, or a solution containing these organic solvents (for example, a solution containing an ester-based organic solvent, a solution containing a ketone-based organic solvent, etc.) It is reactive in acidic environments such as solutions of organic solvents and solutions containing olefinic organic solvents, so it is particularly suitable for situations where solvents such as strongly acidic cation exchange resins cannot be used.

As the liquid to be processed in the metal removal method of the present invention, ultrapure water used as cleaning water for semiconductor processes, photoresist dissolving solvents or strippers, wafer cleaners, etc. that require very few impurities are used. Liquids are especially good. In addition, the metal impurity content in the liquid to be treated in the metal removal method of the present invention is not particularly limited. However, the metal removal method of the present invention is suitable for applications that require the removal of very few impurities (such as liquids that require the use of The content of metal impurities in the liquid is less than 10 ng/L). Therefore, the content of metal impurities in the liquid to be processed in the metal removal method of the present invention is preferably 10 to 1000 ng/L. Especially optimal is 10~500ng/L.

As metal impurities in the liquid to be processed, metal ions such as Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd, and Pb can be cited. H-type chelating resin has excellent performance in removing multivalent metal ions such as Fe, Cu, Ni, etc.

The H-type chelate resin used in the method for removing metals from liquids of the present invention is converted into H-type by contacting Na-type, Ca-type, Mg-type, and other metal ion-type chelate resins with inorganic acids and performing acid treatment. In other words, H-type chelate resin is a metal ion-type chelate resin that is treated with inorganic acid.

The functional groups of the H-type chelate resin in the method for removing metals from liquids of the present invention are not particularly limited as long as they can coordinate with metal ions to form chelates. Examples include: imine diacetate groups, Aminomethylphosphate group, iminopropionic acid group, etc. have functional groups such as amine group, thiol group, etc. Among these, functional groups having an amine group are preferred as the functional group of the chelate resin, from the viewpoint of improving the removal properties of many polyvalent metal ions, such as imine diacetyl group, amine methyl group Phosphate group and iminopropionic acid group are particularly preferred.

As a matrix of H-type chelate resin, styrene-divinylbenzene copolymer can be cited.

The H-type chelating resin can have any structure of gel structure, macroporous structure, or porous structure.

The exchange capacity of H-type chelating resin is preferably 0.50~2.50eq/L-R, particularly preferably 1.00~2.50eq/L-R. The average particle diameter (harmonic average diameter) of the H-type chelate resin is not particularly limited, but is preferably 300 to 1000 μm, particularly preferably 500 to 800 μm. In addition, the average particle size of the H-type chelate resin is a value measured by a laser diffraction particle size distribution measuring device.

H-type chelate resin is obtained by contacting a metal ion type chelate resin such as Na type, Ca type, Mg type, etc. with an inorganic acid to perform acid treatment.

Examples of the metal ion type chelating resin include: CR-10 and CR-11 manufactured by Mitsubishi Chemical Corporation, Duolite C-467 manufactured by Sumika Chemtex Corporation, MC-700 manufactured by Sumitomo Chemical Corporation, and Lewatit TP207 manufactured by Lanxess Corporation. , Lewatit TP208, Lewatit TP260), S930, S950 made by Purolite Company.

Examples of inorganic acids that the metal ion-type chelating resin comes into contact with include hydrochloric acid, sulfuric acid, and nitric acid. Among these, as the inorganic acid, hydrochloric acid and sulfuric acid are preferred from the viewpoint of safety. In addition, when converting from Ca type, there is a risk of calcium sulfate precipitating, so hydrochloric acid is preferred. The concentration of the inorganic acid is preferably 0.1 to 6.0N, particularly preferably 1.0 to 4.0N.

The method of bringing the inorganic acid into contact with the metal ion type chelating resin is not particularly limited, and the contact method, contact temperature, contact time, etc. can be appropriately selected.

After the inorganic acid contacts the metal ion-type chelating resin, the H-type chelating resin converted into H-type is washed with water to remove excess inorganic acid. Only the hydrogen bonds between the functional genes in the chelating resin and the inorganic acid, etc. And bonded, so water washing cannot completely remove excess inorganic acid. Therefore, the inorganic acid used in the acid treatment will remain in the H-type chelating resin.

Examples of the anion exchange resin used in the method for removing metals from liquids of the present invention include OH type strong basic anion exchange resin, free base type weak basic anion exchange resin, and the like.

Examples of the anion exchange group of the strongly basic anion exchange resin include quaternary ammonium groups.

Examples of the matrix of the strongly basic anion exchange resin include styrene-divinylbenzene copolymer and acrylic acid-divinylbenzene copolymer.

The strong basic anion exchange resin can have any structure including gel structure, macroporous structure, and porous structure.

The anion exchange capacity of the strong basic anion exchange resin is preferably 0.50~2.00eq/L-R, and particularly preferably 0.80~1.50eq/L-R. The average particle diameter (harmonic average diameter) of the strongly basic anion exchange resin is not particularly limited, but is preferably 300 to 1000 μm, particularly preferably 500 to 800 μm. In addition, the average particle size of the strongly basic anion exchange resin is a value measured by a laser diffraction particle size distribution measuring device.

Examples of strong basic anion exchange resins include Diaion SA10A and SA12A manufactured by Mitsubishi Chemical Corporation, Duolite A113OH manufactured by Sumika Chemtex, Lewatit MonoPlus M500 manufactured by Lanxess, and A400 manufactured by Purolite.

In the metal removal method from a liquid of the present invention, when the liquid to be treated is an organic solvent (for example, an ester-based organic solvent) that hydrolyzes in an alkaline environment, hydrolysis of the liquid to be treated can be made difficult to occur, The anion exchange resin is preferably a free base type weakly basic anion exchange resin.

Examples of the anion exchange groups of the free base weakly basic anion exchange resin include primary amine groups, secondary amine groups, and tertiary amine groups. Among these, as the anionic group, a tertiary amine group is preferred.

Examples of the matrix of the free base type weakly basic anion exchange resin include styrene-divinylbenzene copolymer and acrylic acid-divinylbenzene copolymer.

The free base type weakly basic anion exchange resin can have any structure including a gel structure, a macroporous structure, and a porous structure.

The anion exchange capacity of the free base type weakly basic anion exchange resin is preferably 0.50 to 2.50eq/L-R, and particularly preferably 1.00 to 2.00eq/L-R. The neutral salt decomposition capacity of the free base type weakly basic anion exchange resin is preferably 0.25eq/L-R or less, and particularly preferably is greater than 0.01eq/L-R and less than 0.15eq/L-R. The average particle diameter (harmonic average diameter) of the free base type weakly basic anion exchange resin is not particularly limited, but is preferably 300 to 1000 μm, particularly preferably 500 to 800 μm. In addition, the average particle size of the free base type weakly basic anion exchange resin is a value measured by a laser diffraction particle size distribution measuring device.

Examples of the free base type weakly basic anion exchange resin include Diaion WA30 manufactured by Mitsubishi Chemical Corporation, Duolite A368MS manufactured by Sumika Chemtex, Lewatit MP62 manufactured by Lanxess, Lewatit MonoPlus MP64, and A100 manufactured by Purolite.

Furthermore, in the method for removing metals from liquids of the present invention, the liquid to be treated is contacted with an H-type chelating resin mixed with an anion exchange resin to remove metals from the liquid, thereby obtaining a treated liquid from which metal impurities have been removed. In other words, in the metal removal method from liquid of the present invention, the liquid to be treated is brought into contact with a mixture of H-type chelating resin and anion exchange resin.

The method of mixing the anion exchange resin with the H-type chelating resin is not particularly limited as long as the ion exchange resin is uniformly dispersed in the mixture of the H-type chelating resin and the anion exchange resin.

The mixing amount of the anion exchange resin is 0.10 to 100.0 volume % relative to the H-type chelating resin, preferably 0.10 to 50.0 volume %, and more preferably 0.10 to 5.00 volume %. When the mixing amount of the anion exchange resin is within the above range, the effect of removing inorganic acid leaked from the H-type chelating resin becomes higher. On the other hand, if the mixing amount of the anion exchange resin is less than the above range, the removal of the acid leaked from the H-type chelating resin becomes insufficient, and inorganic acid is mixed into the treatment liquid; on the other hand, if it is greater than the above range, the acid leaked from the H-type chelate resin will be removed when the treatment When an organic solvent is hydrolyzed in an alkaline environment, there is a risk of hydrolysis of the liquid being processed.

The method of bringing the liquid to be treated into contact with the H-type chelate resin mixed with an anion exchange resin is not particularly limited. An example of the method is as follows: filling a resin packed tower with a mixture of the H-type chelating resin and anion exchange resin, so that the liquid to be treated The method of filling the tower with resin; the method of bringing the mixture into contact with the liquid to be treated in the reaction tank, etc.

The treatment conditions when the liquid to be treated contacts the H-type chelating resin mixed with anion exchange resin can be appropriately selected. The liquid flow rate is preferably 1.0 to 20L/L-resin/hr, and particularly preferably 1.0 to 5.0L/L- Resin/hr, and the liquid flow temperature is preferably 5 to 60°C, particularly preferably 10 to 30°C.

In the metal removal method from liquid of the present invention, since an anion exchange resin exists in the vicinity of the H-type chelating resin, the anion-exchange resin quickly captures the metal particles removed from the H-type chelating resin by bringing the liquid to be treated into contact with the H-type chelating resin. The inorganic acid leaked from the resin can prevent the inorganic acid from being mixed into the treatment liquid.

In the method for removing metals from liquids of the present invention, when the liquid to be treated is an organic solvent (such as an ester organic solvent) that is hydrolyzed in an alkaline environment, the anion exchange resin is a free base type weakly basic anion exchanger. The resin is preferable from the viewpoint of making it difficult for the liquid to be treated to undergo hydrolysis.

The anion exchange resin mixed H-type chelating resin of the present invention is an H-type chelating resin mixed with an anion exchange resin. It is characterized in that the mixing amount of the anion exchange resin relative to the H-type chelating resin is 0.10 to 100.0 volume %.

The H-type chelate resin and the anion exchange resin of the anion exchange resin mixed H-type chelate resin of the present invention are the same as the H-type chelate resin and the anion exchange resin of the metal removal method from the liquid of the present invention.

The anion exchange resin mixed H-type chelating resin of the present invention is an H-type chelating resin mixed with anion exchange resin. In other words, the anion exchange resin mixed H-type chelating resin of the present invention is a mixture of H-type chelating resin and anion exchange resin.

In the anion exchange resin mixed with the H-type chelating resin of the present invention, the mixing amount of the anion exchange resin is 0.10 to 100.0 volume % relative to the H-type chelating resin, preferably 0.10 to 50.0 volume %, and more preferably 0.10 ~5.00 volume%. When the mixing amount of the anion exchange resin is within the above range, the effect of removing inorganic acid leaked from the H-type chelating resin becomes higher. On the other hand, if the mixing amount of the anion exchange resin is less than the above range, the removal of the inorganic acid leaked from the H-type chelate resin becomes insufficient, and the inorganic acid is mixed into the treatment liquid; on the other hand, if it is greater than the above range, when When handling organic solvents that hydrolyze in an alkaline environment, there is a risk of hydrolysis of the liquid being treated.

The present invention is useful in removing metals from ester-based organic solvents (for example, PGMEA, isopropyl acetate, and other organic solvents that are hydrolyzed in an alkaline environment). The anion exchange resin mixed H-type chelating resin is preferably a free base weakly basic anion exchange resin. [Example]

Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.

(Example 1) Free base weakly basic anion exchange resin B1 (0.20 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C1. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H type chelating resin A1 was 0.10% by volume. Next, 100.0 mL of anion exchange resin mixed H-type chelating resin C1 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, pure water 1 for testing was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration in the collected solution. The results are shown in Table 1.

・H-type chelating resin: 1N hydrochloric acid 4eq/L-resin to Na-type imine diacetic acid-type chelating resin (manufactured by Dow Chemical Co., Ltd., Amberlite IRC748 (cation exchange capacity 1.45eq/L-resin, blended average diameter 550μm) ))Contact handler ・Free base type weakly basic anion exchange resin: Made by Dow Chemical Co., Ltd., Amberlite IRA96SB, total exchange capacity 1.32eq/L-resin, neutral salt decomposition capacity 0.20eq/L-resin) ・Test pure water 1: chloride ion concentration >0.1mg/L

(Example 2) Free base weakly basic anion exchange resin B1 (10.0 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C2. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 5.00% by volume. Next, 100.0 mL of anion exchange resin mixed with H-type chelating resin C2 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, pure water 1 for testing was passed through the column at a water flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration in the collected solution. The results are shown in Table 1.

(Example 3) Free base weakly basic anion exchange resin B1 (200.0 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C3. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 100.0% by volume. Next, 100 mL of anion exchange resin mixed with H-type chelating resin C3 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, pure water 1 for testing was passed through the column at a water flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration in the collected solution. The results are shown in Table 1.

(Comparative example 1) Fill 100 mL of H-type chelating resin A1 into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, pure water 1 for testing was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration in the collected solution. The results are shown in Table 1.

(Comparative example 2) Free base weakly basic anion exchange resin B1 (0.10 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C4. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 0.05% by volume. Next, 100 mL of anion exchange resin mixed with H-type chelating resin C4 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, pure water 1 for testing was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration in the collected solution. The results are shown in Table 1.

【Table 1】

An implementation in which the free base type weakly basic anion exchange resin B1 is mixed with the H-type chelating resin A1, and the mixing amount of the free base type weakly basic anion exchange resin B1 relative to the H-type chelating resin A1 is within the scope of the present invention. In Examples 1 to 3, the chloride ions are below the detection limit, indicating that inorganic acid leakage can be prevented. On the other hand, in Comparative Example 1, which contains only H-type chelate resin A1 and no free-base type weakly basic anion exchange resin B1, there are many chloride ions, indicating a large amount of leakage of inorganic acid. Furthermore, although the free base type weakly basic anion exchange resin B1 is mixed with the H-type chelating resin A1, the mixing amount of the free base type weakly basic anion exchange resin B1 is smaller than that of the H-type chelating resin A1. In Example 2, chloride ions were detected even though they were very small, thus showing the effect of preventing the leakage of inorganic acid if the mixing amount of the free base type weakly basic anion exchange resin B1 is small compared to the H-type chelating resin A1. become inadequate.

(Example 4) Free base weakly basic anion exchange resin B1 (0.20 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C1. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H type chelating resin A1 was 0.10% by volume. Next, 100.0 mL of anion exchange resin mixed H-type chelating resin C1 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2. ・Test solvent 2: PGMEA (polypropylene glycol monomethyl ether acetate), chloride ion concentration >0.1mg/L, acetic acid concentration 20mg/L, sodium concentration 400ng/L, moisture 130ppm

(Example 5) Free base weakly basic anion exchange resin B1 (10.0 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C2. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 5.00% by volume. Next, 100 mL of anion exchange resin mixed with H-type chelating resin C2 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

(Example 6) OH type strong basic anion exchange resin B2 (0.20 mL) was mixed and dispersed in H type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H type chelating resin C5. At this time, the mixing amount of the OH type strong basic anion exchange resin B2 with respect to the H type chelating resin A1 was 0.10% by volume. Next, 100.0 mL of anion exchange resin mixed with H-type chelating resin C5 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

(Example 7) Free base weakly basic anion exchange resin B1 (200.0 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C3. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 100.0% by volume. Next, 100 mL of anion exchange resin mixed with H-type chelating resin C3 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

・OH type strong basic anion exchange resin: Amberjet 4002(OH)-HG manufactured by Organo Co., Ltd., total exchange capacity and neutral salt decomposition capacity 1.05eq/L-resin, blended average diameter 600μm.

(Comparative example 3) Fill 100 mL of H-type chelating resin A1 into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

(Comparative example 4) Free base weakly basic anion exchange resin B1 (0.10 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C4. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H-type chelating resin A1 was 0.05% by volume. Next, 100.0 mL of anion exchange resin mixed with H-type chelating resin C4 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

(Comparative example 5) Free base weakly basic anion exchange resin B1 (250.0 mL) was mixed and dispersed in H-type chelating resin A1 (200.0 mL) to prepare anion exchange resin mixed H-type chelating resin C6. At this time, the mixing amount of the free base type weakly basic anion exchange resin B1 with respect to the H type chelating resin A1 was 125.0% by volume. Next, 100.0 mL of anion exchange resin mixed with H-type chelating resin C6 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

(Comparative example 6) 100.0 mL of strongly acidic cation exchange resin D1 was filled into an acrylic column with an inner diameter of 1.8 cm and a height of 100 cm. Next, the test solvent 2 was passed through the column at a flow rate of 1L/hr (SV=10), and 1L of the initial outflow was collected. Next, measure the chloride ion concentration, sodium concentration, acetic acid concentration, and moisture in the collection liquid. The results are shown in Table 2.

・Strongly acidic cation exchange resin D1: Made by Dow Chemical Co., Ltd., Amberjet 1024H, total exchange capacity: 2.25eq/L-resin, blended average diameter 650μm

【Table 2】

The free base type weakly basic anion exchange resin B1 or the OH type strong basic anion exchange resin B2 is mixed with the H-type chelating resin A1, and the mixing amount of the anion exchange tree relative to the H-type chelating resin A1 is within the range of the present invention. In Examples 4 to 7 of the range, the chloride ions are below the detection limit, indicating that leakage of inorganic acid can be prevented. Furthermore, in Examples 4 to 7, since the acetic acid concentration did not change or the change was small, it was shown that hydrolysis of the solvent did not occur or, even if it occurred, it was limited to a small amount. On the other hand, in Comparative Example 3, which contains only H-type chelate resin A1 and no free-base type weakly basic anion exchange resin B1, there are many chloride ions, indicating a large amount of leakage of inorganic acid. Furthermore, although the free base type weakly basic anion exchange resin B1 is mixed with the H-type chelating resin A1, the mixing amount of the free base type weakly basic anion exchange resin B1 is smaller than that of the H-type chelating resin A1. In Example 4, chloride ions were detected even though they were very small. This shows that if the mixing amount of the free base type weakly basic anion exchange resin B1 is small compared to the H-type chelating resin A1, the effect of preventing the leakage of inorganic acid will be reduced. Not enough. Furthermore, in Comparative Example 5 in which a large amount of the free base type weakly basic anion exchange resin B1 was mixed with respect to the H-type chelate resin A1, and in Comparative Example 6 in which only the strongly acidic cation exchange resin D1 was used, no detection was performed. However, the acetic acid concentration became 2 to 5 times higher than that of chloride ions, indicating that solvent hydrolysis occurred in large quantities.

without.

Claims (7)

A method for removing metals from liquids, which is to remove metals by contacting the liquid to be treated with an H-type chelating resin obtained by mixing an anion exchange resin that is a free base type weakly basic anion exchange resin and contacting it with an inorganic acid to perform acid treatment. The metal in the liquid to be treated is characterized by a mixing amount of the anion exchange resin of 0.10 to 100.0 volume % relative to the H-type chelating resin, and the liquid to be treated is an organic solvent, and the organic solvent is an ester system Organic solvents, solutions containing ester-based organic solvents, ketone-based organic solvents, solutions containing ketone-based organic solvents, olefin-based organic solvents, or solutions containing olefin-based organic solvents. The method for removing metal from liquid according to claim 1, wherein the functional group of the H-type chelating resin has an amine group. For example, the method of removing metal from liquid according to claim 1 or 2, wherein the functional group of the H-type chelating resin is an imine diacetate group, an aminomethyl phosphate group or an imine propionate group. As claimed in claim 3, the method for removing metals from liquids, wherein the neutral salt decomposition capacity of the free base type weakly basic anion exchange resin is 0.25 eq/L-R or less. An anion exchange resin mixed H-type chelating resin, which is an H-type chelating resin obtained by mixing an anion exchange resin of a free base type weakly basic anion exchange resin and contacting an inorganic acid for acid treatment, and is characterized by: The mixing amount of the anion exchange resin relative to the H-type chelating resin is 0.10~100.0% by volume, and the liquid to be treated is an organic solvent, and the organic solvent is an ester-based organic solvent containing A solution of an ester-based organic solvent, a ketone-based organic solvent, a solution containing a ketone-based organic solvent, an olefin-based organic solvent, or a solution containing an olefin-based organic solvent. The anion exchange resin of claim 5 is mixed with an H-type chelating resin, wherein the functional group of the H-type chelating resin has an amine group. For example, the anion exchange resin of claim 5 or 6 is mixed with an H-type chelating resin, wherein the functional group of the H-type chelating resin is an iminodiacetic acid group, an aminomethyl phosphate group or an imine propionic acid group.