JP6562459B2 - Metal ion adsorption separation method - Google Patents

Description

The present invention relates to a method for adsorbing and separating metal ions in water using polyvinylamine crosslinked polymer particles.

Strict drainage regulations have been established for metals contained in industrial wastewater, particularly metals such as mercury, cadmium, copper, and zinc, which have a harmful effect on the human body, and further treatment effects are required. In recent years, the demand for metal resources has increased. In particular, rare metals and precious metals are used as essential materials in various fields such as semiconductor lasers and battery materials, and their reserves are limited and the supply amount is limited. There is a demand for the recovery of metals from waste and waste liquid.
Under these circumstances, attempts have been made to treat metal ions by adding a chelating agent and a chelating resin to the waste water. Various chelating agents and chelate resins have been devised so far. For example, Patent Document 1 discloses an aminophosphate chelate resin production method, Patent Document 2 discloses iminodiacetic acid, N-methyl-D-glucamine, or polyethylene. A chelating agent having a functional group selected from imine, in Patent Document 3, a semimetal adsorbent comprising a polyallylamine derivative having a sugar side chain, in Patent Document 4, a method for producing an acylated polyallylamine, in Patent Document 5, In an adsorbent in which a functional group capable of forming a complex with a semimetal is introduced into a polymer mainly composed of poly N-vinylamines, in Patent Document 6, a polyamine-type chelate resin and a metal solution are brought into contact with each other. In the method for removing a metal component, Patent Document 7, as a method for adsorbing or separating an electrolyte from an electrolyte solution, it has a polyvinylamine structure. How to use the cross-linked copolymer is disclosed respectively that. These patent documents suggest that a polymer having a primary amino group is effective for adsorption of metal ions. However, currently used chelate resins may have problems in cost and may not provide a satisfactory adsorption effect. Therefore, there is a demand for chelate resins that can be easily and efficiently manufactured and can be efficiently adsorbed and separated from chelate resins used for conventional metal ion adsorption.

JP-A-5-320233 JP 2005-2414 A JP 2000-279803 A Japanese Patent Laid-Open No. 9-286816 JP 2005-325269 A JP 2007-302938 A JP-A-6-238270

An object of the present invention is to efficiently adsorb and remove metal ions from industrial wastewater or the like. Furthermore, it is providing the chelate resin which can be manufactured simply and efficiently and has the adsorbability excellent with respect to the metal ion.

As a result of intensive studies to solve the above-mentioned problems, polyvinyl carboxylic acid amide crosslinked polymer particles are obtained by suspension polymerization of N-vinylcarboxylic amide in salt water in the presence of a crosslinking monomer and a dispersant. The present inventors have found that polyvinylamine crosslinked polymer particles obtained by hydrolyzing after removing salts and the like by washing with water are effective for metal ion adsorption.

That is, in the present invention, N-vinylcarboxylic acid amide and a crosslinkable monomer are suspension-polymerized in salt water in the presence of a dispersant to obtain polyvinylcarboxylic acid amide crosslinked polymer particles, and then the crosslinked polymer is hydrolyzed. The present invention relates to a metal ion adsorption treatment application of polyvinylamine crosslinked polymer particles obtained by decomposing.

According to the present invention, metal ions in water can be efficiently adsorbed by using polyvinylamine crosslinked polymer particles that are easily and efficiently obtained without using an organic solvent.

Hereinafter, the present invention will be described in detail.

The manufacturing method of the polyvinylamine crosslinked polymer particle in this invention is demonstrated. As a production method, first, suspension polymerization generally used is applied. That is, suspension polymerization in salt water in the present invention includes N-vinylcarboxylic acid amide, a crosslinkable monomer, a monomer that can be copolymerized with N-vinylcarboxylic acid amide as necessary, a polymerization initiator, and It can be carried out by suspending the dispersant in brine and stirring the mixture at an arbitrary strength to generate monomer droplets and radical polymerization. The particle size of the monomer droplets is controlled by the dispersant and the stirring strength, but is 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm.

Examples of N-vinylcarboxylic acid amide monomers used in the present invention include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylpropion. Examples include amide, N-methyl-N-vinylpropionamide, N-vinylbutyramide, N-vinylisobutyramide, and preferably N-vinylformamide and N-vinylacetamide. In addition to the monomer of N-vinylcarboxylic acid amide, a monomer copolymerizable with N-vinylcarboxylic acid amide may be used. (Meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N'-dialkyl (meth) acrylamide, N, N'-dialkylaminoalkyl (meth) acrylamide, alkali metal salt or ammonium salt of (meth) acrylamide alkanesulfonic acid, alkali metal salt or ammonium salt of (meth) acrylic acid, Hydroxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acryloyloxyalkyl-trimethylammonium salt, alkali metal salt or ammonium salt of (meth) acryloyloxyalkanesulfonic acid, N- Nirupiroridon, diallyl - dialkyl ammonium salts, vinyl pyridine, vinyl imidazole, vinyl pen Jill trialkylammonium salts, alkali metal salts or ammonium salts of vinylsulfonic acid. May be used only one of these Two or more kinds may be combined. Particularly preferred is acrylonitrile.

Examples of the crosslinkable monomer include aromatic polyvinyl compounds such as divinylbenzene, trivinylbenzene, and divinyltoluene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, and trimethylolpropane tri Poly (meth) acrylates such as (meth) acrylate, methylenebisacrylamide, and the like can also be used. However, since poly (meth) acrylate, methylenebisacrylamide and the like are easily hydrolyzed, it is preferable to use an aromatic divinyl compound. Most preferred is divinylbenzene. In addition, allyl ethers such as triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, tetraallyloxyethane, pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether, poly ( Use may also be made of (meth) allyloxyalkanes. Among these, allyl ethers can be preferably used. The addition rate is in the range of 0.1 to 50% by mass with respect to the monomer, and preferably in the range of 0.1 to 20% by mass. If it exceeds 5% by mass, it is difficult to obtain spherical particles with N-vinylcarboxylic acid amide alone, so it is preferable to use a monomer that can be copolymerized with N-vinylcarboxylic acid amide. The addition ratio of the monomer capable of copolymerization is used in the range of 0.1 to 50% by mass with respect to all monomers. In particular, acrylonitrile is preferably used.

As the polymerization initiator, an azo- or peroxide-based polymerization initiator such as 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) is used. valeronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis-2-amidinopropane dihydrochloride, 4,4'-azobis-4-cyanovaleric acid, 2,2 ' - azobis [2- (5-methyl - 2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and the like, ammonium peroxodisulfate Or potassium, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2- Examples thereof include ethyl hexanoate. Of these, oil-soluble initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferable. Further, two or more initiators may be used in combination. The addition rate is usually 0.02 to 5% by mass, preferably 0.05 to 2% by mass, based on the monomer.

  Examples of the salt include ammonium sulfate, sodium sulfate, ammonium chloride, sodium chloride, calcium chloride and the like, and among these, ammonium sulfate is particularly preferable. These may be used alone or in combination. The addition rate is in the range of 30 to 100% by mass with respect to water, and if it is less than 30% by mass, the N-vinylcarboxylic acid amide is not separated into two phases, and the effect of the salt is sufficiently obtained at 100% by mass, It is not economical to add over 100% by mass. Preferably it is 50-90 mass%, More preferably, it is 60-90 mass%.

As the dispersant, a polymer dispersant is preferable. The polymer dispersant can be used either ionic or nonionic, but is preferably ionic. As the ionic polymer, a cationic monomer (meth) acryloyloxyethyltrimethylammonium chloride, dimethyldiallylammonium chloride, or the like is polymerized, but the co-polymerization of these cationic monomers and nonionic monomers. Coalescence can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N′-dimethylacrylamide, acrylonitrile, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, and the like. Can be mentioned. Examples of the nonionic polymer dispersant include polyvinyl alcohol and polyethylene glycol polyacrylamide. The weight average molecular weight of the ionic polymer dispersant is 5,000 to 5,000,000, preferably 50,000 to 3,000,000. Moreover, as a weight average molecular weight of a nonionic polymer dispersing agent, it is 1000-100,000, Preferably it is 1000-50,000. The addition rate is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass, based on water.

The polymerization reaction is usually performed at a temperature of 30 ° C. to 100 ° C. and for a time of 1 hour to 15 hours.

After the polymerization, salt, dispersant, unreacted monomer and the like can be removed by washing with water.

The copolymer particles are purified by the method described above and then subjected to hydrolysis. Hydrolysis of N-vinylcarboxylic acid amide crosslinked polymer particles can be carried out under basic and acidic conditions. To obtain free polyvinylamine crosslinked polymer particles, hydrolysis must be carried out under basic conditions. Is preferred. In order to obtain salt-type polyvinylamine crosslinked polymer particles, it is preferable to hydrolyze under acidic conditions.

A suitable base for hydrolysis is not particularly limited as long as the pH can be adjusted to a range of 8 to 14 during hydrolysis, and an aqueous solution of sodium hydroxide, potassium hydroxide or ammonia is most preferably used. The addition rate is preferably 0.05 to 2.0, more preferably 0.4 to 1.2 equivalents relative to the formyl group of the polymer.

The acid suitable for the hydrolysis is not particularly limited as long as the pH can be adjusted to a range of 0 to 5 during the hydrolysis, and includes inorganic acids such as hydrohalic acid, sulfuric acid, nitric acid and phosphoric acid, and one carbon atom. Examples thereof include organic acids such as mono- and dicarboxylic acids, sulfonic acids, benzenesulfonic acids, and toluenesulfonic acids in the range of ˜5, and it is particularly preferable to use hydrohalic acid and hydrogen halide gas, and use hydrohalic acid. Most preferred. The addition rate is preferably 0.05 to 2.0, more preferably 0.4 to 1.2 equivalents relative to the formyl group of the polymer.

  Polyvinylamine crosslinked polymer particles can be obtained by washing with water after hydrolysis. In the case of base hydrolysis, free-type purified polyvinylamine crosslinked polymer particles are obtained, and in the case of acid hydrolysis, salt-type purified polyvinylamine crosslinked polymer particles are obtained.

  Next, the method for adsorbing and separating metal ions by the polyvinylamine crosslinked polymer particles in the present invention will be described. The polyvinylamine cross-linked polymer particles in the present invention are applied to general water treatment applications as a chelate resin. In general, a column is filled and drainage is passed to adsorb metal ions. In addition, after adding to a target liquid, it mixes by arbitrary stirring conditions, such as turbulent flow and a laminar flow, and adsorb | sucks a target object. In other words, it exhibits a high adsorption capacity for metal ions in various industrial and process wastewaters, but it is also possible to adsorb acidic substances, formaldehydes, organic compounds and the like. In addition, the crosslinked polymer particles in the present invention are preferably spherical, and the spherical polymer tends to have a high ability to adsorb metal ions, and when used in a column as an adsorbent, the packing efficiency is high and the flow path is high. There are advantages such as stability, separation efficiency is increased, and processing capacity is improved.

  The polyvinylamine cross-linked polymer particles in the present invention have a high adsorption ability for metal ions, but among metal ions, higher adsorption ability for heavy metal ions such as platinum ions, palladium ions, ruthenium ions, gold ions and copper ions. Show.

 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded. First, the polyvinylamine polymer particle in this invention was manufactured, and the adsorption capacity of a metal ion was evaluated. The comparative product is a general-purpose product used for adsorption of heavy metal ions as a chelate resin, and polyamine type chelate resin CR20 manufactured by Mitsubishi Chemical, which is also described in JP-A-2007-302938, was used.

(Production Example 1)
A 500 mL four-necked flask was charged with 100 g of demineralized water, 64.0 g of ammonium sulfate, and 1.00 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000), stirred and dissolved. A polymerization bath was used. N-vinylformamide 33.4 g, divinylbenzene 2.80 g, acrylonitrile 4.00 g, azo polymerization initiator 2, 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure) 0.12 g (manufactured by Yakuhin Kogyo Co., Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed and stirred at 180 rpm while replacing the inside of the flask with nitrogen. After 30 minutes, the temperature was raised, and polymerization was carried out at 40 ° C. for 3 hours and then at 70 ° C. for 2 hours. After the polymerization, filtration, washing with water and filtration were performed to obtain 35.1 g of polymer spherical particles in a water-containing state. The solid content was 42.4%. 23.5 g of the reaction product thus obtained was placed in a four- necked flask, 23.40 g of a 48 mass% aqueous sodium hydroxide solution was added, and the mixture was hydrolyzed at 80 ° C. for 5 hours with stirring. Washing with water and filtration yielded 19.7 g of polyvinylamine spherical particles containing water. As a result of microscopic observation, spherical particles of 50 μm to 2 mm were observed. The polymer particles thus obtained are referred to as chelate resin 1.

(Production Example 2)
A 500 mL four-necked flask was charged with 100 g of demineralized water, 64.0 g of ammonium sulfate, and 1.00 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000), stirred and dissolved. A polymerization bath was used. N-vinylformamide 33.4 g, pentaerythritol triallyl ether (Neoallyl P-30, manufactured by Daiso Corporation) 1.00 g, acrylonitrile 1.00 g, azo polymerization initiator 2, 2′-azobis (4-methoxy- 2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.12 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed and stirred at 180 rpm while replacing the inside of the flask with nitrogen. After 30 minutes, the temperature was raised, and polymerization was carried out at 40 ° C. for 3 hours and then at 70 ° C. for 2 hours. After the polymerization, filtration, washing and filtration were performed to obtain 210 g of polymer spherical particles containing water. The solid content was 15.7%. 150 g of the reaction product thus obtained was placed in a four- necked flask, 14.0 g of a 48% by mass aqueous sodium hydroxide solution was added, and the mixture was hydrolyzed at 80 ° C. for 5 hours with stirring. Washed with water and filtered to obtain 253 g of polyvinylamine spherical particles containing water. As a result of microscopic observation, spherical particles of 50 μm to 2 mm were observed. The polymer particles thus obtained are referred to as chelate resin 2.

(Example 1) Platinum ion adsorption test Potassium tetrachloroplatinate was dissolved in ion-exchanged water, adjusted to 1 L of a 10 ppm solution, and then divided into 500 mL portions. 10.0 mg of each of the chelate resins 1 and 2 wet with water was added to the platinum ion solution, followed by stirring at 40 rpm using a stirrer. After 2 hours and 24 hours from the start of stirring, the supernatant liquid is sampled, the solution is filtered through a 0.2 μm filter, 1% of aqua regia of the obtained liquid is added, and the remaining amount of platinum ions is analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Comparative Example 1) Platinum ion adsorption test Potassium tetrachloroplatinate was dissolved in ion-exchanged water, and 500 mL of a 10 ppm solution was prepared. 10.0 mg of a polyamine chelate resin CR20 (comparative product) manufactured by Mitsubishi Chemical in a wet state with water was added to the platinum ion solution, and the mixture was stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant liquid is sampled, the solution is filtered through a 0.2 μm filter, 1% of aqua regia of the obtained liquid is added, and the remaining amount of platinum ions is analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Example 2) Palladium ion adsorption test Palladium acetate was dissolved in a small amount of acetone, and then adjusted to 10 ppm using ion-exchanged water. 500 mL of the palladium solution was measured in a beaker, 10.0 mg each of chelate resins 1 and 2 wet with water was added, and the mixture was stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant was sampled, the solution was filtered through a 0.2 μm filter, 1% of aqua regia was added to the resulting solution, and the remaining amount of palladium ions was analyzed by ICP emission spectrometry. It measured with the apparatus (ICPS-7510, Shimadzu Corporation make use), and the residual amount of palladium ion was measured by ICP emission analysis. The test results are shown in Table 1.

(Comparative Example 2) Palladium ion adsorption test Palladium acetate was dissolved in a small amount of acetone, and then adjusted to 10 ppm using ion-exchanged water. 10.0 mg of a comparative product wet with water was added to 500 mL of the palladium solution, and the mixture was stirred at 40 rpm using a stirring bar. After 2 hours and 24 hours from the start of stirring, the supernatant was sampled, the solution was filtered through a 0.2 μm filter, 1% of aqua regia was added to the resulting solution, and the remaining amount of palladium ions was analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Example 3) Adsorption test of ruthenium ions 1 L of a ruthenium 1000 ppm standard sample for ICP emission analysis was diluted to 10 ppm, adjusted to pH 4 with hydrochloric acid, filtered to remove insoluble matters, and each 500 mL. Divided into 10.0 mg of the chelate resins 1 and 2 wet with water was added to each of the ruthenium solutions, and the mixture was stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant liquid is sampled, the solution is filtered through a 0.2 μm filter, aqua regia for 1% of the obtained liquid is added, and the remaining amount of ruthenium ions is analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Comparative Example 3) Adsorption test of ruthenium ions 500 mL of a solution obtained by diluting a ruthenium 1000 ppm standard sample for ICP emission analysis to 10 ppm was prepared, adjusted to pH 4 with hydrochloric acid, and the insoluble matter was removed by filtration. 10.0 mg of a comparative product wet with water was added to the ruthenium solution, followed by stirring at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant liquid is sampled, the solution is filtered through a 0.2 μm filter, aqua regia for 1% of the obtained liquid is added, and the remaining amount of ruthenium ions is analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Example 4) Gold ion adsorption test A solution obtained by diluting a standard 1000 ppm gold for ICP emission analysis to 10 ppm was adjusted to 1 L, adjusted to pH 4 with hydrochloric acid, and then divided into 500 mL portions. 10.0 mg of the chelate resins 1 and 2 wet with water was added to each of the gold solutions, and the mixture was stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant was sampled, the solution was filtered through a 0.2 μm filter, 1% of aqua regia was added to the resulting solution, and the remaining amount of gold ions was analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1. The test results are shown in Table 1.

(Comparative Example 4) Gold ion adsorption test 500 mL of a solution obtained by diluting a standard 1000 ppm gold for ICP emission analysis to 10 ppm was prepared and adjusted to pH 4 with hydrochloric acid. 10.0 mg of a comparative product wet with water was added to the gold solution and stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant was sampled, the solution was filtered through a 0.2 μm filter, 1% of aqua regia was added to the resulting solution, and the remaining amount of gold ions was analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

Example 5 Iridium Ion Adsorption Test 500 mL of a solution prepared by diluting an iridium 1000 ppm standard sample for ICP emission analysis to 10 ppm was prepared and adjusted to pH 4 using hydrochloric acid. 10.0 mg of chelate resin 2 wet with water was added to the iridium solution, followed by stirring at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant was sampled, the solution was filtered with a 0.2 μm filter, 1% of the resulting solution was added aqua regia, and the remaining amount of iridium ions was analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

Comparative Example 5 Iridium Ion Adsorption Test 500 mL of a solution prepared by diluting an iridium 1000 ppm standard sample for ICP emission analysis to 10 ppm was prepared and adjusted to pH 4 using hydrochloric acid. 10.0 mg of a comparative product wet with water was added to the iridium solution, and the mixture was stirred at 40 rpm using a stir bar. After 2 hours and 24 hours from the start of stirring, the supernatant liquid is sampled, the solution is filtered through a 0.2 μm filter, 1% of aqua regia of the obtained liquid is added, and the remaining amount of platinum ions is analyzed by ICP emission spectrometry. It was measured with an apparatus (ICPS-7510, manufactured by Shimadzu Corporation). The test results are shown in Table 1.

(Table 1)

Chelate resins 1 and 2 both adsorb more metal ions than the comparative product 24 hours after the start of stirring. Among them, it was found that platinum ions, palladium ions, and gold ions have a feature that the chelating resin 1 has a large amount of adsorption 2 hours after the start of stirring and has a high adsorption rate.

(Example 6) Copper ion adsorption test Copper sulfate pentahydrate was dissolved in ion-exchanged water to prepare 500 mL of a 113.6 ppm copper ion solution. 100 mg of the chelate resin 1 wet with water was added to 200 g of the copper ion solution, and the mixture was stirred at 40 rpm using a stirrer. Supernatant liquid is sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of copper ions in the obtained liquid is measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Comparative Example 6) Copper ion adsorption test Copper sulfate pentahydrate was dissolved in ion-exchanged water to prepare 500 mL of a copper ion 113.6 ppm solution. 100 mg of Mitsubishi Chemical polyamine chelate resin CR20 (comparative product) wet with water was added to 200 g of the copper ion solution, and the mixture was stirred at 40 rpm using a stir bar. Supernatant liquid is sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of copper ions in the obtained liquid is measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Example 7) Adsorption test of copper ions Copper sulfate pentahydrate and calcium chloride (anhydrous) were dissolved in ion-exchanged water, and 500 mL of a solution containing 79.7 ppm of copper ions and 100 ppm of calcium ions was prepared. 100 mg of chelate resin 1 wet with water was added to 200 g of the solution, and the mixture was stirred at 40 rpm using a stir bar. Supernatant liquid is sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of copper ions in the obtained liquid is measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Comparative Example 7) Copper ion adsorption test Copper sulfate pentahydrate and calcium chloride (anhydrous) were dissolved in ion-exchanged water, and 500 mL of a solution containing 79.7 ppm of copper ions and 100 ppm of calcium ions was prepared. 100 mg of polyamine-type chelate resin CR20 (comparative product) manufactured by Mitsubishi Chemical in a wet state with water was added to 200 g of the solution, and stirred at 40 rpm using a stir bar. Supernatant liquid is sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of copper ions in the obtained liquid is measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Example 8) Adsorption test of zinc ions Zinc chloride was dissolved in ion-exchanged water to prepare 500 mL of a 61.7 ppm solution of zinc ions. 100 mg of the chelate resin 1 wet with water was added to 200 g of the zinc ion solution, followed by stirring at 40 rpm using a stirrer. Supernatant liquid was sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of zinc ions in the resulting liquid was measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Comparative Example 8) Zinc ion adsorption test Zinc chloride was dissolved in ion-exchanged water to prepare 500 mL of a 61.7 ppm solution of zinc ions. 100 mg of Mitsubishi Chemical polyamine type chelate resin CR20 (comparative product) wet with water was added to 200 g of the zinc ion solution and stirred at 40 rpm using a stir bar. Supernatant liquid was sampled 24 hours after the start of stirring, filtered through a 0.2 μm filter, and the remaining amount of zinc ions in the resulting liquid was measured with an atomic absorption spectrophotometer (AA-6800, manufactured by Shimadzu Corporation). did. The test results are shown in Table 2.

(Table 2)

When the chelate resin in this invention was added, it has confirmed that the adsorption amount of copper ion and zinc ion was high compared with the comparative product.

Claims (4)

Suspension polymerization in a salt water containing N-vinylcarboxylic acid amide and a crosslinkable monomer, wherein the addition rate of the salt is in the range of 50 to 90% by mass with respect to water in the presence of a dispersant. A method for adsorbing and separating metal ions, comprising adding polyvinylamine crosslinked polymer particles obtained by hydrolyzing the obtained crosslinked polymer particles to water. A dispersant in brine containing N-vinylcarboxylic amide and a crosslinkable monomer, wherein the dispersant is polymerized with (meth) acryloyloxyethyltrimethylammonium chloride or dimethyldiallylammonium chloride; and Polyvinylamine obtained by hydrolyzing the crosslinked polymer particles obtained by suspension polymerization in the presence of one or more dispersants selected from copolymers of these cationic monomers and nonionic monomers A method for adsorbing and separating metal ions, comprising adding crosslinked polymer particles to water. The method for adsorbing and separating metal ions according to claim 1 or 2 , wherein the crosslinkable monomer is at least one selected from an aromatic polyvinyl compound or allyl ethers. The method for adsorbing and separating metal ions according to any one of claims 1 to 3, wherein the metal ions are heavy metal ions.