JP2022055387A - Adsorption separation method of metalloid ion - Google Patents

Abstract

To develop a chelate resin that is produced simply and efficiently and can efficiently separate by adsorbing ions of elements of the groups 15 and 16 of the periodic table among metalloid ions, especially a selenium ion and an arsenic ion.SOLUTION: N-vinylcarboxylic acid amide and a cross-linkable monomer are subjected to suspension polymerization in brine in the presence of a dispersant to obtain cross-linked polymer particles of polyvinyl carboxylic acid amide. The obtained cross-linked polymer of polyvinyl carboxylic acid amide is then hydrolyzed. The cross-linked polymer particles of polyvinylamine is used as a chelate resin to efficiently separate by adsorbing ions of elements of the groups 15 and 16 of the periodic table among metalloid ions in water, especially a selenium ion and an arsenic ion.SELECTED DRAWING: None

Description

The present invention relates to a method for adsorbing and separating group 15 and group 16 element ions of the Periodic Table of the Elements, particularly selenium or arsenic ion, among the metalloid ions containing hemimetal ions using polyvinylamine crosslinked polymer particles. ..

Many of the elements classified as metalloids are toxic, and among them, arsenic and antimony of group 15 and selenium and tellurium of group 16 of the Periodic Table of the Elements have tap water quality management target setting items and water pollution. The emission standard value is set or a monitoring item is required.
Arsenic is widely distributed in the crust and is naturally released by volcanic activity and artificially released into the environment by mining ore and fossil fuels and industrial activities, and circulates in the atmosphere, water, soil and biosphere. All living things contain arsenic. Further, the alloy is used as a semiconductor material for LEDs, semiconductor lasers and the like.
On the other hand, arsenic is highly toxic and has been used as a pesticide, rodenticide, and wood preservative by utilizing its toxicity.
From such a background, the allowable concentration is 0.1 mg / L as the wastewater standard, and the standard value of the tap water quality standard item is 0.01 mg / L or less.
There are many problems of water pollution caused by arsenic in Japan, mainly due to wastewater from abandoned mines and geothermal power plants and industrial waste. As a method for removing arsenic ions existing in water, a coprecipitation method, a catalytic method, and an adsorption method are known. Currently, the coprecipitation method is mainly used, but a large amount of waste is generated especially after the treatment, and there is a problem in the treatment cost (for example, Japanese Patent Application Laid-Open No. 2003-19404). In the catalyst method, for example, a method of reducing and removing arsenic ions by hydrogen aeration using rhodium-supported alumina shown in JP-A-9-327964 as a catalyst has been proposed, but there are problems in catalyst cost and complexity of the removal process.
Various adsorbents have been proposed for the adsorption method, and although the removal process is relatively simple, there are problems such as insufficient arsenic ion removal performance and adsorbent cost, so the adsorbent is highly efficient and easy to use. Is desired at present.
Selenium is widely present in nature and is a trace essential element in living organisms, but since the difference between the required amount and the amount of toxicity manifestation is small, damage occurs even if the intake is insufficient or excessive. The effects of selenium on the human body may cause skin disorders, vomiting, generalized selenium, nervousness, anemia, gastrointestinal disorders and the like.
On the other hand, selenium is widely used in the manufacture of electrical materials, catalysts, etc. by utilizing the coloring of glass, decolorizing agents and photoconductivity, and is therefore contained in wastewater from glass factories, semiconductor factories, etc. It may elute from the soil of the former factory site. Against this background, the Water Pollution Control Law sets a uniform wastewater standard of 0.1 mg / liter. It is known that selenium dissolved in water is a tetravalent or hexavalent oxyanion, but no effective wastewater treatment technology has been found for hexavalent selenium at present, and more efficient selenium is used. Development of a processing method for selenium is desired.
Currently, the most commonly used method for treating selenium is co-precipitation treatment with an iron salt or an aluminum salt. Although such a method has a sufficient effect on tetravalent selenium, it has an effect on hexavalent selenium. Has the problem of being low.
As an effective treatment method for hexavalent selenium, Japanese Patent No. 3956978 states that hexavalent selenate ion is reduced with a divalent iron salt, a metal salt, or the like to form a selenite ion, and then a co-precipitation method is used. However, there are problems that the treatment process is complicated because the reduction treatment step is required, the efficiency of the reduction treatment is low, and a large amount of reducing agent is required.
Japanese Unexamined Patent Publication No. 9-308895 discloses a wastewater treatment method using an aluminum compound, a magnesium compound and the like. However, this method is operably complicated because it is a coprecipitation treatment of selenium using an aluminum compound, a magnesium compound, or the like after a reduction pretreatment with an anaerobic organism.
Further, Japanese Patent Application Laid-Open No. 2004-89924 discloses a selenium wastewater treatment method using amorphous iron hydroxide (III), but the treatment of high-concentration selenium wastewater is insufficient, and further improvement is desired. It was rare.
An object of the present invention is to solve the above problems regarding the removal of metalloid ions, especially group 15 and group 16 elemental ions of the Periodic Table of the Elements, particularly selenium and arsenic ions, and to provide an efficient adsorption separation method with a simpler process. To provide.

Japanese Patent Application Laid-Open No. 2003-19404 Japanese Unexamined Patent Publication No. 9-327694 Japanese Patent No. 3956978 Japanese Unexamined Patent Publication No. 9-308895 Japanese Unexamined Patent Publication No. 2004-89924

An object of the present invention is to efficiently adsorb and remove metalloid ions, especially group 15 and group 16 elemental ions of the Periodic Table of the Elements, particularly selenium and arsenic ions, from industrial wastewater, groundwater and the like. Furthermore, it is an object of the present invention to provide a chelate resin which can be easily and efficiently produced and has excellent adsorption ability for metalloid ions, especially group 15 and group 16 element ions of the Periodic Table of the Elements, particularly selenium and arsenic ions. ..

As a result of diligent studies to solve the above problems, polyvinylcarboxylic acid amide crosslinked polymer particles produced by suspending and polymerizing N-vinylcarboxylic acid amide in salt water in the presence of a crosslinkable monomer and a dispersant were obtained. , The polyvinylamine crosslinked polymer particles obtained by washing and removing salts and the like with water and then hydrolyzing are effective for adsorbing semi-metal ions, especially group 15 and group 16 element ions in the element periodic table, especially selenium and arsenic ions. I found that.

That is, the present invention is a polyvinylamine obtained by suspend-polymerizing N-vinylcarboxylic acid amide and a crosslinkable monomer in salt water in the presence of a dispersant to hydrolyze the polyvinylcarboxylic acid amide crosslinked polymer particles. It relates to semi-metal ions of crosslinked polymer particles, especially group 15 and group 16 element ions of the element periodic table, particularly selenium and arsenic ion adsorption treatment applications.

According to the present invention, by using polyvinylamine crosslinked polymer particles that can be easily and efficiently obtained without using an organic solvent, metalloid ions in water, especially group 15 and group 16 element ions of the Periodic Table of the Elements, are used. In particular, selenium and arsenic ions can be efficiently adsorbed.

Hereinafter, the present invention will be described in detail.

The method for producing polyvinylamine crosslinked polymer particles in the present invention will be described. As a manufacturing method, first, a commonly used suspension polymerization is applied. That is, in the suspension polymerization in salt water in the present invention, an N-vinylcarboxylic acid amide, a crosslinkable monomer, a monomer capable of copolymerizing with N-vinylcarboxylic acid amide if necessary, a polymerization initiator, and a polymerization initiator, and It can be carried out by suspending the dispersant in salt water, stirring at an arbitrary intensity to generate monomer droplets, and radically polymerizing the monomer droplets. The particle size of the monomer droplets is controlled by the dispersant and the stirring intensity, but is 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm.

Examples of the monomer of N-vinylcarboxylic acid amide used in the present invention include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, and N-vinylpropion. Examples thereof include amides, N-methyl-N-vinylpropionamides, N-vinylbutylamides, N-vinylisobutylamides, and N-vinylformamides and N-vinylacetamides are preferable. In addition to the monomer of N-vinylcarboxylic acid amide, a monomer capable of copolymerizing with N-vinylcarboxylic acid amide may be used, and (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N'-dialkyl (meth) acrylamide, N, N'-dialkylaminoalkyl (meth) acrylamide, alkali metal or ammonium salt of (meth) acrylamide alkane sulfonic acid, alkali metal or ammonium salt of (meth) acrylic acid, Hydroxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acryloyloxyalkyl-trimethylammonium salt, alkali metal or ammonium salt of (meth) acryloyloxyalkanesulfonic acid, N-vinylpyrrolidone, diallyl-dialkyl Examples thereof include ammonium salt, vinyl pyridine, vinyl imidazole, vinyl penzyltrialkylammonium salt, alkali metal salt or ammonium salt of vinyl sulfonic acid, and one of these may be used, or two or more thereof may be combined. Is also good. Acrylonitrile is particularly preferable.

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) acrylate 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. The most preferable is divinylbenzene. In addition, allyl ethers such as triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallyl amine, tetraallyloxyetane, pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether, poly ( Meta) Alyloxyalcan and the like can also be used. 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, preferably in the range of 0.1 to 20% by mass. If it exceeds 5% by mass, it becomes difficult to obtain spherical particles only with N-vinylcarboxylic acid amide, so it is preferable to use a monomer copolymerizable with N-vinylcarboxylic acid amide. The addition rate of the copolymerizable monomer is used in the range of 0.1 to 50% by mass with respect to all the monomers. In particular, it is preferable to use acrylonitrile.

Examples of the polymerization initiator include azo-based and peroxide-based polymerization initiators, for example, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2, 2'-azobis (2-methylpropionitrile), 2, 2'-azobis-2-amidinopropane hydrochloride, 4,4'-azobis-4-cyanovaleric acid, 2, 2'- Azobis [2- (5-methyl-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, etc., peroxodisulfate ammonium or potassium, Examples thereof include hydrogen peroxide, benzoylperoxide, lauroylperoxide, octanoylperoxide, succinicperoxide, t-butylperoxy-2-ethylhexanoate and the like. Of these, oil-soluble initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferred. In addition, 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 with respect to 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. Further, 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 does not separate into two phases, and if it is 100% by mass, the effect of the salt is sufficiently obtained. It is uneconomical to add more than 100% by mass. It is preferably 50 to 90% by mass, and more preferably 60 to 90% by mass.

As the dispersant, a polymer dispersant is preferable. As the polymer dispersant, both ionic and nonionic can be used, but ionic is preferable. The ionic polymer is obtained by polymerizing (meth) acryloyloxyethyltrimethylammonium chloride, dimethyldiallylammonium chloride, etc., which are cationic monomers, and the co-weight of these cationic monomers and nonionic monomers is used. Coalescence can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N'-dimethylacrylamide, acrylonitrile, diacetoneacrylamide, 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 50 to 5 million, preferably 50,000 to 3 million. The weight average molecular weight of the nonionic polymer dispersant is 1,000 to 100,000, preferably 1,000 to 50,000. The addition rate is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass with respect to water.

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

After the polymerization, salts, dispersants, unreacted monomers 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, but in order to obtain free polyvinylamine crosslinked polymer particles, hydrolysis is performed under basic conditions. Is preferable. In order to obtain salt-type polyvinylamine crosslinked polymer particles, it is preferable to hydrolyze them under acidic conditions.

As a suitable base for hydrolysis, there is no limitation as long as the pH can be in the range of 8 to 14 at the time of hydrolysis, and it is most preferable to use an aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia. The addition rate is preferably 0.05 to 2.0, more preferably 0.4 to 1.2 equivalents with respect to the formyl group of the polymer.

The acid suitable for hydrolysis is not limited as long as the pH can be in the range of 0 to 5 during hydrolysis, and an inorganic acid such as hydrohalogen acid, sulfuric acid, nitric acid, or phosphoric acid, and 1 carbon number. Mono and organic acids in the range of to 5 and organic acids such as dicarboxylic acid, sulfonic acid, benzenesulfonic acid and toluenesulfonic acid can be exemplified, and it is particularly preferable to use hydrohalogenated acid and hydrogen halide gas, and hydrohalogenated acid is used. Is most preferable. The addition rate is preferably 0.05 to 2.0, more preferably 0.4 to 1.2 equivalents, based on the formyl group of the polymer.

Polyvinylamine crosslinked polymer particles can be obtained by washing with water or the like after hydrolysis. In the case of base hydrolysis, free purified polyvinylamine crosslinked polymer particles are obtained, and in the case of acid hydrolysis, salt 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 crosslinked polymer particles in the present invention are applied to general water treatment applications as chelate resins. Generally, the column is filled and drainage or the like is passed through to adsorb metal ions. Alternatively, after being added to the target liquid, it is mixed under arbitrary stirring conditions such as turbulent flow and laminar flow to adsorb the target object. That is, it exhibits high adsorption ability for metal ions in various industrial and process wastewater, but it can also adsorb other acidic substances, formaldehydes, organic compounds and the like. Further, the crosslinked polymer particles in the present invention are preferably spherical, and if they are spherical, they tend to have a high adsorption capacity for metal ions, and when used as an adsorbent in a column, the filling efficiency is high and the flow path is high. There are advantages such as stability, higher separation efficiency, and improved processing capacity.

The polyvinylamine crosslinked polymer particles in the present invention exhibit high adsorption and separation ability with respect to metalloid ions, especially group 15 and group 16 element ions in the Periodic Table of the Elements, particularly selenium and arsenic ions.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. First, the polyvinylamine polymer particles of the present invention were produced, and the adsorption ability of selenium and arsenic ions was evaluated. As the comparative product, a general-purpose product used for adsorbing heavy metal ions as a chelate resin, and a polyamine type chelate resin CR-20 manufactured by Mitsubishi Chemical Corporation, which is also described in JP-A-2007-302938, was used.

(Manufacturing example)
100 g of demineralized water, 64.0 g of ammonium sulfate, and 1.00 g of polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) are put into a 500 mL four-necked flask, and the mixture is stirred and dissolved. , A polymer bath. N-vinylformamide 33.4 g, divinylbenzene 2.80 g, acrylonitrile 4.00 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2, 4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 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 the inside of the flask was replaced with nitrogen while stirring at 180 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 40 ° C. for 3 hours, followed by 70 ° C. for 2 hours. After the polymerization, the polymer was filtered, washed with water, and filtered to obtain 35.1 g of water-containing polymer spherical particles. The solid content was 42.4%. 23.5 g of the reaction product thus obtained was placed in a 4-neck flask, 23.40 g of a 48 mass% sodium hydroxide aqueous solution was added, and the mixture was hydrolyzed at 80 ° C. for 5 hours with stirring. The particles were washed with water and filtered to obtain 19.7 g of water-containing polyvinylamine spherical particles. As a result of microscopic observation, spherical particles of 50 μm to 2 mm were observed. The polymer particles thus obtained are designated as chelate resin A.

(Example 1) As (V) ion adsorption test An aqueous solution containing As (V) of 0.1 × 10 ^-3 moldm ^-3 was prepared, and the pH of the aqueous solution was 0.1 moldm ^-3 HCl or NaOH aqueous solution. It was adjusted by adding a small amount. 20 mg of the adsorbent chelate resin A was added to 15 cm ³ of the prepared aqueous solution, and the mixture was shaken for 24 hours in a constant temperature bath at a shaking speed of 120 rpm at 30 ° C. After that, the pH was measured by filtering with a hydrophilic PTFE membrane filter (ADVANTEC 13HP045AN) having a pore size of 0.45 μm, and the concentration of the remaining adsorbed species was measured using an atomic absorptiometer (Shimadzu AA-7000) before and after adsorption. The adsorption rate (Adsorption [%]) to the adsorbent was calculated from the change in the concentration of.
Furthermore, 20 mg of the adsorbent chelate resin A was added to 15 cm ³ of an aqueous solution in which the initial concentration was changed in the range of 0.1 × 10 ^-3 to 9.0 × 10 ^-3 moldm ^-3 , and an adsorption experiment was conducted in the same manner. Asked.
The initial pH at this time was adjusted so that the adsorption rate of As (V) was maximized.
Table 1 shows the saturated adsorption amount calculated from the Langmuir equation based on these experimental results. Table 2 shows the ratio (%) of the adsorption rate to the saturated adsorption amount at each pH.

(Comparative Example 1) As (V) Ion Adsorption Test In Example 1, all operations were performed in the same manner except that the polyamine-based chelate resin CR-20 (manufactured by Mitsubishi Chemical Corporation) was replaced with the chelate resin A. CR-20 The saturated adsorption amount of As (V) was determined. The results are shown in Table 1. Table 3 shows the ratio (%) of the adsorption rate to the saturated adsorption amount at each pH.

(Example 2) Adsorption test of Se (IV) ion In Example 1, Se (IV) was subjected to the same procedure except that Se (IV) was replaced with As (V) which is an adsorption species. The saturated adsorption amount was determined. The results are shown in Table 1. Table 4 shows the ratio (%) of the adsorption rate to the saturated adsorption amount at each pH.

(Comparative Example 2) Se (IV) Ion Adsorption Test In Example 2, all the steps were performed in the same manner except that the polyamine-based chelate resin CR-20 (manufactured by Mitsubishi Chemical Corporation) was replaced with the chelate resin A. CR-20 The saturated adsorption amount of Se (IV) was determined. The results are shown in Table 1. Table 5 shows the ratio (%) of the adsorption rate to the saturated adsorption amount at each pH.

(Example 3) Adsorption test of Se (VI) ion In Example 1, Se (VI) was subjected to the same procedure except that Se (VI) was replaced with As (V) which is an adsorption species. The saturated adsorption amount was determined. The results are shown in Table 1.

(Comparative Example 3) Se (VI) Ion Adsorption Test In Example 3, the same procedure was performed except that the polyamine-based chelate resin CR-20 (manufactured by Mitsubishi Chemical Corporation) was replaced with the chelate resin A. CR-20 The saturated adsorption amount of Se (VI) was determined. The results are shown in Table 1.

(Example 4) Detachment test A desorption experiment was performed for As (V). Based on the fact that the adsorption rate decreased at a pH lower than the result of the adsorption experiment, 20 mg of the chelate resin A adsorbed with As (V) was shaken with 0.1 or 1.0 moldm ^-3 hydrochloric acid 15 cm ³ for 24 hours. Later, the concentration of As (V) eluted in the aqueous solution was quantified to calculate the desorption rate [%].
The results are shown in Table-6.

(Table-1)

吸着剤はキレート樹脂Ａ、^＊Ａｓ（Ｖ）イオンの飽和吸着率に対する割合 (Table-2) (Example 1)

Adsorbent is chelate resin A, ^* Ratio of As (V) ions to saturated adsorption rate

吸着剤はキレート樹脂ＣＲ－２０、^＊Ａｓ（Ｖ）イオンの飽和吸着率に対する割合 (Table 3) (Comparative Example 1)

Adsorbent is chelate resin CR-20, ^* Ratio of As (V) ions to saturated adsorption rate

吸着剤はキレート樹脂Ａ、^＊Ｓｅ（ＩＶ）イオンの飽和吸着率に対する割合 (Table-4) (Example 2)

Adsorbent is chelate resin A, ^* Ratio of Se (IV) ion to saturated adsorption rate

吸着剤はキレート樹脂ＣＲ－２０、^＊Ｓｅ（ＩＶ）イオンの飽和吸着率に対する割合 (Table-5) (Comparative Example 2)

Adsorbent is chelate resin CR-20, ^* Ratio of Se (IV) ion to saturated adsorption rate

(Table-6) (Example 4)

As is clear from the results shown in Table 1, the adsorbent according to the present invention includes As (V) ion, Se (IV) ion, and Se (VI) ion, all of which are similar amine resin-based adsorbents used in Comparative Examples. It can be seen that it exhibits extremely high adsorptivity as compared with the chelate resin.
The adsorbent according to the present invention is more dependent on the pH dependence of the As (V) ion adsorbent shown in Table 2 and Table 3 and the Se (IV) ion adsorbed property shown in Table 4 and Table-5. It can be seen that it exhibits good adsorptivity over a wide pH range.
Furthermore, since the detachability shown in Table 6 can be regenerated extremely easily, it can be judged that the value is extremely high industrially.

As described in detail above, the invention of this application provides a new technical means capable of efficiently removing As (V) ions, Se (IV) ions, Se (VI) ions and the like from wastewater and the like. be able to.

Claims (7)

Polyvinylamine crosslinked polymer particles produced by hydrolysis of crosslinked polymer particles obtained by suspension polymerization in the presence of a dispersant in salt water containing N-vinylcarboxylic acid amide and a crosslinkable monomer are placed in water. A method for adsorbing and separating semi-metal ions, which comprises adding them. The adsorption separation method according to claim 1, wherein the metalloid ion is an elemental ion of Group 15 or Group 16 of the Periodic Table of the Elements. The adsorption separation method according to claim 2, wherein the elemental ions of Group 15 or Group 16 are selenium or arsenic ions. The adsorption separation method according to claim 1, wherein the crosslinkable monomer is one or more selected from aromatic polyvinyl compounds and allyl ethers. A method for adsorbing and separating a metalloid ion according to claim 1, wherein the polyvinylamine crosslinked polymer particles are regenerated with an acid and the metalloid ion is repeatedly adsorbed and separated. The polyvinylamine crosslinked polymer particles according to claim 2, which have adsorbed the metalloid ions of Group 15 or 16 of the Periodic Table of the Elements, are regenerated with an acid, and the repeated metalloid ions are Group 15 or 16 of the Periodic Table of the Elements. A method for adsorbing and separating metalloid ions. A method for adsorbing and separating selenium or arsenic ions, which comprises regenerating the polyvinylamine crosslinked polymer particles having adsorbed selenium or arsenic ions with an acid and repeatedly adsorbing and separating selenium or arsenic ions.