KR100260839B1 - Chelating resins with heavy metal-adsorptivity - Google Patents

Abstract

PURPOSE: Disclosed is a chelate resin for adsorption of heavy metals. CONSTITUTION: The chelate resin is prepared by the continuous polymerization process by the polymerization and hydrolysis step of stylene and carboxylic acid monomer and divinyl benzene and the hydrolysis and addition step of a (O=P) functional group in side chain of copolymer resin. The chelate resin is represented by the formula I where M represents H, Na, and K, n is 0 or 1, in case z is 0, x and y is 1, in case z is 1, x is 0 and y is 1.

Description

Chelating resin for heavy metal ion adsorption

The present invention relates to a chelate resin for adsorption of heavy metal ions, and more particularly, a monomer having a carboxyl group and a styrene-based monomer such as styrene or chloromethyl styrene, which is polymerized with divinylbenzene as a crosslinking agent. The phosphate group was further introduced into the phenyl group or the chloromethylphenyl group bonded as the side chain group of the copolymer, and the basic skeleton of the chelate functional group of the copolymer resin was benzene as a spacer. It is stable to acid-alkali and has excellent reusability, as well as containing phosphono and carboxyl groups useful for adsorption of heavy metal ions at the same time to further strengthen the chelate formation capacity of heavy metal ions represented by the following formula (1) It relates to a chelate resin for ion adsorption.

Formula 1

In Chemical Formula 1, M represents a hydrogen atom, a sodium atom or a potassium atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1.

Chelate resins known to date include chelate resins containing phosphono groups as functional groups [J. Appl. Polym. Sci., 29, 2045 (1984) and U.S. Patent No. 5,457,163 have shown good adsorption capacity for heavy metal ions such as uranium, lead, mercury and the like, and chelate resins containing carboxyl groups as functional groups. 138,046 and Japanese Patent Application Laid-open No. Hei 8-10,763 have excellent cation exchange capacity and are effectively used for iron ion removal. For known chelate resins containing phosphono groups as functional groups, see J. Appl. Polym. The chelate resin shown in Sci., 29, 2045 (1984) has functional groups placed only in the side chain portion of the copolymer resin, and the chelate resin shown in US Pat. No. 5,457,163 distributes the functional groups evenly in the main and side chains of the copolymer. The ions are induced to chelate well.

In this regard, a chelating agent or a resin associated with the phosphono-based functional group and another chelate functional group is exemplified as follows. 1) chelating agents applied with phosphoric acid groups and amine groups [J. Appl. Polym. Sci., 33 (4), 1275-81 (1987) and Japanese Patent Laid-Open No. 3-237,007] were effective for the adsorption of metal ions such as copper, lead, arsenic, gallium, and indium, and 2) phosphate groups, amines Resin (US Pat. No. 5,534,611) to which a group, a carboxyl group, and the like are applied together was used as a dispersant to suppress scale. In addition, in connection with the above 2), 3) an amine group and a carboxyl group, together with a resin (German Patent Publication No. 3,621,025 (1987)), were used to induce bleaching functions by making iron salts or oxidizing silver (Ag). .

Conventional chelate resins described above each have a phosphono group or a carboxyl group alone as a functional group, and the chelate resins having each of these functional groups are different from each other. Therefore, if the phosphono group and the carboxyl group at the same time as a functional group having the characteristics described in the above 1) to 3) evenly can be utilized as a chelate resin. In addition, it may be more effective if the carboxyl group is arranged in the main chain of the copolymer resin and the phosphono group is arranged in the side chain while having a skeleton structure similar to that of US Patent No. 5,457,163 exemplified above.

In the present invention, a carboxyl group structure capable of chelate formation is introduced into the main chain, which is a basic skeleton of the copolymer resin, and a phosphono group for chelate formation is introduced into the phenyl group or chloromethylphenyl group, which is a side chain of the copolymer resin, to form a basic skeleton of the copolymer resin. Completed the present invention by making the carboxyl group and the concave-convex structure arranged in the main chain with the phosphono group disposed in the side chain within the apex, so that the chelate formation ability is maintained to be larger, thereby greatly improving the adsorption capacity for heavy metal ions. It was.

Therefore, the present invention has a very high chelate formation ability because the different chelate functional groups are introduced, and the chelate functional groups formed in the copolymer resin are directly bonded to the carbon atoms, and thus used in the repeated regeneration process of adsorption-desorption. It is an object of the present invention to provide a chelate resin for adsorption of heavy metal ions, which is remarkably improved by preventing hydrolysis of acid or alkaline solutions.

The present invention is characterized by the chelate resin for adsorption of heavy metal ions represented by the following formula (1).

Formula 1

In Chemical Formula 1, M represents a hydrogen atom, a sodium atom or a potassium atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1.

In addition, the present invention is a suspension copolymerization of the styrene monomer represented by the following formula (2) and the carboxylic acid ester monomer represented by the following formula (3) with a divinylbenzene crosslinking agent and then hydrolyzed to obtain a copolymer resin represented by the following formula (4) To manufacture; And

Another characteristic of the method for preparing a chelate resin for adsorption of heavy metal ions represented by the following Chemical Formula 1, wherein the phosphono group is further introduced into the side chain of the copolymer resin represented by Chemical Formula 4, and then subjected to a hydrolysis reaction. have.

Formula 1

In the formulas above, R represents a lower alkyl group having 1 to 8 carbon atoms; M represents a hydrogen atom, a sodium atom or a potassium atom; X represents a hydrogen atom or a chlorine atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1.

Referring to the present invention in more detail as follows.

The present invention relates to a chelate resin represented by Chemical Formula 1 having excellent reusability and adsorption capacity of heavy metal ions. The chelate resin is a divinylbenzene crosslinking agent for a carboxyl ester monomer having a structure that can be converted into a styrene-based monomer and a carboxyl group. After copolymerization using a hydrolyzate to form a carboxyl group structure capable of chelation in the basic skeleton of the copolymer resin, and further convertible to a phosphono group for chelate formation in a phenyl group or a chloromethylphenyl group which is a side chain of the copolymer resin basic skeleton After the functional group is introduced, it is prepared by a method of converting it into a phosphono group by hydrolysis or oxidation simultaneously with hydrolysis.

As a result, the chelating resin represented by Chemical Formula 1 according to the present invention has a carboxyl group disposed on the main chain of the basic skeleton and a phosphono group which is completely different from the side chain thereof, thereby enhancing the ability to form a chelate according to two kinds of functional group combinations. The phosphono group substituted by the side chain phenyl group or the chloroalkylphenyl group is made to improve the chelate formation ability by making the carboxyl group and the functional group of the main chain form an uneven structure.

In addition, the chelating resin represented by Chemical Formula 1 according to the present invention has a structure in which chelating functional groups are directly bonded to carbon atoms, so that each of the chelating resins is hydrolyzed in the presence of an acid or alkaline solution during regeneration in which adsorption-desorption processes are repeated. Since the structure of the functional group does not desorb, it does not contaminate the solution and has good chelate formation as well as durability that can be reused.

If the manufacturing process of the chelate resin represented by the formula (1) according to the present invention having the characteristics as described above is schematically shown in the following scheme 1.

In Scheme 1: R represents a lower alkyl group having 1 to 8 carbon atoms; M represents a hydrogen atom, a sodium atom or a potassium atom; X represents a hydrogen atom or a chlorine atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1.

First, a diluent and a radical initiator are added to the styrene monomer represented by the formula (2), the carboxylic acid ester monomer represented by the following formula (3) and the divinylbenzene crosslinking agent, followed by suspension polymerization at 40 to 100 ° C. for 2 to 50 hours. The copolymer resin is hydrolyzed at 40 to 130 ° C. for 1 to 60 hours in the presence of an acid catalyst to prepare a copolymer resin represented by Chemical Formula 4, wherein a carboxyl group is introduced into the main chain of the copolymer resin. Then, a phosphon group is introduced and hydrolyzed into a phenyl group or a chloromethylphenyl group, which is a side chain of the basic skeleton of the copolymer resin represented by Formula 4, to prepare a chelate resin represented by Formula 1, which is the object of the present invention.

Styrene-based monomer represented by the formula (2) used in the preparation of the chelate resin according to the present invention is styrene or p-methyl chloride. Examples of the carboxylic acid ester monomer represented by the general formula (3) include dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumalate, and itaconic acid butyl ester. The carboxylic acid ester monomer represented by the formula (3) is preferably used in the range of 0.05 to 0.6 molar ratio (maximum in solution polymerization) with respect to 1 mole of the styrene monomer. If the amount of the carboxylic acid ester monomer is less than 0.05 molar ratio, the chelate Since the effect is insignificant and the molar ratio exceeding 0.6 mole ratio, a non-spherical copolymer is obtained, which is not preferable because the specific surface area of the chelating resin is remarkably lowered.

The polymerization method of the present invention is a suspension polymerization method between a lipophilic styrenic monomer and a hydrophilic carboxylic acid ester monomer, and the polymer is formed into a spherical shape so that the inside contains a large amount of lipophilic styrene-based structure. In the outer side of the sphere, a lot of hydrophilic carboxylic acid ester structure is arranged.

In addition, divinylbenzene, which is used as a crosslinking agent during copolymerization, gives mechanical strength to the styrene-based spherical copolymer and serves as a ladder of a network structure in which heavy metal ions can enter and exit. Divinylbenzene is preferably used at a ratio of 2.0 to 30% by weight based on the total amount of monomers. If the amount is less than 2.0% by weight, the network structure does not act as a ladder. Larger surface area decreases and the adsorption effect decreases, which is not good.

In the present invention, the diluent that can be used in the copolymerization is a small amount of organic diluent such as toluene, cyclohexane, etc., which is used in an amount of 2.0 to 20% by weight based on the total amount of the monomers used. This diluent is used as a precipitant in the copolymerization reaction to form a physical concavo-convex structure on the surface of the spherical copolymer. After the reaction, the diluent is physically mixed in the spherical copolymer and dried to dry the specific surface area of the spherical copolymer. Will become large.

Meanwhile, in the present invention, a radical polymerization method is used, wherein as the radical initiator, benzoyl peroxide, p, p'-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, di-t-butyl perox A peroxide initiator, such as a seed, potassium peroxide, or ammonium peroxide, an azo radical initiator, such as bis azoisobutylonitrile, etc. can be used.

In addition, the copolymerization method of the present invention uses a radical suspension polymerization method, wherein the suspending agent is methyl cellulose, partially hydrolyzed polyvinyl alcohol, polyvinylpyrrolidone or a mixture thereof. The amount of the suspending agent used is 0.01 to 4.0% by weight, particularly preferably 0.1 to 2.0% by weight based on the total amount of the monomer used.

In general, such suspension polymerization is made in the aqueous dispersion (aqueous dispersion), the radical polymerization occurs in the aqueous dispersion even in the copolymerization method of the present invention, wherein the weight ratio (α value) of water to the organic monomers is preferably 0.5 to 15 weight ratio. If the amount of water used is less than 0.5 weight ratio, the viscosity becomes so large that it is difficult to obtain a uniform aqueous phase, whereas if the amount of water exceeds 15 weight ratio, the productivity is lowered and the amount of energy consumed is required to heat a large amount of water. Will not.

According to the present invention, the particle size of the spherical copolymer is controlled from the amount of the suspending agent and the weight ratio between the water and the organic monomers in the aqueous phase.

Thus, the hydrolysis of the copolymer resin obtained in the present invention adds 2-10 times the weight ratio of ethanol and 1-20 times the weight ratio of concentrated hydrochloric acid per weight of the dry copolymer resin, and is maintained at 40-130 ° C. for 1-60 hours. Subsequent purification can be accomplished by blowing off the volatile components, washing the residue with water and methanol and then drying.

On the other hand, the reaction of introducing the phosphon group into the phenyl group or the chloromethylphenyl group which is the side chain of the copolymer resin skeleton represented by the formula (4) prepared by the method for the copolymerization is performed in the presence or absence of a substituent on the phenyl group which is the side chain of the copolymer resin skeleton The method may vary. In the case of the copolymer resin represented by Chemical Formula 4a having a phenyl side chain group as shown in Scheme 2, the Friedel-Craft reaction was performed using phosphorus trichloride (PCl ₃ ) and aluminum trichloride (AlCl ₃ ) as a catalyst. After that, hydrolysis and oxidation reaction are carried out, and neutralization reaction with sodium or potassium hydroxide is carried out as necessary to prepare a chelate resin represented by the target formula (1a). On the contrary, in the case of the copolymer resin represented by the formula (4b) having a chloromethylphenyl side chain, it is reacted with triethyl phosphite (TEP), followed by hydrolysis, and neutralized with sodium hydroxide or potassium hydroxide as necessary for the purpose. To prepare another chelate resin represented by the formula (1b).

In Scheme 2: R represents a lower alkyl group having 1 to 8 carbon atoms; M represents a hydrogen atom, a sodium atom or a potassium atom; X represents a hydrogen atom or a chlorine atom; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1.

Phosphono group introduction reaction as shown in Scheme 2 is carried out at 40 to 100 ℃ temperature, hydrolysis and / or oxidation reaction at 40 to 130 ℃ temperature, and neutralization reaction at room temperature.

On the other hand, in the present invention, a method of introducing a chloromethyl group into a phenyl group which is a side chain of a copolymer resin obtained by using a styrene monomer is copolymerized using chloromethyl styrene containing a chloromethyl group as a monomer, or first, a styrene copolymer resin is used. And reacted with 0.01 to 10 times by weight of chloromethylmethyl ether in a 2 to 20 times weight ratio of cyclohexane solution per resin by using 0.01 to 10 times weight ratio of aluminum chloride as a catalyst, and then the reaction mixture was separated by filtration and distilled water and methanol. Prepared by washing and drying.

Such a present invention will be described in detail based on the following examples, but the present invention is not limited thereto.

Examples 1 to 36: Preparation of Chelate Resin Containing Phosphono and Carboxyl Groups Simultaneously

In a reactor with a stirrer, monomers as shown in the following Table 1 were added, and 0.2 wt% of benzoyl peroxide as a polymerization initiator was added to the total amount of monomers, and the ratio of these monomers to water was 2.5. 1% methylcellulose solution was used as a dispersant.

The suspension polymerization was maintained at 70 ° C. for 25 hours, and the resulting polymerization product was filtered and washed with water, which was dried for 48 hours in a vacuum dryer maintained at 60 ° C. and then filtered through a 60/80 mesh sieve.

Introduction of the carboxyl group to the main chain of the copolymer resin was carried out by adding 4 parts by weight of methanol and 3 parts by weight of concentrated hydrochloric acid per weight of the dried resin obtained by copolymerizing the dibutyl maleate monomer, and refluxing the mixture at 90 ° C. for 42 hours. The purification was carried away by volatiles and the residue was washed with distilled water and dried.

Subsequently, triethyl phosphite is reacted at 70 ° C. for 30 hours or chloromethylphenyl group, which is a side chain of the basic resin skeleton, is reacted at 70 ° C. for 30 hours, or 8 parts by weight of cyclohexane per weight of the copolymer resin is 0.25 parts by weight of chloride. After reacting 0.25 weight ratio of phosphorus trichloride at an aluminum catalyst for 30 hours at 70 DEG C, and oxidizing each of them simultaneously with hydrolysis for 42 hours at 90 DEG C in the presence of an acid catalyst, the reaction was filtered and washed with water and methanol. It dried under vacuum at 60 degreeC for 48 hours, and produced the yellow spherical chelating resin [H-type functional group].

The composition, the content of each functional group and the adsorption amount of heavy metal ions of the obtained chelate resin are shown in Table 1 below.

In addition, using each chelate resin prepared above, the corresponding heavy metal ions were repeatedly adsorbed / desorbed (desorbed with 1 M hydrochloric acid at room temperature for 24 hours, neutralized with 1 M caustic soda and washed). , And the adsorption amount of each ion is shown in Table 2 below.

In addition, each of the chelating resins prepared above was put in a 1M aqueous solution of caustic soda at room temperature, stirred for 3 hours, filtered, washed, and dried to convert the functional groups of the carboxyl or phosphono groups in the chelate resin into sodium salt type [Na type]. Then, the adsorption amount of each ion was measured and shown in Table 3 below.

Example Chelate resin (H type, new) The adsorption amount of ^a heavy metal ion Composition of resin (mol) Ion exchange amount ^d (meq / g-resin) Pb ²⁺ Cd ²⁺ Cu ²⁺ Hg ²⁺ UO ₂ ²⁺ Methyl Chloride Styrene Divinylbenzene ^b Carboxylic acid ester ^c Carboxyl group Phosphono groups One 1.00 - 0.18 (13.6) ^e - - 5.01 1.36 0.31 0.19 0.55 0.21 2 1.00 - 0.23 (14.3) 0.12 (M) ^f 0.84 4.45 1.74 1.36 1.24 0.47 0.18 3 1.00 - 0.25 (14.0) 0.22 (M) 1.43 3.68 1.93 1.76 1.61 0.43 0.15 4 1.00 - 0.32 (15.6) 0.31 (M) 1.70 2.98 1.96 1.80 1.65 0.35 0.13 5 1.00 - 0.38 (16.7) 0.42 (M) 1.84 2.79 1.96 1.83 1.65 0.25 0.09 6 1.00 - 0.41 (16.7) 0.48 (M) 1.96 2.64 1.99 1.85 1.67 0.26 0.06 7 1.00 - 0.31 (14.0) 0.44 (F) 1.53 2.46 1.63 1.50 1.34 0.19 0.05 8 1.00 - 0.33 (14.0) 0.44 (I) 2.03 3.05 1.95 1.78 1.59 0.23 0.14 9 - 1.00 0.21 (15.1) 0.07 (M) 0.51 3.92 1.68 1.57 1.48 0.52 0.20 10 - 1.00 0.21 (14.3) 0.12 (M) 0.84 4.62 1.79 1.66 1.52 0.49 0.19 11 - 1.00 0.26 (15.7) 0.18 (M) 1.27 3.54 1.94 1.77 1.64 0.40 0.16 12 - 1.00 0.32 (16.0) 0.31 (M) 1.72 3.07 1.95 1.80 1.65 0.43 0.13 ^a Adsorption amount of heavy metal ions is calculated by calculating the difference in concentration of solution after adding 0.2g of sample to 20 ml of each ion solution at pH 4.27 and 21.2 ppm. ^b All the amount used in the copolymerization is considered to have reacted. ^c Calculated by elemental analysis. ^d Calculated by neutralization titration and phosphorus analysis. ^e % by weight relative to total monomer usage. ^f carboxylic acid ester; M: dibutyl maleate, F: dibutyl maleate, I: itaconic acid.

Example Chelated Resin (Type H, 4 Reuses) The adsorption amount of ^a heavy metal ion Composition of resin (mol) Ion exchange amount ^d (meq / g-resin) Pb ²⁺ Cd ²⁺ Cu ²⁺ Hg ²⁺ UO ₂ ²⁺ Methyl Chloride Styrene Divinylbenzene ^b Carboxylic acid ester ^c Carboxyl group Phosphono groups 13 1.00 - 0.18 (13.6) ^e - - 5.01 1.38 0.31 0.18 0.54 0.20 14 1.00 - 0.23 (14.3) 0.12 (M) ^f 0.84 4.45 1.73 1.35 1.24 0.47 0.17 15 1.00 - 0.25 (14.0) 0.22 (M) 1.43 3.68 1.92 1.74 1.59 0.43 0.15 16 1.00 - 0.32 (15.6) 0.31 (M) 1.70 2.98 1.96 1.79 1.65 0.34 0.11 17 1.00 - 0.38 (16.7) 0.42 (M) 1.84 2.79 1.95 1.82 1.64 0.25 0.08 18 1.00 - 0.41 (16.7) 0.48 (M) 1.96 2.64 1.98 1.83 1.65 0.24 0.05 19 1.00 - 0.31 (14.0) 0.44 (F) 1.53 2.46 1.62 1.49 1.33 0.18 0.05 20 1.00 - 0.33 (14.0) 0.44 (I) 2.03 3.05 1.94 1.75 1.57 0.21 0.13 21 - 1.00 0.21 (15.1) 0.07 (M) 0.51 3.92 1.67 1.55 1.47 0.51 0.19 22 - 1.00 0.21 (14.3) 0.12 (M) 0.84 4.62 1.78 1.64 1.51 0.47 0.18 23 - 1.00 0.26 (15.7) 0.18 (M) 1.27 3.54 1.93 1.76 1.64 0.38 0.15 24 - 1.00 0.32 (16.0) 0.31 (M) 1.72 3.07 1.94 1.79 1.63 0.41 0.12 ^a Adsorption amount of heavy metal ions is calculated by calculating the difference in concentration of solution after adding 0.2g of sample to 20 ml of each ion solution at pH 4.27 and 21.2 ppm. ^b All the amount used in the copolymerization is considered to have reacted. ^c Calculated by elemental analysis. ^d Calculated by neutralization titration and phosphorus analysis. ^e % by weight relative to total monomer usage. ^f carboxylic acid ester; M: dibutyl maleate, F: dibutyl fumarate, I: itaconic acid.

Example Chelate resin (Na type, new article) The adsorption amount of ^a heavy metal ion Composition of resin (mol) Ion exchange amount ^d (meq / g-resin) Pb ²⁺ Cd ²⁺ Cu ²⁺ Hg ²⁺ UO ₂ ²⁺ Methyl Chloride Styrene Divinylbenzene ^b Carboxylic acid ester ^c Carboxyl group Phosphono groups 25 1.00 - 0.18 (13.6) ^e - - 5.01 1.80 1.74 1.65 2.11 2.04 26 1.00 - 0.23 (14.3) 0.12 (M) ^f 0.84 4.85 1.93 1.90 1.88 2.05 1.93 27 1.00 - 0.25 (14.0) 0.22 (M) 1.43 3.68 2.08 2.06 2.05 1.98 1.94 28 1.00 - 0.32 (15.6) 0.31 (M) 1.70 2.98 2.12 2.09 2.07 2.00 1.88 29 1.00 - 0.38 (16.7) 0.42 (M) 1.84 2.79 2.10 2.08 2.06 2.07 1.91 30 1.00 - 0.41 (16.7) 0.48 (M) 1.96 2.64 2.07 2.06 2.04 2.02 2.12 31 1.00 - 0.31 (14.0) 0.44 (F) 1.53 2.46 1.78 1.72 1.69 1.68 2.03 32 1.00 - 0.33 (14.0) 0.44 (I) 2.03 3.05 1.96 1.87 1.82 1.85 2.12 33 - 1.00 0.21 (15.1) 0.07 (M) 0.51 3.92 1.93 1.84 1.78 2.07 1.97 34 - 1.00 0.21 (14.3) 0.12 (M) 0.84 4.62 2.02 2.00 1.98 2.00 1.94 35 - 1.00 0.26 (15.7) 0.18 (M) 1.27 3.54 2.04 2.01 1.99 1.99 1.97 36 - 1.00 0.32 (16.0) 0.31 (M) 1.72 3.07 2.07 2.03 2.01 2.01 1.91 ^a Adsorption amount of heavy metal ions is calculated by calculating the difference in concentration of solution after stirring for 28 hours by adding 0.2g of sample (100% adsorption amount is converted to 2.12) in 20 ml of each ion solution at pH 4.27 and 21.2 ppm. ^b All the amount used in the copolymerization is considered to have reacted. ^c Calculated by elemental analysis. ^d Calculated by neutralization titration and phosphorus analysis. ^e % by weight relative to total monomer usage. ^f carboxylic acid ester; M: dibutyl maleate, F: dibutyl fumarate, I: itaconic acid.

Comparative Examples 1-7: Preparation of Chelate Resin Containing Phosphono Group

In a reactor equipped with a stirrer, monomers as shown in the following Table 4 were added, and 0.2 wt% of benzoyl peroxide as a polymerization initiator was added to the total amount of the monomers, and the ratio (α value) with these monomers was 2.5. , 1% aqueous methylcellulose solution was used as a dispersant.

The suspension polymerization was maintained at 70 ° C. for 25 hours, and the resulting polymerization product was filtered and washed with water, which was dried for 48 hours in a vacuum dryer maintained at 60 ° C. and then filtered through a 60/80 mesh sieve.

The introduction of the phosphono group to the main chain of the copolymer resin was carried out by hydrolysis by refluxing at 90 ° C. for 42 hours with 4 parts by weight of methanol and 3 parts by weight of hydrochloric acid per weight of the dried copolymer resin obtained by the copolymerization reaction. The purified product was flushed with volatiles and the residue was washed with distilled water and dried.

Then, to introduce the phospho group to the phenyl group, which is the side chain of the copolymer resin skeleton, 8 weight ratio of cyclohexane per weight of the copolymer resin in which the phosphono group was introduced only in the main chain, and 0.25 weight ratio in the presence of 0.25 weight ratio of aluminum chloride catalyst. After phosphorus trichloride was reacted at 70 ° C. for 30 hours, the reaction mixture was filtered and washed with water and methanol and dried.

Here, the dried reactant was oxidized simultaneously with hydrolysis at 80 ° C. for 20 hours using 10% by weight of nitric acid solution having a concentration of 2% per weight. This was then vacuum dried at 60 ° C. for 48 hours to produce a yellow spherical phosphate chelate resin.

The composition, functional group content and heavy metal ion adsorption amount of the obtained chelate resin were as shown in Table 4 below.

Comparative example Chelate resin The adsorption amount of ^a heavy metal ion Composition of resin (mol) Functional group content ^d (mmol / mg-resin) Pb ²⁺ Cd ²⁺ Cu ²⁺ Hg ²⁺ UO ₂ ²⁺ Methyl Chloride Styrene Divinylbenzene ^b Vinylphosphonate ^c Backbone chain One - 1.00 0.1467 (14.8) ^e 0.0251 4.2 19.9 1.85 0.64 1.18 1.89 0.58 2 - 1.00 0.1660 (15.1) 0.0746 9.8 14.3 2.06 0.79 1.39 1.99 0.87 3 - 1.00 0.2122 (15.7) 0.1878 19.5 10.9 2.08 1.57 1.49 2.10 1.49 4 - 1.00 0.2593 (16.0) 0.3153 23.8 7.3 2.10 0.92 1.42 1.97 1.19 5 - 1.00 0.3259 (16.4) 0.4780 27.2 3.2 0.42 0.41 0.31 1.90 1.06 6 1.00 - 0.1354 (14.4) - - 27.4 0.04 0.11 0.04 0.10 0.31 7 1.00 - 0.1354 (14.4) - - 34.6 1.41 0.36 0.08 0.69 1.01 ^a Adsorption amount of heavy metal ions is calculated by calculating the difference in concentration of solution after adding 0.2g of sample to 20 ml of each ion solution at pH 4.27 and 21.2 ppm. ^b All the amount used in the copolymerization is considered to have reacted. ^c Component content is calculated by elemental analysis with bis- (2-chloroethyl) vinylphosphonate. ^d Calculated by neutralization titration and phosphorus analysis. ^e % by weight of total monomer usage.

As can be seen in Table 1 and Table 2, the chelate resin represented by the formula (1) according to the present invention is two different chelate functional groups, that is, phosphono group (O = P) and carboxyl group (O = C) is combined Among them, H-type chelate resins exhibit strong adsorption characteristics for certain heavy metal ions (eg, Cd and Cu), and Na-type chelate resins exhibit excellent adsorption characteristics for most heavy metal ions. Therefore, when preparing a chelate resin, the chelate resin is prepared in consideration of the content of each functional group bonded to the main chain and the side chain, the content of the crosslinking agent, the specific surface area, and the reusability from adsorption-desorption, etc., according to the purpose of use. It has the effect of greatly improving the adsorption and reusability.

Claims (7)

Chelating resin for adsorption of heavy metal ions represented by the following formula (1). Formula 1 In Chemical Formula 1, M represents a hydrogen atom, a sodium atom or a potassium atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1. In preparing chelate resin for heavy metal ion adsorption, To prepare a copolymer resin represented by the following formula (4) by suspending copolymerization of the styrene monomer represented by the following formula (2) and the carboxylic acid ester monomer represented by the following formula (3) with a divinylbenzene crosslinking agent and then hydrolyzed; And A method for preparing a chelate resin for adsorption of heavy metal ions represented by the following Chemical Formula 1, further comprising introducing a phosphono group into the side chain of the copolymer resin represented by Chemical Formula 4 and then performing a hydrolysis reaction. Formula 2 Formula 3 Formula 4 Formula 1 In the formulas above, R represents a lower alkyl group having 1 to 8 carbon atoms; M represents a hydrogen atom, a sodium atom or a potassium atom; X represents a hydrogen atom or a chlorine atom; n is 0 or 1; x = y = 1 for z = 0 and x = 0 and y = 1 for z = 1. The method of claim 2, wherein the carboxylic acid ester represented by the formula (3) is selected from dibutyl maleate, dibutyl fumarate and itaconic acid butyl ester, and used for chelate resin for heavy metal ion adsorption. . The method of claim 2, wherein the suspension co-polymerization reaction is carried out at a temperature of 40 ~ 130 ° C. According to claim 2, wherein the additional phosphono group introduction reaction to the copolymer resin side chain is a Friedel-Craft reaction using a copolymer resin represented by the following formula (4a) with phosphorus trichloride (PCl ₃ ) and aluminum trichloride (AlCl ₃ ) catalyst Method for producing a chelate resin for heavy metal ions adsorption, characterized in that carried out by (Fridel-Craft reaction). In Formula 4a: x = y = 1 when z = 0, x = 0, y = 1 when z = 1. The method of claim 2, wherein the additional phosphono group introduction reaction into the copolymer resin side chain is made by reacting tributyl phosphite with a copolymer resin represented by the following Chemical Formula 4b. . In Chemical Formula 4b: when z = 0, x = y = 1, and when z = 1, x = 0 and y = 1. The method for preparing chelate resin for adsorption of heavy metal ions according to claim 5 or 6, wherein the phosphono group introduction reaction is performed at a temperature of 40 to 100 ° C.