KR20130091891A - Ion exchange resin and method for fabricating the same - Google Patents

Abstract

PURPOSE: An ion-exchange resin and a manufacturing method thereof are provided. Under the manufacturing method of the ion-exchange resin, the formation of methyl chloride is maximized to produce an ion-exchange resin with high functionality and the specific surface area of the ion-exchange resin is maximized to increase the ion exchange capacity of the ion-exchange resin. CONSTITUTION: A manufacturing method of an ion-exchange resin comprises the steps of: preparing a macromolecular bead by mixing styrene monomer and divinyl benzene in an aqueous solution, mixing the macromolecular bead in the aqueous solution, alkyl halide material, and a reaction catalyst to drive the chloromethylation reaction for producing a resin with methyl chloride, and reacting the resin having methyl chloride with amine material to attach an amine group to the resin with methyl chloride. In the steps, the organic solvent is dichloroethane, the alkyl halide material is chloromethylmethylether and the reaction catalyst is ferric chloride (FeCl3). [Reference numerals] (AA) Styrene / Divinylbenzene; (BB) Polymer bead; (CC) CM resin; (DD) Resin after amine reaction; (EE) Resin after OH regeneration reaction

Description

Ion exchange resin and method for fabricating the same

The present invention relates to an ion exchange resin and a method for manufacturing the same, and more particularly, to a high specific surface area and high density of functional groups attached through a chloromethylation reaction to which a specific catalyst and reaction conditions are applied and an additional chemical reaction after the chloromethylation reaction. It relates to an ion exchange resin capable of producing an ion exchange resin having a and a method for producing the same.

Ion exchange resin is a polymer material for exchanging and purifying an ionic substance dissolved in a solution by combining an ion exchange functional group with a polymer beads having a fine three-dimensional structure. That is, the mobile ions of the ion exchange resin are replaced with other ions in the solution to remove the ionic substance. The performance and characteristics of the ion exchange resin may vary depending on the type, density, crosslinking degree and specific surface area of the ion exchange group. Is determined.

In order to increase the ion exchange capacity of the ion exchange resin, the functional group for ion exchange must be formed in the resin with high density.In the case of the anion exchange resin for removing anions from the solution, a polymer using styrene monomer and divinylbenzene After preparing a resin (Styrene / Divinylbenzene copolymer bead) is attached to the carbon chloride (methyl chloride group) to the benzene ring of the resin is prepared by the amination reaction. At this time, the chloromethylation reaction is important to attach a methyl chloride group to the benzene ring. Various methods for this have been introduced.

The most common method is to attach a haloalkylatuing agent such as chloromethylmethyl ether (CMME) using a Friedel-Crafts catalyst (US Patent No. 2,632,000). 2,616,877, 2,642,417, 2,632,001, 2,992,544 and the like. As the hazards of chloromethyl methyl ether (CMME) are reported, chloromethylation reaction is generated by generating chloromethyl methyl ether during the reaction using a mixture of formalin, chlorosulfonic acid, methanol, etc., without using chloromethyl methyl ether directly. ) Also has the disadvantage of generating excess sulfuric acid and low reaction efficiency. In addition to this, there is a technique for making polymer beads using chloromethylated styrene attached as a monomer instead of a simple styrene monomer to introduce a high density chloromethyl group. However, German Patent No. 2,218,126 is used in this method. It is reported that functionalized styrene is very expensive compared to simple styrene, and it is difficult to commercialize.

On the other hand, one of the factors that have an important effect on the characteristics and performance of the ion exchange resin is the specific surface area of the ion exchange resin. Recently, studies have been made on the preparation of ion exchange resins having a high specific surface area for various purposes such as high performance adsorbents and hydrogen storage materials. Among them, a widely used method is a high-crosslinking reaction method based on a Friedel-Crafts reaction using a metal chloride catalyst. In general, nanopore is formed by connecting bridges between benzenes of styrene through Friedel-Crafts catalysis using various linker materials having chlorine groups in divinylbenzene and styrene monomer-based polymer resins. Higher cross-linking reactions are used a lot (US Pat. Nos. 3,729,457, 4,191,813, 5,137,926). In addition, U.S. Patent No. 5,416,124 proposes a method of inducing a high crosslinking reaction after attaching a methyl chloride group to a styrene / divinylbenzene polymer resin through a chloromethylation reaction. Recently, a method of preparing a polymer resin having a methyl chloride group by using styrene having a methyl chloride group as a monomer instead of a simple styrene monomer, and then inducing a further high crosslinking reaction using a metal chloride catalyst has been reported. . This method is capable of producing ion exchange resins with high specific surface area of 2000m ² / g due to high density of methyl chloride, but it is difficult to commercialize because of high production cost of styrene attached with methyl chloride group (Macromolecules 2006, 39, 627-632; Chemistry of Materials 2006, 18, 4430-4435.

US Patent No. 2,632,000 US Patent No. 2,616,877 US Patent No. 2,642,417 US Patent No. 2,632,001 US Patent No. 2,992,544 United States Patent No. 3,729,457 United States Patent No. 4,191,813 US Patent No. 5,137,926 US Patent No. 5,416,124 Macromolecules 2006, 39, 627-632 Chemistry of Materials 2006, 18, 4430-4435

The present invention has been made to solve the above problems, ions having a high specific surface area and a high density of functional groups attached through the chloromethylation reaction, a specific catalyst and the reaction conditions, further chemical reaction after the chloromethylation reaction An object of the present invention is to provide an ion exchange resin and a method of manufacturing the same that can produce exchange resins.

Method for producing an ion exchange resin according to the present invention for achieving the above object is to form a polymer bead by mixing a styrene monomer and divinylbenzene in an aqueous solution, the polymer bead, alkyl halide material and reaction in an organic solvent Mixing a catalyst to induce a chloromethylation reaction to prepare a resin with methyl chloride group and reacting the resin with methyl chloride group with an amine material to attach an amine group to the resin with methyl chloride group It comprises a, the organic solvent is dichloroethene (DCE), the alkyl halide material is chloromethyl methyl ether (CMME), the reaction catalyst is characterized in that the iron chloride (FeCl ₃ ).

After attaching the amine group, the resin to which the amine group is attached may be reacted with sodium hydroxide to convert the ionic form of the resin from Cl ⁻ to OH ⁻ .

The resin having a methyl chloride group formed through the chloromethylation reaction was swelled in an organic solvent, and a ferric chloride (FeCl ₃ ) reaction catalyst was added thereto to form pores on the surface of the resin through a high crosslinking reaction. It is characterized by expanding the specific surface area, and the organic solvent uses dichloroethene (DCE).

In the high crosslinking reaction, the iron chloride is added 35 to 45wt% relative to the CMized resin, and the reaction temperature in the high crosslinking reaction is 60 to 80 ° C. In addition, the amine material is a tertiary amine, the tertiary amine includes trimetalamine (TMA), dimethylethylamine (DMEA).

The ion exchange resin according to the present invention induces a chloromethylation reaction by mixing a styrene monomer and divinylbenzene in an aqueous solution to form a polymer bead, and mixing the polymer bead, an alkyl halide material and a reaction catalyst in an organic solvent. By preparing a resin having a methyl chloride group, reacting the resin having a methyl chloride group with an amine material, attaching an amine group to the resin having a methyl chloride group, and through the chloromethylation reaction Expanding the specific surface area of the resin by swelling the formed resin with methyl chloride group in an organic solvent and adding a ferric chloride (FeCl ₃ ) reaction catalyst to form pores on the surface of the resin through a high crosslinking reaction, and is reacted with sodium hydroxide, the amine group attached to the resin, the ionic form of the resin Cl ^- conversion into ^- OH in It is characterized in that it is formed through the process.

The ion exchange resin and its manufacturing method according to the present invention has the following effects.

By optimizing the combination of the organic solvent, the alkyl halide material, and the reaction catalyst in the chloromethylation reaction to swell the polymer beads, the formation of the methyl chloride group can be maximized, and a high functional group ion exchange resin can be prepared.

In addition, by applying dichloroethene (DCE) and iron chloride as organic solvents and reaction catalysts to CM resins, high cross-linking reactions are induced to maximize the specific surface area of ion exchange resins, thereby increasing the ion exchange capacity of ion exchange resins. You can.

1 is a process reference diagram for explaining a method for producing an ion exchange resin having a high density of functional groups.
2 is a process reference diagram for explaining a method for producing an ion exchange resin having a high specific surface area.
Figure 3a and Figure 3b is a reference diagram showing the pore size distribution before and after the high cross-linking reaction of the gel-form CMized resin.
Figure 4 also shows the specific surface area analysis results according to the reaction time of the high cross-linking reaction of the gel-form CMized resin.
5 is a reference diagram showing the results of the specific surface area analysis according to the catalytic amount change of the high cross-linking reaction of the gel-form CMized resin.
6 is an electron microscope (SEM) image before and after the reaction of the gel-form CMized resin.
Figure 7 is a reference diagram showing the results of the specific surface area analysis according to the reaction time and the amount of catalyst changes in the high crosslinking reaction of the pore-form CMization resin.

The present invention maximizes the efficiency of methyl chloride group generation by applying an optimal organic solvent, alkyl halide material and reaction catalyst during the chloromethylation reaction, thereby producing a highly functional ion exchange resin. It features. In addition, after the chloromethylation reaction, using a dichloroethene (DCE, dichloroethane) and a metal chloride to induce the Friedel-Crafts reaction has another feature to prepare a high specific surface ion exchange resin. Dichloroethene (DCE) as an organic solvent, chloromethylmethyl ether (CMME) as an alkyl halide material, and zinc chloride (ZnCl) as a reaction catalyst to maximize the production efficiency of methyl chloride during chloromethylation reaction ₂ ), a metal chloride such as iron chloride (FeCl ₃ ) may be used.

Hereinafter, an ion exchange resin and a method of manufacturing the same according to the present invention will be described in detail with reference to the accompanying drawings. As described above, the present invention is characterized in the production of an ion exchange resin having a high density functional group and an ion exchange resin having a high specific surface area, Figure 1 is a process for explaining a method for producing an ion exchange resin having a high density functional group 2 is a reference diagram for explaining a method of preparing an ion exchange resin having a high specific surface area.

First, the manufacturing method of the ion exchange resin which has a high density functional group is demonstrated. Referring to Figure 1, the production method of the ion exchange resin having a high-density functional group according to the present invention is largely 1) the polymerization reaction of styrene and divinylbenzene, 2) chloromethylation reaction of polymer beads, 3) amination Reaction, 4) OH regeneration.

The above-mentioned 1) polymerization reaction of styrene and divinylbenzene is a reaction in which a styrene monomer and divinylbenzene are mixed in an aqueous solution to form polymer beads. The aqueous solution in which the styrene monomer and the divinylbenzene are mixed is reacted for 12 hours or more at a temperature of 70 to 90 ° C, and the polymer beads generated after the reaction are dried after washing with water.

Subsequently, the chloromethylation reaction of the polymer beads is performed 2). Specifically, in order to swell the polymer beads formed through the polymerization reaction of styrene and divinylbenzene, the polymer beads are placed in an organic solvent and mixed with an alkyl halide material. The alkyl halide material serves to form an alkyl halide group in the benzene ring of the polymer bead, and the alkyl halide group serves to partially substitute and bind an amine group in a subsequent amination reaction. Chloromethylmethyl ether (CMME) is used as the alkyl halide material.

In this state, a reaction catalyst, that is, metal chloride, is added to the organic solvent to induce the chloromethylation reaction. Iron chloride (FeCl ₃ ) or zinc chloride (ZnCl ₂ ) is used as the metal chloride. Through the catalytic reaction by the metal chloride, the alkyl halide group of the benzene ring is converted into a methyl chloride group (CH ₂ Cl ⁻ ), and a resin having a methyl chloride group is completed. After the chloromethylation reaction is completed, the organic solvent is heated to a predetermined temperature or more to remove dichloroethene (DCE) and chloromethylmethyl ether (CMME), and the resin with methyl chloride group is washed with water and dried. The resin provided with the methyl chloride group will hereinafter be referred to as 'chloromethylated resin'.

In order to provide a high-density functional group in the ion exchange resin, the adhesion efficiency of the amine group should be increased. In order to increase the adhesion efficiency of the amine group, the production efficiency of the methyl chloride group should be improved. In order to increase the production efficiency of methyl chloride group, in the present invention, as described above, dichloroethene (DCE) is an organic solvent that swells the polymer beads, the alkyl halide material is chloromethylmethyl ether (CMME), and the reaction catalyst is chloride. The use of metal is indicated. Experiments confirmed that the reaction efficiency of the chloromethylation reaction is maximized when the combination of dichloroethene (DCE), chloromethylmethyl ether (CMME) and metal chlorides (particularly, iron chloride) is maximized.

In the state where CMization resin is completed, the said 3) amination reaction is performed. Amination reaction is reaction which makes an amine group adhere to the benzene ring of CMization resin. In detail, the CMized resin formed through the chloromethylation reaction is mixed with room temperature water and NaCl, and then additionally added toluene to swell the CMized resin at 50 to 70 degrees. Subsequently, after lowering the temperature to room temperature again, the amine material is mixed, and the temperature is again raised to 50 to 70 degrees and then reacted for 4 hours or more. Through the amination reaction, the chlorine group (Cl ⁻ ) of the methyl chloride group of the CM resin is substituted with an amine group (N (CH ₃ ) ₃ ⁺ ), and the chlorine group (Cl ⁻ ) is an amine group (N (CH _3). ) Weakly combined with ₃ ⁺ ). When the amination reaction is completed, heating to a predetermined temperature or more to remove toluene and unreacted amine, and the resin is washed with water and dried.

On the other hand, as the amine material in the amination reaction can be used both primary amine, secondary amine, tertiary amine, considering the selectivity of the phosphate ions and nitrate ions of the ion exchange resin, tertiary amines, that is, trimethylamine ( TMA) or dimethylethylamine is preferred.

After the amination reaction, the 4) OH regeneration reaction proceeds. The OH regeneration reaction converts the ionic form of the resin that has undergone an amination reaction from Cl ⁻ to OH ⁻ . When the aminated resin is reacted with sodium hydroxide, the ionic form of the resin is converted from Cl ⁻ to OH ⁻ . The reason why the ion type of the resin is converted from Cl ⁻ to OH ⁻ is because the OH type resin has better ion exchange performance for anions than the Cl type resin.

In the above, the manufacturing method of the ion exchange resin which has a high density functional group was demonstrated. Next, a method for producing an ion exchange resin having a high specific surface area will be described.

The method for producing an ion exchange resin having a high specific surface area is basically a method for producing an ion exchange resin having a high density of functional groups, that is, 1) polymerization reaction of styrene and divinylbenzene, 2) chloromethylation reaction of polymer beads, The process of 3) amination reaction, 4) OH regeneration reaction is applied, and additional chemical reaction is applied between 2) chloromethylation reaction of polymer beads and 3) amination reaction.

Specifically, 2) in the state in which the CM-ized resin is prepared through the chloromethylation reaction of the polymer beads, the specific surface area of the resin is expanded through the hypercrosslinking reaction based on the Friedel-Crafts reaction (FIG. 2).

Looking at the specific process is as follows. First, the CMized resin formed by the chloromethylation reaction is put in a dichloroethene (DCE) solvent and swelled at room temperature for 2 hours or more. In addition to the dichloroethene (DCE) solvent, hexane (hexane), chlorobenzene may be used as an organic solvent. Subsequently, iron chloride (FeCl ₃ ) is added to the organic solvent as a reaction catalyst and mixed at a temperature of 10 degrees or less for 2 hours or more. Then, the temperature is raised to 50 degrees or more and reacted for 30 minutes to 24 hours. Through the reaction, the hydrogen chloride (HCl) component of the methyl chloride group is separated and the remaining carbon (C) component is adsorbed to the other benzene ring. By this reaction, many pores are formed on the surface of the CM resin, and thus the specific surface area is ultimately increased. Is expanded. In the above reaction, dichloroethene (DCE) is most effective as an organic solvent for resin swelling, and reaction efficiency is highest when iron chloride (FeCl ₃ ) is used as a reaction catalyst. After completion of the reaction, the organic solvent and the reaction catalyst are washed well in order of methanol, acetone (including 0.5 M HCl) and methanol, and then the resin is washed with water and dried. The dried resin undergoes an amination reaction and an OH regeneration reaction.

On the other hand, during the high crosslinking reaction, the reaction catalyst, that is, iron chloride is added 35 ~ 45wt% compared to the CM resin. As the amount of the reaction catalyst decreases, the specific surface area of the resin decreases. When the amount of the reaction catalyst is less than 35wt% compared to the CM resin, the specific surface area increases little, and at 45wt%, the specific surface area is saturated. Moreover, reaction temperature is 60-80 degreeC, and reaction time converges to the highest value in 12 hours or more. When the reaction temperature is 80 ° C or higher, the structure of the resin is destroyed, and when it is 60 ° C or lower, pore formation is limited. The gel-type resin has a higher specific surface area after the reaction than the porous resin, which is considered to be due to the chloromethylation reaction of the gel-type resin better than the porous resin.

In the above, the manufacturing method of the ion exchange resin which has high density functional group which concerns on this invention, and the manufacturing method of the ion exchange resin which have high specific surface area were demonstrated. Hereinafter, the production of the ion exchange resin and the characteristics of the prepared ion exchange resin according to an embodiment of the present invention will be described.

≪ Example 1 >

Styrene and divinylbenzene were mixed in an aqueous solution, and then reacted in the reactor at 50 ° C. for at least one day. The polymer beads produced after the reaction were washed with water and dried. 100 g of the obtained polymer beads were poured into a dichloroethene (DCE) solvent and swelled. At the same time, 200 g of chloromethyl methyl ether (CMME) was added and mixed at a low temperature. In general, 40 g of iron chloride (FeCl ₃ ) catalyst was added instead of the zinc chloride (ZnCl ₂ ) catalyst used in the chloromethylation reaction, and the reaction was performed for about one day. After the reaction, the reactor temperature was lowered and water was added to terminate the reaction. Next, the reactor temperature was heated to 95 degrees or more to remove the remaining chloromethyl methyl ether after the reaction with dichloroethene as a solvent, and the resin was washed with clean water to prepare a CM-functionalized resin functionalized with methyl chloride group. After drying the functionalized CM chloride resin with methyl chloride group, the weight was 152 g, which was 52 g higher than before reaction, which was about 25% of 200 g of chloromethyl methyl ether added to the reaction.

<Example 2>

A high crosslinking reaction was performed on a gel type CM resin with a methyl chloride group attached thereto. 5 g of the gel-type CM resin prepared in Example 1 was added to 40 ml of dichloroethene (DCE) and swelled at room temperature for 2 hours. Next, ₂ g of FeCl ₃ was added and mixed well for 2 hours or more at a temperature of 10 degrees or less. Then, the reaction was carried out under the conditions of the following I, II, III.

I) The reactor temperature was set at 60, 70, 80 degrees and reacted with stirring for 24 hours to see the effect on the reaction temperature.

II) The reaction was carried out for 30 minutes to 24 hours at 70 degrees to see the effect on the reaction time.

Ⅲ) To see the effect on the amount of catalyst, the reaction temperature was set to 70 degrees, the reaction time was set to 24 hours and the amount of iron chloride was changed from 2 g to 0.2 g per 5 g of the resin.

After completion of the reaction, wash the resin thoroughly with methanol and acetone (including 0.5 M HCl) to prevent dichloroethene and iron chloride from remaining in the resin, and then use the resin at 80 ° C for specific surface area (BET) analysis. After sufficient drying in a vacuum oven, specific surface area analysis was performed using a Micromeritics ASAP 2010 instrument.

The reaction temperature by BET value of CM resin of gel increased with the specific surface area value of the temperature after the high-ranking cross-linking reaction of the reaction around 0.8 m ² / g up to a maximum of 1,200 ~ 1,300 m ² / g. At 78 degrees, some of the resins fractured during the reaction, resulting in a relatively low specific surface area value (468 m ² / g). Gel-type CMized resins also produced nanopores (nanopores) after the reaction, and the increase in specific surface area was determined by nanopores (see FIGS. 3A and 3B).

The reaction time was changed from 30 minutes to 24 hours, and then the BET value was analyzed. A BET value of up to 1,392 m ² / g was obtained and the reaction was found to saturate within 12 hours (see FIG. 4). The reaction occurred rapidly at the beginning of the high-crosslinking reaction of the ion exchange resin, and obtained a BET value of 921 m ² / g, which is 66% of the maximum value at 30 minutes.

After the reaction temperature was fixed at 70 ° C and the reaction time was set to 24 hours, the amount of catalyst (FeCl ₃ ) was changed. When the amount of catalyst per 5g of resin was lowered to 2g or less, the specific surface area of the resin was lowered after the reaction. When using 0.2 g of catalyst at 1/10 level, a BET value of 526 m ² / g was obtained, which is 41% of the maximum value (see FIG. 5).

The surface of the gel-type CMized resin before and after the high crosslinking reaction was observed using an electron microscope (SEM) and an optical microscope. As a result of observing the surface of the resin by magnification of up to 200,000 times through an electron microscope (SEM), it was confirmed that the surface of the resin was roughly roughened by a high crosslinking reaction, and no crack was found on the surface of the resin (see FIG. 6). ). As a result of observing a plurality of resins using an optical microscope, no cracks were found on the surface of the resin after the reaction, and the size of the resin was also 200 ~ 600 ㎛, which was not different from before the reaction.

<Example 3>

The high crosslinking reaction was carried out in the same manner as in Example 2 with respect to the porous CMized resin having a methyl chloride group attached to the inside prepared in Example 1. The BET value for the reaction temperature of the pore-type CM resin was obtained at a maximum specific surface area of 1,269 m ² / g at 80 degrees, which is somewhat lower than the maximum specific surface area of 1,400 m ² / g after the reaction of the gel type resin. It is presumed that the density of the methyl chloride group attached to the CM-type CM resin is somewhat lower than that of the gel-type CM resin. In the effect of the reaction according to the reaction time, it is judged that the reaction is saturated within 12 hours as in the gel type CMized resin (see FIG. 7A). In the effect of the catalyst amount change, the specific surface area of the pore-type resin was less than that of the gel-type CM resin, and the specific surface area value of 1,000 m ² / g or more was used when 0.5g of catalyst per 5g of resin was used. (See FIG. 7B).

When other Lewis acid catalysts (AlCl ₃ , ZnCl _2, etc.) were used in addition to the iron chloride catalyst used in the high crosslinking reaction, the specific surface area of the resin after the reaction was less than 100 m ² / g, which was significantly lower than that of the iron chloride catalyst. .

<Example 4>

The high specific surface area resin prepared in Example 3 was again subjected to the chloromethylation reaction performed in Example 1, followed by an amination reaction to introduce an amine group into the CMized resin. First, 100 g of CMized resin was added to a reactor, and water was sufficiently added, followed by stirring for 1 hour. Next, 100 g of an organic solvent was added thereto, and the resin was swollen at a temperature of 30 degrees or more. After lowering the temperature again, trimethylamine (trimethyl amine, TMA) 200g was added, the amination reaction was performed at 70 degrees or more, the temperature was cooled again, and water was added to terminate the reaction. To remove the organic solvent and residual amine (TMA), water was added to the reactor, heated at 95 ° C. or more, and then cooled slowly to wash and dry the resin. Finally, Cl-type anion exchange resin was prepared in which the trimethylamine was covalently attached to the phenyl group of the resin and the ion was equilibrated with the trimethylamine as the counter ion. It was about 55% in 200 g of trimethylamine added to the reaction. The average particle size of the prepared ion exchange resin was about 0.5 mm.

Example 5 Ion Exchange Experiment

Embodiment the three anions commonly present in the wastewater by applying a resin of high specific surface area of the produced pore type in Example ^{_{4 (PO 4 3-, NO 3}} -, F -) continuous to increase the ion exchange capacity and selectivity for Ion exchange experiments were performed. First, the prepared resin was filled in a column before the ion exchange reaction experiment, and the ion type was changed from Cl type to OH type using 8% caustic soda (NaOH). In particular, three kinds of phosphate ions of the anion (PO ₄ ^3- -P) and nitrate ions (NO ₃ ^- -N) is anion deulyimyeo fluoride ion (F ^-) that must be removed during the treatment, so causing eutrophication and cyanosis For manufacturing The selected resin was selected to confirm the increase in selectivity for phosphate ions and nitrate ions. In addition, the experiment was carried out by simultaneously applying the same pore type of resin sold commercially for comparison with the ion exchange resin produced through the present invention. The stock solution was prepared using KH ₂ PO ₄ , KNO ₃ , NaCl, NaF, and CaCl ₂ reagents in secondary distilled water, and then diluted with secondary distilled water in the experiment to obtain the desired final concentration (20 mg / L each). Used after lowering. Anion exchange resins were charged to the column (100 mL total volume) at 30% (v / v), and then subjected to external pressure to minimize the size of the pores between the resins. The flow rate was fixed at 1 bed volume (30 mL) per minute using a metering pump at the bottom of the column so that the solution containing the anions connected to the top of the column was continuously discharged. In performing the ion exchange experiment, the concentration of anions in the effluent was analyzed using Ion Chromatography (IC) instrument to check the ion exchange capacity for each anion exchanged by the resin. The ion exchange capacity was converted in consideration of the removal amount based on the initial amount of anion, and when the volume of the resin injected into the column was 1 bed volume, the solution corresponding to 3,000 bed volume was passed through the column filled with resin. The exchange capacity of the resin for each anion was calculated. The final ion exchange capacity for each anion was calculated in consideration of the amount and molecular weight of anion removed per 1 g of ion exchange resin prepared.

Referring to Table 1, the high specific surface area resin prepared in the present invention showed an ion exchange capacity of about 4.1 times higher for phosphate ions and an ion exchange capacity of about 6.1 times higher for nitrate ions than commercial resins. This was due to the improved ion exchange performance of the resin due to the increase in specific surface area and density of the amine group, the ion exchange group. However, for fluorine ions, the ion exchange capacity of the resin prepared in the present invention was found to be only 1.4 times higher than that of a commercial resin, indicating higher selectivity for phosphoric acid and nitric acid. Therefore, the ion exchange resin prepared in the present invention shows high efficiency due to the high specific surface area and high selectivity for phosphate ions and nitrate ions. Due to these characteristics, it is effective to remove phosphate ions and nitrate ions in the water system. It was confirmed that it can be applied.

 Comparison of Ion Exchange Capacity for Anions
Resin Type
Ion exchange capacity for each anion per resin weight
(mg anion / g resin) F- NO ₃ ^-- N PO ₄ ^3- -P Sample 1: Commercial Ion Exchange Resin 19.6 24.1 27.0 Sample 2: ion exchange resin of the present invention 27.7 148.1 109.7

Claims (8)

Mixing styrene monomer and divinylbenzene in an aqueous solution to form polymer beads;
Preparing a resin having a methyl chloride group by inducing a chloromethylation reaction by mixing the polymer beads, an alkyl halide material and a reaction catalyst in an organic solvent; And
Reacting the resin with the methyl chloride group with an amine material to attach the amine group to the resin with the methyl chloride group,
The organic solvent is dichloroethene (DCE), the alkyl halide material is chloromethyl methyl ether (CMME), the reaction catalyst is iron chloride (FeCl ₃ ) method of producing an ion exchange resin, characterized in that.
According to claim 1, After the step of attaching the amine group,
A method of producing an ion exchange resin, characterized by further comprising the step of reacting a resin with an amine group with sodium hydroxide to convert the ionic form of the resin from Cl ⁻ to OH ⁻ .
The method of claim 1, wherein the resin having a methyl chloride group formed through the chloromethylation reaction,
A method of producing an ion exchange resin, characterized by expanding the specific surface area of a resin by swelling in an organic solvent and adding a ferric chloride (FeCl ₃ ) reaction catalyst to form pores on the surface of the resin through a high crosslinking reaction.
The method of claim 3, wherein the organic solvent is dichloroethene (DCE).
[4] The method of claim 3, wherein the ferric chloride is added in an amount of 35 to 45 wt% with respect to the CMized resin during the high crosslinking reaction.
The method of claim 3, wherein the reaction temperature during the high crosslinking reaction is 60 ~ 80 ℃ manufacturing method of the ion exchange resin.
The method of claim 1, wherein the amine material is a tertiary amine, and the tertiary amine comprises trimetalamine (TMA) and dimethylethylamine (DMEA).
A process of forming a polymer bead by mixing a styrene monomer and divinylbenzene in an aqueous solution, and inducing a chloromethylation reaction by mixing the polymer bead, an alkyl halide material, and a reaction catalyst in an organic solvent, thereby preparing a methyl chloride group. Preparing a resin, reacting the resin with the methyl chloride group with an amine material, attaching an amine group to the resin with the methyl chloride group, and preparing the resin with the methyl chloride group formed through the chloromethylation reaction. Swelling in an organic solvent and adding a ferric chloride (FeCl ₃ ) reaction catalyst to form pores on the surface of the resin through a high crosslinking reaction to expand the specific surface area of the resin, and to add amine-containing resin to sodium hydroxide and reacting, the ion type of the resin Cl ^- specific being formed in a process for converting a ^- OH in Ion exchange resin made with gong.

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