KR102048978B1 - Non-agglomerating mixed bed ion exchange resin and method for preparing the same - Google Patents

Abstract

The present invention includes a cation exchange resin and an anion exchange resin pretreated with a specific water soluble cation polymer electrolyte and a specific water soluble anion polymer electrolyte, so that the cation exchange resin and the anion exchange resin can be easily separated without agglomeration between each other, The present invention relates to a non-aggregated mixed layer ion exchange resin having low total organic carbon (organic matter) elution and not falling in specific resistance, and a method of manufacturing the same.

Description

NON-AGGLOMERATING MIXED BED ION EXCHANGE RESIN AND METHOD FOR PREPARING THE SAME}

The present invention includes a cation exchange resin pretreated with a specific water soluble cationic polyelectrolyte and an anion exchange resin pretreated with a specific water soluble anionic polyelectrolyte so that the cation exchange resin and the anion exchange resin can be easily separated without agglomeration between each other. The present invention relates to a non-aggregated mixed layer ion exchange resin having a low total organic carbon (organic substance) elution and a low specific resistance, and a method for producing the same.

Mixed layer (or mixed phase) ion exchange resins are used for the purpose of removing ionic impurities from liquids in the electronics industry, thermal power plants, and nuclear power plants. The mixed layer ion exchange resin is a cation exchange resin and an anion exchange resin filled in the same resin bottom.

By the way, when a cation exchange resin and an anion exchange resin are filled in the same tower, these resins are entangled with each other and it is known that aggregation arises. When such agglomeration occurs, problems such as channeling of the resin (a phenomenon in which the resin filled due to the fixation of the cation exchange resin and the anion exchange resin does not become the maximum filling and the volume expands) or mutual surface contamination occur.

In order to prevent such aggregation, various methods are examined. First, a method of coating a surface of an anion exchange resin has been developed. For example, Japanese Patent Publication No. 1998 (Pyeongsung 10) -156194 discloses an anion exchange pretreated by contact with a sulfonated poly (vinyl aromatic) polymer electrolyte. A resin and a mixed phase ion exchange resin using the same are disclosed. However, when the sulfonated poly (vinyl aromatic) polyelectrolyte is coated on the anion exchange resin, aggregation does not occur, but a large amount of total organic carbon (organic matter) is eluted, and the specific resistance decreases. There is a problem that the exchange resin is not easily separated.

As an example of coating a cation exchange resin, Japanese Patent Laid-Open No. 1982 (Digestion 57) -21978 describes a strong acidity treated with a cationic polymer electrolyte in a plurality of boiler treatment methods of passing boiler plurality to a mixed-bottom ion exchange resin device. A technique characterized by using a cation exchange resin is disclosed. In addition, Japanese Patent Laid-Open No. 1998 (Pyung Hwa 10) -202118 discloses an ion exchange resin formed by attaching a linear polymer electrolyte having a molecular weight of 50,000 or more to the surface. However, these documents only describe the cationic polyelectrolyte, and the compounds which are exemplified are the primary to tertiary amines to quaternary ammonium groups directly or through alkyl groups of polystyrenes such as poly (trimethyl ammonium methylstyrene) or the like. Combined form; And primary to tertiary amines to quaternary ammonium groups bound to polymers of (meth) acrylic acid, such as vinyl pyridine or derivatives thereof, or poly (methacryl oxyethyl trimethyl ammonium), through ester bonds or amide bonds. In addition, Japanese Patent Laid-Open No. 1980 (Digestion 55) -67539 discloses a technique characterized by pretreating a cation exchange resin with a water-soluble cationic polymer electrolyte containing a quaternary amine structure.

However, according to the researches of the present inventors, the cation exchange resin treated with these compounds has a problem that many total organic carbons (organic matters) are eluted, the specific resistance decreases, and the cation exchange resin and the anion exchange resin are not easily separated. Does not cause problems.

The present invention includes a cation exchange resin pretreated with a specific water soluble cationic polyelectrolyte and an anion exchange resin pretreated with a specific water soluble anionic polyelectrolyte so that the cation exchange resin and the anion exchange resin can be easily separated without agglomeration between each other. It is a technical object of the present invention to provide a non-aggregated mixed layer ion exchange resin having a low elution of total organic carbon (organic matter) and a low specific resistance, and a method for producing the same.

One embodiment of the present invention to solve the above technical problem, a) an anion exchange resin pretreated with a water-soluble anionic polymer electrolyte having a sulfonated structure; And b) a cation exchange resin pretreated with a water soluble cationic polymer electrolyte having a quaternary ammonium salt structure.

Another embodiment of the present invention, a pre-treatment step of the anion exchange resin coating the anion exchange resin with a water-soluble anionic polymer electrolyte having a sulfonated structure; And a pretreatment step of the cation exchange resin which coats the cation exchange resin with a water-soluble cation polymer electrolyte having a quaternary ammonium salt structure.

The mixed layer ion exchange resin according to the present invention can be completely separated without clumping between the cation exchange resin and the anion exchange resin, and in particular, the total organic carbon (organic matter) eluted from the polymer electrolyte coated on the cation exchange resin and the anion exchange resin. This low, no drop in specific resistance shows an excellent effect compared to the mixed layer ion exchange resin produced by a general treatment method.

Hereinafter, the present invention will be described in more detail.

A non-cohesive mixed layer ion exchange resin according to the present invention includes a) an anion exchange resin pretreated with a water-soluble anionic polyelectrolyte having a sulfonated structure; And b) a cation exchange resin pretreated with a water soluble cationic polyelectrolyte having a quaternary ammonium salt structure.

In addition, the method for producing a non-aggregated mixed layer ion exchange resin according to the present invention comprises the steps of pre-treatment of an anion exchange resin coating the anion exchange resin with a water-soluble anionic polymer electrolyte having a sulfonated structure; And pretreatment of the cation exchange resin with the cation exchange resin coated with a water soluble cationic polymer electrolyte having a quaternary ammonium salt structure.

The water soluble anionic polyelectrolyte having a sulfonated structure used in the present invention can be used in free acid form or in the form of a water soluble salt such as, for example, sodium, potassium or ammonium salts. Specifically, the water-soluble anionic polyelectrolyte having a sulfonated structure may be a copolymer of acrylic acid and sulfonated acrylamide, preferably a copolymer of acrylic acid and acrylamide methylpropane sulfonic acid, and more preferably, It may be a compound having a structural unit represented by 1.

[Formula 1]

In Formula 1, n and m each independently represent an integer of 1 to 10.

The water-soluble anionic polymer electrolyte may be a copolymer of acrylic acid and sulfonated acrylamide in a molar ratio of 2:98 to 98: 2, but is not limited thereto.

The water-soluble anionic polymer electrolyte useful in the practice of the present invention has a number average molecular weight (Mn) in the range of 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 12,000 to 200,000, most preferably 15,000 to 100,000. Number average molecular weights are based on aqueous phase gel permeation chromatography (GPC) using suitable molecular weight standards.

In addition, the water-soluble cationic polyelectrolyte having a quaternary ammonium salt structure used in the present invention may be used in the form of a free acid or in the form of a water-soluble salt such as, for example, chloride, hydroxide or ammonium salt. Specifically, the water-soluble cationic polyelectrolyte having a quaternary ammonium salt structure may be a compound having an intramolecular cyclic quaternary ammonium salt structure, preferably a copolymer of an intramolecular cyclic quaternary ammonium salt and acrylamide, more preferably. Preferably it may be a copolymer of diallyldimethylammonium and acrylamide, and even more preferably, may be a compound having a structural unit represented by the following formula (2).

[Formula 2]

In Formula 2, x and y each independently represent an integer of 1 to 10.

The water soluble cationic polymer electrolyte may be copolymerized acrylamide and diallyldimethylammonium in a molar ratio of 2:98 to 98: 2, but is not limited thereto.

The water-soluble cationic polymer electrolyte useful in the practice of the present invention has a number average molecular weight ranging from 10,000 to 1,000,000, preferably 12,000 to 500,000, more preferably 15,000 to 200,000, most preferably 20,000 to 150,000. Number average molecular weights are based on aqueous phase gel permeation chromatography (GPC) using suitable molecular weight standards.

As used herein, “pretreated with a water soluble cationic polyelectrolyte” or “pretreated with a water soluble anionic polyelectrolyte” reduces the surface charge of a cation exchange resin or an anion exchange resin by pretreatment with a water soluble cationic polymer electrolyte or a water soluble anionic polymer electrolyte. It means to let.

The pretreatment method of the anion exchange resin by the water soluble anion polymer electrolyte may be any method capable of adhesion of the water soluble anion polymer electrolyte without decomposition of the anion exchange resin. For example, there is a method in which an aqueous solution containing a water-soluble anionic polymer electrolyte and an anion exchange resin is added to the reactor so that they are in proper contact with each other. One of the possible ways of bringing them into contact can include slow stirring of the water soluble anionic polyelectrolyte, anion exchange resin and water in the reactor. Part or all of the surface of the anion exchange resin is coated by contact with a water soluble anionic polyelectrolyte. The anion exchange resin is preferably sufficiently coated with a water-soluble anionic polymer electrolyte so as not to decrease the anion exchange capacity by adjusting the molecular weight and the amount of coating of the water-soluble anion polymer electrolyte.

Likewise, the pretreatment method of the cation exchange resin with the water soluble cationic polymer electrolyte may be any method capable of adhesion of the water soluble cationic polymer electrolyte without decomposition of the cation exchange resin. For example, there is a method in which an aqueous solution containing a water soluble cationic polymer electrolyte and a cation exchange resin is added to the reactor so that they are in proper contact with each other. One of the possible ways of bringing them into contact can include slow stirring of the water soluble cationic polyelectrolyte, cation exchange resin and water in the reactor. Part or all of the cation exchange resin surface is coated by contact with a water soluble cationic polyelectrolyte. The cation exchange resin is preferably sufficiently coated with a water soluble cationic polymer electrolyte to control the molecular weight and the amount of coating of the water soluble cationic polymer electrolyte so that the cation exchange capacity is not lowered.

The throughput of the water soluble anionic polyelectrolyte should be an amount suitable to reduce the surface charge represented by the anion exchange resin beads, in particular a medium amount of the water soluble anionic polyelectrolyte. The range is 10 to 500 mg, preferably 15 to 150 mg, most preferably 20 to 100 mg per liter of anion exchange resin. The pretreatment temperature is in the range of 25 to 80 ° C, preferably 25 to 40 ° C. The pretreatment period depends on the pretreatment temperature, but the range is generally 0.1 to 24 hours, preferably 0.5 to 2 hours. The anion exchange resin is washed with an appropriate amount of deionized water after pretreatment.

The added water soluble anionic polymer electrolyte substantially adheres quantitatively to the anion exchange resin. Therefore, the coating amount of the water-soluble anion polyelectrolyte is in the range of 10 to 500 mg, preferably 15 to 150 mg, more preferably 20 to 100 mg per liter of the anion exchange resin.

The throughput of the water soluble cationic polyelectrolyte should be in an amount suitable to reduce the surface charge represented by the cation exchange resin beads, in particular moderate amount of the water soluble cationic polyelectrolyte. The range is 10 to 500 mg, preferably 15 to 150 mg, most preferably 20 to 100 mg per liter of cation exchange resin. The pretreatment temperature is in the range of 25 to 80 ° C, preferably 50 to 60 ° C. The pretreatment period depends on the pretreatment temperature, but the range is generally 0.1 to 24 hours, preferably 0.5 to 2 hours. The cation exchange resin is washed with an appropriate amount of deionized water after pretreatment.

The water soluble cationic polymer electrolyte added substantially adheres quantitatively to the cation exchange resin. Therefore, the coating amount of the water-soluble cationic polymer electrolyte is in the range of 10 to 500 mg, preferably 15 to 150 mg, more preferably 20 to 100 mg per liter of the cation exchange resin.

In this specification, the term "ion exchange resin" is a term generally used in the art. Generally, this refers to a gel type or macroreticular type of ion exchange resin, which may be a weakly acidic or strongly acidic cation exchange resin, or a weakly basic or strongly basic anion exchange resin. The type of cation exchange resin or anion exchange resin in the present invention is not particularly limited, and known resins used in the art may be used.

The cation exchange resin and the anion exchange resin are, for example, a monovinylidene aromatic crosslinked polymer or a (meth) acrylic acid ester crosslinked polymer. Specific examples are resins derived from crosslinkers capable of copolymerizing with monovinylidene aromatic monomers such as styrene or vinyl toluene, and resins derived from crosslinkers capable of copolymerizing with acrylic acid monomers such as acrylic acid or methacrylic acid. Preferred crosslinkers are di- or polyvinylidene aromatic reagents such as divinyl benzene and divinyl toluene or ethylene glycol dimethacrylate.

Strongly acidic cation exchange resins have sulfonic acid groups as functional groups, and weakly acidic cation exchange resins have carboxylic acid groups, phosphinic acid groups, phenoxide groups and the like as functional groups. Strongly basic anion exchange resins have quaternary ammonium groups as functional groups, and weakly basic anion exchange resins have primary amino groups, secondary amino groups or tertiary amino groups as functional groups.

The mixed layer ion exchange resin according to the present invention may preferably contain a strongly acidic cation exchange resin and a strong basic anion exchange resin. The strongly acidic cation exchange resin may preferably be a monovinylidene aromatic crosslinked polymer containing sulfonic acid groups, with sulfonated compounds of a monovinylidene aromatic compound and a copolymerizable crosslinking agent particularly preferred. The strong basic anion exchange resin may preferably be a crosslinked polymer of monovinylidene aromatic compounds with quaternary ammonium groups. Among the preferred cation exchange resins and anion exchange resins, the preferred monovinylidene aromatic compound is styrene, and the preferred crosslinking agent is vinyl benzene.

The cation or anion exchange resin used in the present invention can typically be prepared in the form of polymer beads having an average volume particle diameter in the range of about 0.15 to about 1.2 millimeters (mm), preferably about 0.4 to about 0.7 mm.

Commercially available representative cation exchange resins suitable for use in the mixed bed ion exchange resins of the present invention are, for example, Trilite ™ MC-08H or Trilite ™ MC-10H. Typical representative anion exchange resins suitable for use in the mixed bed ion exchange resins of the present invention are, for example, Trilite ™ MA-12OH or Trilite ™ MA-10OH. Trilite is a trademark of Samyang Corporation

In the mixed layer ion exchange resin of the present invention, the filling rate of the cation exchange resin and the anion exchange resin may vary depending on the purpose of use of the ion exchange resin, but is generally 1/99 to 99/1 as the volume ratio of the cation exchange resin / anion exchange resin. , Preferably from 1/10 to 10/1, most preferably from 1/2 to 2/1.

As used herein, the term “reduce surface charge” means that the surface charge of the cation exchange resin beads is reduced in proportion to the surface charge of the untreated cation exchange resin by pretreatment of the cationic polymer electrolyte, or the surface of the anion exchange resin beads. This means that the charge is reduced in proportion to the surface charge of the untreated anion exchange resin by the pretreatment of the anionic polymer electrolyte The reduction of the surface charge of the pretreated, cation exchange resin or anion exchange resin is the pretreated cation exchange resin and the pretreated anion. This is evidenced by the reduction of aggregation (clumping) between the exchange resins.

In the present specification, aggregation can be readily measured using conventional techniques known to those skilled in the art. For example, known accumulations of cation exchange resins and anion exchange resins may be mixed, mixed layer resins may be deposited, and the volume of the deposited mixed layer resins may be measured. Agglomeration can be determined by increasing the volume of the mixed layer resin after comparing the total volume of the cation exchange resin and the anion exchange resin constituents.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

EXAMPLE

EXAMPLE  One

As a water soluble cationic polyelectrolyte Preprocessed  Preparation of Strong Acid Cation Exchange Resin

After filling 500 ml of deionized water in 2L reactor, 1L of strongly acidic cation exchange resin (trade name: Trilite MC-08H) was added, followed by a total of 17 mg of N, N-dimethyl-N-2-propenyl having a number average molecular weight of 120,000. -2-propene-1-aluminum chloride polymer 2-propeneamide [INCI Name: Polyquaternium-7] (manufactured by Lubrizol Chemical Co.) was dissolved in 50 ml of deionized water as a water-soluble cationic polyelectrolyte and introduced into the reactor. Strongly acidic cation exchange resin pretreated with a water soluble cationic polymer electrolyte by stirring for 30 minutes, then warming to 60 ° C., then stirring for 1 hour and then cooled to room temperature, and washing the strong acid cation exchange resin twice with 500 ml of deionized water through a filter. Got.

As a water-soluble anionic polyelectrolyte Preprocessed  Strong base anion exchange resin

500 ml of deionized water was charged in a 2 L reactor, and then 1 L of a strong basic anion exchange resin (trade name: Trilite MA-12OH) was added, followed by a total of 20 mg of acrylic acid-2-acrylamido-2-methyl having a number average molecular weight of 100,000. Propane sulfonic acid copolymer (AA / AMPS, manufactured by Shandong Taihe Water Treatment Technologies Co.) was dissolved in 50 ml of deionized water as a water-soluble anionic polyelectrolyte and introduced into the reactor. After stirring at 40 ° C. for 1 hour, a strong base anion exchange resin pretreated with a water soluble anion polymer electrolyte was obtained by washing the strong base anion exchange resin twice with 500 ml of deionized water through a filter.

Coagulation and Resolution  Test Methods

A volume of 250 ml of strongly acidic cation exchange resin was measured using a measuring cylinder, and the volume was measured while tapped and deposited under the water surface. A volume of 250 ml of strongly basic anion exchange resin was measured using a scalpel and the volume was measured while tapped and deposited under water. The two resins were each filled in a 1000 ml measuring cylinder equipped with a glass stopper. The mixed resin was allowed to settle and the total volume recorded. The volume increase from 500 ml filled is due to aggregation.

Analysis value: 500 (no aggregation)

How to check separation

This operation simulates the preparation of the mixed layer ion exchange resin, the initial use of the ultrapure water equipment of the mixed resin, and the resin separation by subsequent backwashing. A volume of 192 ml of strongly basic anion exchange resin was measured using a scalpel and the volume was measured while tapped and deposited under water. A volume of 128 ml of strongly acidic cation exchange resin was measured using a scalpel and the volume was measured while tapped and deposited under water.

The two resins were filled in a glass column having a 2 inch diameter. The resin was mixed with nitrogen gas at a flow rate of 4 L / min for 30 minutes. The mixed resin was then filled into a glass column of 2.5 cm in diameter. Ultrapure water (specific resistance 18.24 Mb.cm, Total Organic Carbon (TOC) 1.0 ppb) was flowed for 2 hours at SV (space velocity) 2 and then stopped to operate, and the resin was allowed to stand in the column for 10 hours. The mixed resin was then transferred to a 2 inch diameter glass backwash column. The interphase resin was backwashed with deionized water at a sufficient flow rate for 10 minutes until it doubled the filled resin height. The flow rate was reduced to zero. Water was drained to the bottom of the column at a rate of about 100 ml / min. The height from the column bottom and the total length of the bottom of the boundary between the cation resin and anion resin layers were recorded. The volume percentages of the anionic and cationic layers were calculated. Complete separation gives 60% by volume of the anionic layer by this test.

Resistivity and Total Organic Carbon ( TOC ) How to check

200 ml of the cation exchange resin of Example 1 and 300 ml of the anion exchange resin were mixed and filled into a column (30 mm in diameter). Since ultrapure water (Resistance: 18.24 MW.cm, Total Organic Carbon (TOC): 1.0 ppb) was flowed for 3 hours at a space velocity of 30, then the specific resistance and total organic carbon (TOC) were measured in real time.

EXAMPLE  2

Example, except that the content of N, N-dimethyl-N-2-propenyl-2-propene-1-aluminum chloride polymer 2-propeneamide having a number average molecular weight of 120,000 was changed from 17 mg to 60 mg In the same manner as in 1, a strongly acidic cation exchange resin pretreated with a water-soluble cationic polyelectrolyte was prepared.

In addition, a strong base anion exchange resin pretreated with a water-soluble anionic polymer electrolyte was prepared in the same manner as in Example 1.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

EXAMPLE  3

A strong base anion exchange resin pretreated with a water-soluble anionic polyelectrolyte was prepared in the same manner as in Example 1, except that the content of acetic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer was changed from 20 mg to 60 mg. It was.

In addition, a strongly acidic cation exchange resin pretreated with a water-soluble cationic polymer electrolyte was prepared in the same manner as in Example 1.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

Comparative example  One

In the same manner as in Example 1, a strong acid cation exchange resin pretreated with a water soluble cationic polymer electrolyte was prepared, and the strong base anion exchange resin was not pretreated with a water soluble anion polymer electrolyte.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

Comparative example  2

In the same manner as in Example 1, a strong base anion exchange resin pretreated with a water soluble anion polymer electrolyte was prepared, and the strong acid cation exchange resin was not pretreated with a water soluble cationic polymer electrolyte.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

Comparative example  3

A strong acid cation exchange resin and a strong base anion exchange resin were obtained in the same manner as in Example 1, except that both the strong acid cation exchange resin and the strong base anion exchange resin were not pretreated with a polymer electrolyte.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

Comparative example  4

After filling 500 ml of deionized water in a 2 L reactor, 1 L strong acid cation exchange resin (trade name: Trilite MC-08H) was added, and 17 mg of poly (4-vinyl pyridine) dissolved in 0.1 N sulfuric acid having a number average molecular weight of 14,000 was water-soluble cationic polymer. It was dissolved in 50 ml of deionized water as an electrolyte and introduced into the reactor. Thereafter, the mixture was stirred at 60 ° C. for 1 hour, and then cooled to room temperature. The strong acid cation exchange resin was pretreated with a water soluble cationic polymer electrolyte by washing the strong acid cation exchange resin twice with 500 ml of deionized water through a filter.

In addition, 500 ml of deionized water was charged into a 2L reactor, and then 1L of a strong base anion exchange resin (trade name: Trilite MA-12OH) was added, followed by 20 mg of sodium polystyrene sulfonate having a number average molecular weight of 10,000 in 50 ml of deionized water as a water-soluble anionic polymer electrolyte. Dissolved and added to the reactor. Thereafter, the mixture was stirred at 40 ° C. for 1 hour, followed by washing the strong basic anion exchange resin twice with 500 ml of deionized water through a filter to obtain a strong basic anion exchange resin pretreated with a water-soluble anionic polymer electrolyte.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

Comparative example  5

Strongly acidic cation exchange resin pretreated with a water-soluble cationic polymer electrolyte in the same manner as in Comparative Example 4, except that the content of poly (4-vinyl pyridine) dissolved in 0.1N sulfuric acid having a number average molecular weight of 14,000 was changed from 17 mg to 100 mg. Was prepared.

Also, except that the content of sodium polystyrene sulfonate having a number average molecular weight of 10,000 was changed from 20 mg to 66 mg, a strong basic anion exchange resin pretreated with a water-soluble anionic polymer electrolyte was prepared in the same manner as in Comparative Example 4.

Thereafter, a cohesion and resolution test was conducted in the same manner as in Example 1, the degree of separation was checked, and the specific resistance and total organic carbon (organic matter) were checked.

As shown in Table 1, in Examples 1 to 3 according to the present invention, since the cation exchange resin is pretreated with a specific water soluble cationic polymer electrolyte, and the anion exchange resin is also pretreated with a specific water soluble anionic polymer electrolyte, No aggregation occurred in the cohesion test, and complete separation could be performed in the separation test.

On the other hand, in Comparative Examples 1 and 2, in which only one of the cation exchange resin and the anion exchange resin was pretreated with the polymer electrolyte, aggregation did not occur, but the cation exchange resin and the anion exchange resin did not completely separate. That is, when only one of the cation exchange resin and the anion exchange resin is pretreated with a polymer, no aggregation occurs, but it can be seen that complete separation is not achieved in the mixed phase separation degree.

In addition, in the case of Comparative Example 3 in which neither the cation exchange resin nor the anion exchange resin was pretreated with the polymer electrolyte, it can be seen that a lot of aggregation occurred and no separation was performed.

In Comparative Examples 4 and 5, wherein the cation exchange resin was pretreated with a conventional water soluble cationic polymer electrolyte, and the anion exchange resin was also pretreated with a conventional water soluble anionic polymer electrolyte, as the amount of the water soluble cationic polymer electrolyte and the water soluble anionic polymer electrolyte was increased. Although the cohesiveness and the separability have been improved to some extent, it can be seen that the coagulation has not been completely blocked, and that complete separation has not been achieved.

In addition, as shown in Table 1, the specific resistance and total organic carbon (TCO) measurement results for the Examples and Comparative Examples, in the case of Examples 1 to 3 according to the present invention, significant decrease in specific resistance and increase in total organic carbon (TOC) However, in Comparative Examples 4 and 5 not according to the present invention, the specific resistance was low and the total organic carbon (TOC) was high.

Particularly, in contrast to Example 1 and Comparative Example 4, although the amount of the water-soluble cationic polymer electrolyte and the water-soluble anionic polymer electrolyte is the same, Comparative Example 4 without using a specific water-soluble cationic polymer electrolyte and a specific water-soluble anionic polymer electrolyte It can be seen that the decrease in resistivity and the increase in total organic carbon (TOC) are significant.

In addition, compared to Comparative Examples 4 and 5, it can be seen that the total organic carbon (TOC) elution increases as the amount of the water-soluble cationic polymer electrolyte and the water-soluble anionic polymer electrolyte increases.

Therefore, as in Examples 1 to 3 according to the present invention, when the cation exchange resin is pretreated with a specific water soluble cationic polymer electrolyte, and the anion exchange resin is also pretreated with a specific water soluble anionic polymer electrolyte, the amount of the polymer electrolyte is reduced so as to reduce the total organic matter. While elution of carbon (TOC) can be lowered, the drop in specific resistance can be prevented.

Claims (16)

a) an anion exchange resin pretreated with a water soluble anion polyelectrolyte having a sulfonated structure of 20 to 60 milligrams per liter of anion exchange resin; And
b) a cation exchange resin pretreated with a water soluble cationic polymer electrolyte having a quaternary ammonium salt structure of 17 to 60 milligrams per liter of cation exchange resin,
A water-soluble anionic polyelectrolyte having a sulfonated structure is a compound having a structural unit represented by the following formula (1),
Water-soluble cationic polymer electrolyte having a quaternary ammonium salt structure is a compound having a structural unit represented by the following formula (2),
Mixed layer ion exchange resin:
[Formula 1]

In Formula 1, n and m each independently represent an integer of 1 to 10,
[Formula 2]

In Formula 2, x and y each independently represent an integer of 1 to 10. delete delete The mixed layer ion exchange resin of claim 1, wherein the cation exchange resin is a strongly acidic cation exchange resin and the anion exchange resin is a strong basic anion exchange resin. The mixed layer ion exchange resin according to claim 4, wherein the strongly acidic cation exchange resin is a monovinylidene aromatic crosslinked polymer containing a sulfonic acid group, and the strong basic anion exchange resin is a crosslinked polymer of a monovinylidene aromatic compound and a quaternary ammonium group. delete delete The method of claim 1, wherein the water-soluble anionic polyelectrolyte having a sulfonated structure has a number average molecular weight ranging from 1,000 to 1,000,000, and acrylic acid and sulfonated acrylamide are copolymerized in a molar ratio of 2:98 to 98: 2. Mixed layer ion exchange resin. The method of claim 1, wherein the water-soluble cationic polymer electrolyte having a quaternary ammonium salt structure has a number average molecular weight in the range of 10,000 to 1,000,000, acrylamide and diallyldimethylammonium are copolymerized in a molar ratio of 2:98 to 98: 2. Mixed layer ion exchange resin. Pretreatment of the anion exchange resin with the anion exchange resin coated with a water-soluble anionic polyelectrolyte having a sulfonated structure of 20 to 60 milligrams per liter of anion exchange resin; And
A pretreatment step of the cation exchange resin, wherein the cation exchange resin is coated with a water-soluble cation polyelectrolyte having a structure of 17-60 milligrams of quaternary ammonium salt per liter of cation exchange resin,
A water-soluble anionic polyelectrolyte having a sulfonated structure is a compound having a structural unit represented by the following formula (1),
Water-soluble cationic polymer electrolyte having a quaternary ammonium salt structure is a compound having a structural unit represented by the following formula (2),
Process for preparing mixed layer ion exchange resin:
[Formula 1]

In Formula 1, n and m each independently represent an integer of 1 to 10,
[Formula 2]

In Formula 2, x and y each independently represent an integer of 1 to 10. delete delete The method of claim 10, wherein the water-soluble anionic polyelectrolyte having a sulfonated structure has a number average molecular weight ranging from 1,000 to 1,000,000, and acrylic acid and sulfonated acrylamide are copolymerized in a molar ratio of 2:98 to 98: 2. And manufacturing method of mixed layer ion exchange resin. 11. The method of claim 10, wherein the water-soluble cationic polymer electrolyte having a quaternary ammonium salt structure has a number average molecular weight ranging from 10,000 to 1,000,000, wherein acrylamide and diallyldimethylammonium are copolymerized in a molar ratio of 2:98 to 98: 2. And manufacturing method of mixed layer ion exchange resin. The method for producing a mixed bed ion exchange resin according to claim 10, wherein the cation exchange resin is a strongly acidic cation exchange resin and the anion exchange resin is a strong basic anion exchange resin. The method of claim 10, wherein the pretreatment step of the anion exchange resin and the pretreatment step of the cation exchange resin are performed at a temperature of 25 ° C. to 80 ° C. for 0.1 to 24 hours.