TWI658865B - Method of manufacturing mixture of anion exchanger and cation exchanger, method of manufacturing mixed bed of anion exchanger and cation exchanger, and method of refining hydrogen peroxide water - Google Patents

Abstract

The invention provides a method for producing a mixture of anion exchanger and cation exchanger, which is characterized by having an anion exchanger conversion step (1), which dissolves carbon dioxide obtained by dissolving carbon dioxide gas in pure water or ultrapure water. Water contacts the mixture of anion exchanger (B) and cation exchanger, and transforms the anion exchanger (B) into anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form, and A mixture of the anion exchanger (A) and the cation exchanger was obtained.

According to the present invention, the anion exchanger in the mixture of the anion exchanger and the cation exchanger can be maintained in the state of the mixture and converted into a bicarbonate ion form or a bicarbonate ion form and a carbonate ion form.

Description

Method for producing mixture of anion exchanger and cation exchanger, method for producing mixed bed composed of anion exchanger and cation exchanger, and method for purifying hydrogen peroxide water

The present invention relates to an anion exchanger, a mixture of an anion exchanger and a cation exchanger, a mixed bed composed of an anion exchanger and a cation exchanger, a method for producing the same, and a method for purifying hydrogen peroxide water.

Hydrogen peroxide water is used as a detergent in paper, wood pulp bleaching, industrial oxidants, wastewater treatment, and semiconductor manufacturing processes, and is used in a wide range of fields. Among them, in the semiconductor manufacturing process, in the field of wet cleaning, ammonia-hydrogen peroxide water (RCA: SC-1) is used to remove particulate pollution, and metal is contaminated. Hydrochloric acid-hydrogen peroxide water (RCA: SC-2), which was ionized and removed, was used for washing, and a large amount of hydrogen peroxide water was used.

Ultra-pure water and reagents for removing such contamination are required to have high purity, and hydrogen peroxide water is also required to have a quality that minimizes various impurities. In particular, some people have pointed out that the presence of metal components such as iron, aluminum, sodium, calcium, and magnesium will cause the semiconductor yield to decrease.

As a method for reducing impurities in hydrogen peroxide water, a method using an ion exchange resin and a method using a reverse osmosis membrane have been proposed. When using an ion exchange resin, if an anion exchange resin is used in the OH form, the decomposition reaction of hydrogen peroxide will proceed and generate heat or generate oxygen, so it is dangerous and cannot be operated safely, so it is adjusted to carbonate ion form and bicarbonate first. Reuse after ionization.

Patent Document 1 describes that by using a mixed-bed ion exchange resin + adsorbent device + mixed-bed ion exchange resin, a metal concentration in hydrogen peroxide water of 0.1 ppb or less and a high organic carbon concentration of 10 ppm or less are obtained. Purity hydrogen peroxide water.

Patent Document 2 describes that hydrogen peroxide cation exchange resin + fluoride ion exchange resin + carbonate ion type or bicarbonate ion type anion exchange resin + hydrogen cation exchange resin can be sequentially contacted to refine hydrogen peroxide water into high purity.

Patent Document 3 describes that an ion exchange resin is first brought into contact with a high-purity mineral acid aqueous solution having a metal component concentration of 0.1 wt. Ppb or less, and then is brought into contact with ultrapure water having a metal component concentration of 0.1 wt. Hydrogen peroxide water.

Patent Document 4 describes a method of bringing crude hydrogen peroxide water into contact with an anion exchange resin made of carbonate with ammonium carbonate or an anion exchange resin made of bicarbonate with ammonium bicarbonate.

Patent Document 5 describes a method for producing a purified hydrogen peroxide solution using a reverse osmosis membrane composed of a polyamide-based or polyvinyl alcohol-based composite membrane.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3715371

[Patent Document 2] Japanese Patent No. 4056695

[Patent Document 3] Japanese Patent No. 3171058

[Patent Document 4] Japanese Patent No. 3608211

[Patent Document 5] Japanese Patent Laid-Open No. 2011-68533

In Patent Documents 1 to 3, when an anion exchange resin is made into an anion exchange resin having a bicarbonate ion form, a carbonate or bicarbonate aqueous solution is generally used. However, the mixture of anion exchange resin and cation exchange resin, and the mixed bed composed of anion exchange resin and cation exchange resin, because of the existence of cation exchange resin, when the anion exchange resin is made into anion exchange resin with bicarbonate ion form, Do not use carbonate or bicarbonate solution. The reason is that the cations of the cation exchange resin are exchanged for carbonate or bicarbonate cations.

In Patent Document 4, ammonium carbonate or ammonium bicarbonate is used to make the anion exchange resin into a carbonate ion form or a bicarbonate ion form. However, as described above, it is a mixture of an anion exchange resin and a cation exchange resin. When mixed with a cation exchange resin, the cations of the cation exchange resin are exchanged for ammonium ions. In addition, if only an anion exchange resin is packed in a resin tower to make a carbonic acid or bicarbonate shape, and then mixed with a cation exchange resin, the workability is not good, and impurities may be contaminated during operation.

Further, in Patent Documents 1 to 3, when anion exchange resin is made into a carbonate ion form or a bicarbonate ion form, a very high concentration carbonate or bicarbonate aqueous solution with a salt concentration of 5 to 15% by weight is generally used. The impurities in the hydrogen peroxide water are removed and refined to a high concentration, because the aqueous solution containing a high concentration of salt is brought into contact with the ion exchange body, even after sufficient washing after regeneration, sodium ions will be caused by contact with the hydrogen peroxide water to cause resin removal from the resin. Dissolve. In addition, a large amount of pure water or ultrapure water must be used for washing.

Patent Document 5 proposes a method using a reverse osmosis membrane. However, since it has been exposed to a high concentration of hydrogen peroxide water, the membrane is degraded and the barrier ratio is reduced.

In Patent Document 4, in order to solve the above-mentioned problems, ammonium carbonate or ammonium bicarbonate is used, but each drug does not have a clear specification value of impurity metals and the like, and even if a part of the metal substance has a specification value, its concentration is still high. problem. Furthermore, because waste liquid is discharged, it also needs to be treated.

Other than hydrogen peroxide water, anion exchange resins have been used to purify various functional waters. In addition, since anion exchange resins can be used in various applications, there is a potential demand for novel anion exchangers that have not been available in the past, and mixtures or mixed beds of novel anion exchangers and cation exchangers that have not existed in the past.

Therefore, the present invention provides an anion exchanger in a mixture of anion exchanger and cation exchanger, or a mixed bed composed of anion exchanger and cation exchanger, so as to maintain the state of the mixture or mixed bed into a bicarbonate ion form. Or a method for producing a mixture of an anion exchanger and a cation exchanger having a bicarbonate ion anion exchanger and a carbonate ion anion exchanger, and a method for producing a mixed bed composed of an anion exchanger and a cation exchanger.

In addition, the present invention provides anion exchangers with high refining performance of hydrogen peroxide water and other water, aqueous solution, or organic solvents refined using anion exchangers, such mixtures or mixed beds of anion exchangers and cation exchangers, and the like. Of manufacturing method.

The present invention also provides an efficient method for purifying hydrogen peroxide water.

Such a problem can be solved by the following invention. that is,

(1) A mixture of anion exchanger and cation exchanger, which is a mixture of anion exchanger (A) and cation exchanger, characterized in that the anion exchanger (A) has a bicarbonate ion form (-HCO ₃ ) An anion exchanger, or an anion exchange having a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ).

(2) A mixture of anion exchanger and cation exchanger, characterized by being obtained by anion exchanger conversion step (1): anion exchanger conversion step (1) is performed by using pure water or ultrapure water The carbon dioxide-dissolved water obtained by dissolving carbon dioxide gas is contacted with a mixture of the anion exchanger (B) and the cation exchanger to transform the anion exchanger (B) into a form having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. An anion exchanger (A) to obtain a mixture of the anion exchanger (A) and the cation exchanger.

(3) A mixture of an anion exchanger and a cation exchanger as described in (1) or (2), wherein the anion exchanger (A) is bicarbonated with respect to the total exchange capacity of the bicarbonate ion form and the carbonate ion form. The ratio of the ionic exchange capacity is 70 equivalent% or more.

(4) A mixed bed composed of an anion exchanger and a cation exchanger, which is a mixed bed composed of an anion exchanger (A) and a cation exchanger packed in an ion exchange tower, and the anion exchanger (A) has a weight carbonate ion type (-HCO ₃₎ of the anion exchanger, or with a bicarbonate ion-shaped (-HCO ₃₎ and the carbonate ion form (-CO ₃₎ of the anion exchanger.

(5) The mixed bed of anion exchanger and cation exchanger according to (4), wherein the anion exchanger (A) has a ratio of the bicarbonate ion form and the carbonate ion form to the total exchange capacity of the bicarbonate ion form. The ratio of exchange capacity is more than 70 equivalent%.

(6) A method for producing a mixture of an anion exchanger and a cation exchanger, which is characterized by having an anion exchanger conversion step (1), which is carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water A mixture of an anion exchanger (B) and a cation exchanger is contacted to transform the anion exchanger (B) into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form to obtain A mixture of the anion exchanger (A) and the cation exchanger.

(7) The method for producing a mixture of an anion exchanger and a cation exchanger according to (6), wherein the anion exchanger (A) has a bicarbonate ion with respect to the total exchange capacity of the bicarbonate ion form and the carbonate ion form. The proportion of the exchange capacity is more than 70 equivalent%.

(8) The method for producing a mixture of an anion exchanger and a cation exchanger according to (6) or (7), wherein in the anion exchanger conversion step (1), the carbon dioxide dissolved water is brought into contact with the anion exchanger (B ) And cation exchanger, the conductivity of carbon dioxide dissolved water after contacting the mixture of anion exchanger (B) and cation exchanger with respect to the carbon dioxide before contacting the mixture of anion exchanger (B) and cation exchanger The ratio of the conductivity of the dissolved water ((conductivity after contact / conductivity before contact) × 100) is 90% or more.

(9) A method for producing a mixed bed composed of an anion exchanger and a cation exchanger, which is characterized by having an anion exchanger conversion step (2), which is carbon dioxide obtained by dissolving carbon dioxide gas in pure water or ultrapure water Dissolved water contacts a mixed bed composed of anion exchanger (B) and cation exchanger packed in an ion exchange tower to transform the anion exchanger (B) into a form having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. The anion exchanger (A), to obtain a mixed bed composed of the anion exchanger (A) and the cation exchanger.

(10) The method for producing a mixed bed composed of an anion exchanger and a cation exchanger according to (9), wherein the anion exchanger (A) has an exchange capacity with respect to the total amount of the bicarbonate ion form and the carbonate ion form, The ratio of the exchange capacity of the bicarbonate ion form is 70 equivalent% or more.

(11) The method for producing a mixed bed composed of an anion exchanger and a cation exchanger according to (9) or (10), wherein in the anion exchanger conversion step (2), the carbon dioxide is supplied to the ion exchange tower to dissolve Water until the ratio of the conductivity of the carbon dioxide dissolved water at the outlet of the ion exchange tower to the conductivity of the carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) becomes 90% the above.

(12) A method for purifying hydrogen peroxide water, which is characterized by having the following steps: anion exchanger conversion step (2), contacting the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water to ion exchange A column-packed mixed bed composed of anion exchanger (B) and cation exchanger to transform the anion exchanger (B) into an anion exchanger having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form ( A) to obtain a mixed bed composed of the anion exchanger (A) and the cation exchanger; in a hydrogen peroxide water refining step, a crude hydrogen peroxide water is supplied to the ion exchange tower, and the crude hydrogen peroxide water is brought into contact A mixed bed composed of the anion exchanger (A) and the cation exchanger to obtain purified hydrogen peroxide water.

(13) The method for purifying hydrogen peroxide water according to (12), wherein in the anion exchanger conversion step (2), the carbon dioxide dissolved water is supplied to the ion exchange tower until the carbon dioxide at the outlet of the ion exchange tower is dissolved The ratio of the conductivity of water to the conductivity of carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100) is 90% or more.

(14) An anion exchanger characterized by being an anion exchanger having a bicarbonate ion form (-HCO ₃ ), or an anion having a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ) Exchange body.

(15) An anion exchanger obtained by dissolving carbon dioxide gas obtained by dissolving carbon dioxide gas in pure or ultrapure water by contacting the OH anion exchanger.

(16) The anion exchanger according to (14) or (15), in which the ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form is 70 Equivalent% or more.

(17) A method for producing an anion exchanger, characterized by having an anion exchanger conversion step (3), in which carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is brought into contact with the anion exchanger (B) In order to transform the anion exchanger (B) into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form, the anion exchanger (A) is obtained.

(18) The method for producing an anion exchanger according to (17), wherein the ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger (A) It is 70 equivalent% or more.

(19) The method for producing an anion exchanger according to (17) or (18), wherein in the anion exchanger conversion step (3), the carbon dioxide dissolved water is brought into contact with the anion exchanger (B) until the anion exchanger is contacted The ratio of the conductivity of carbon dioxide-dissolved water after the exchanger (B) to the conductivity of carbon dioxide-dissolved water before the anion exchanger (B) ((conductivity after contact / conductivity before contact) × 100) ) Is over 90%.

(20) A method for purifying hydrogen peroxide water, comprising the following steps: anion exchanger conversion step (4), contacting carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water to ion exchange Column packed anion exchanger (B) to cross the anion The substitution body (B) is converted into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form; and a hydrogen peroxide water refining step, and supplying crude hydrogen peroxide water to the ion exchange tower, The crude hydrogen peroxide water is brought into contact with the anion exchanger (A) to obtain a purified hydrogen peroxide water.

(21) The method for purifying hydrogen peroxide water according to (20), wherein the anion exchanger conversion step (4) and the hydrogen peroxide water purification step are repeated alternately.

(22) The method for purifying hydrogen peroxide water according to (20) or (21), wherein in the anion exchanger conversion step (4), the carbon dioxide dissolved water is supplied to the ion exchange tower until the ion exchange tower The ratio of the conductivity of the carbon dioxide dissolved water at the outlet to the conductivity of the carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100) is 90% or more.

According to the present invention, a mixture of an anion exchanger and a cation exchanger, or an anion exchanger in a mixed bed composed of an anion exchanger and a cation exchanger can be provided to maintain the state of the mixture or the mixed bed and change to a bicarbonate ion. A method for producing a mixture of anion exchangers and cation exchangers in the form of anion exchangers having a bicarbonate ion form and a carbonate ion form, and a method for producing a mixed bed composed of an anion exchanger and a cation exchanger.

In addition, the present invention can provide hydrogen peroxide water and other anion exchangers with high refining performance using water, aqueous solution or organic solvent purified by anion exchanger, such a mixture or mixed bed of anion exchanger and cation exchanger, and the like. And other manufacturing methods.

Also, according to the present invention, an efficient method for purifying hydrogen peroxide water can be provided.

1‧‧‧PFA ion exchange tower

2‧‧‧ hollow fiber membrane for gas dissolution

3‧‧‧Gas mass flow controller

4‧‧‧CO2 gas cylinder

5‧‧‧ ultra pure water

6‧‧‧ conductivity meter

7, 8‧‧‧ valve

FIG. 1 shows a flowchart of the embodiment.

FIG. 2 shows the change in the conductivity of carbon dioxide dissolved water at the tower inlet and the tower outlet in the embodiment.

FIG. 3 is a graph showing changes with time of acetic acid removal in Examples and Comparative Examples.

The mixture of an anion exchanger and a cation exchanger of the present invention is a mixture of an anion exchanger (A) and a cation exchanger, and the anion exchanger (A) is an anion exchanger having a bicarbonate ion form (-HCO ₃ ), Or an anion exchanger having bicarbonate ion form (-HCO ₃ ) and carbonate ion form (-CO ₃ ).

The mixed bed of anion exchanger and cation exchanger of the present invention is a mixed bed composed of anion exchanger (A) and cation exchanger packed in an ion exchange tower, and the anion exchanger (A) is bicarbonate ion-shaped (-HCO ₃₎ of the anion exchanger, or with a bicarbonate ion-shaped (-HCO ₃₎ and the carbonate ion form (-CO ₃₎ of the anion exchanger.

The anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention are anion exchanges having a bicarbonate ion form (-HCO ₃ ) Or an anion exchanger having a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ), that is, an anion exchanger having an anion exchange group whose opposite anion is a bicarbonate ion (-HCO ₃ ion) Or an anion exchanger having an anion exchange group whose opposite anion is a bicarbonate ion (-HCO ₃ ion) and an anion exchange group whose opposite anion is a carbonate ion (-CO ₃ ion). The anion exchanger (A) is a resin whose matrix is a resin, and an anion exchanger into which an anion exchange group is introduced into the resin. The anion exchanger is a styrene gel-type or MR-type anion exchange resin, and an organic porous anion exchanger. In this specification, the bicarbonate ion form (R-HCO ₃ ) and carbonate ion form (R-CO ₃ ) are described. However, in actual use, the bicarbonate ion form dissociates into R-HCO ₃ ^- and carbonate ion. The form dissociates as R-CO ₃ ^2- .

The mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention is exchanged with respect to the total amount of the bicarbonate ion form and the carbonate ion form. Capacity, ratio of exchange capacity of bicarbonate ion form ((equivalent number of bicarbonate anion exchange group / (equivalent number of bicarbonate anion exchange group + equivalent number of carbonate anion exchange group)) × 100) It is preferably at least 70 equivalent%, particularly preferably at least 75 equivalent%, and even more preferably at least 80 equivalent%. The ratio of the exchange capacity of the bicarbonate ion form to the total of the bicarbonate ion form and the carbonate ion form is within the above range, and the refining performance of hydrogen peroxide water and other water, aqueous solution, or organic solvent refined using an anion exchanger is improved. , So it is ideal.

The mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention may also have a degree that does not adversely affect purification. Ratio of bicarbonate ion form and ion form other than carbonate ion form, total exchange capacity of bicarbonate ion form and carbonate ion form to total exchange capacity of anion exchanger ((((equivalent number of anion exchange group of bicarbonate form + Carbonate anion exchange group equivalent number) / total anion exchange group equivalent number) × 100) It is preferably 50 equivalent% or more, more preferably 60 equivalent% or more, 70 equivalent% or more It is better, more than 80 equivalent% is more preferable, more than 95 equivalent% is more preferable, more than 99 equivalent% is more preferable, and 100 equivalent% is more desirable. Since the ratio of the total exchange capacity of bicarbonate ion form and carbonate ion form to the total exchange capacity is within the above range, the purification performance of hydrogen peroxide water and other water, aqueous solution, or organic solvent refined using an anion exchanger is improved, so ideal.

When the mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention has an ion form other than a bicarbonate ion form and a carbonate ion form, Examples of such an ionic form include a Cl form, an OH form, and the like. In addition, if the amount of OH form in the anion exchanger (A) is too large, the decomposition reaction of hydrogen peroxide is easy to proceed when the hydrogen peroxide water is refined, so when the anion exchanger (A) is used in the purification of hydrogen peroxide In use, the ratio of the OH-shaped exchange capacity to the total exchange capacity in the anion exchanger (A) is preferably 1 equivalent% or less, particularly preferably 0.1 equivalent% or less, and more preferably 0 equivalent%.

In the mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention, as the resin to be introduced into the anion exchange group, styrene is preferred. -Divinylbenzene copolymers are preferred.

The mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention may include a level 4 ammonium group as a functional group, and the ammonium The radical bonded to the nitrogen atom of the radical is only the strongly basic type I of the alkyl group, and the ammonium radical bonded to the nitrogen atom is a functional group of the strong basic type II. Weak basicity having the first to third amine groups as functional groups. Among these, strong basic type I anion exchangers are preferred.

The average particle size of the anion exchange resin when the mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention is a granular anion exchange resin It is preferably 0.2 to 1.0 mm, and particularly preferably 0.4 to 0.8 mm. When the mixture of the anion exchanger and the cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention is an organic porous anion exchanger, the organic porous anion The structure of the exchange body: most of the bubble-like micropores overlap each other, and this overlapping portion becomes a structure in which the open communication holes are formed in a skeleton made of resin, that is, a continuous micropore structure.

The mixture of the anion exchanger and the cation exchanger of the present invention and the cation exchanger of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention are based on a resin, and a cation exchange group is introduced into the resin. The body is a styrene-based gel-type or MR-type cation exchange resin and an organic porous ion exchanger. In the cation exchanger, the resin introduced as a cation exchange group is preferably a styrene-divinylbenzene copolymer.

In the mixture of the anion exchanger and the cation exchanger of the present invention and the cation exchanger of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention, the cation exchange group introduced into the resin includes a sulfonic acid group.

When the mixture of the anion exchanger and the cation exchanger of the present invention and the cation exchanger of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention are granular cation exchange resins, the average particle diameter of the cation exchange resin is smaller than It is preferably 0.2 to 1.0 mm, and particularly preferably 0.4 to 0.8 mm. Again, this When the mixture of the anion exchanger and the cation exchanger of the invention and the cation exchanger of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention are organic porous cation exchangers, the structure of the organic porous anion exchanger : Most of the bubble-like micropores overlap each other, and this overlapping portion becomes a structure in which the open communication holes are formed in a skeleton made of resin, that is, a continuous micropore structure.

In the mixture of the anion exchanger and the cation exchanger of the present invention, the mixture of the anion exchanger (A) and the cation exchanger refers to a mixture of the granular anion exchange resin (A) and the granular cation exchange resin.

In the mixed bed composed of anion exchanger and cation exchanger of the present invention, the mixed bed composed of anion exchanger (A) and cation exchanger includes: (i) granular anion exchange resin (A) and A mixture of granular cation exchange resins mixed with each other to form a bed, that is, a mixed bed, and (ii) anion exchange by a granular anion exchange resin (A), an organic porous anion exchanger (A), and the like The layer formed by the body (A) and the layer formed by a cation exchanger such as a granular cation exchange resin or an organic porous cation exchanger, that is, a layer formed by the anion exchanger (A) layer and the cation exchanger layer Bunk beds.

The method for producing a mixture of an anion exchanger and a cation exchanger of the present invention is characterized by having an anion exchanger conversion step (1), and contacting anion with carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water. A mixture of an exchanger (B) and a cation exchanger to convert the anion exchanger (B) into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form to obtain the anion A mixture of the exchanger (A) and the cation exchanger.

The method for producing a mixed bed composed of an anion exchanger and a cation exchanger according to the present invention is characterized by having an anion exchanger conversion step (2), which is obtained by dissolving carbon dioxide gas in pure water or ultrapure water. The carbon dioxide dissolved water is contacted with a mixed bed composed of an anion exchanger (B) and a cation exchanger packed in an ion exchange tower to transform the anion exchanger (B) into a form having a bicarbonate ion or having a form of a bicarbonate ion. A carbonate ion-formed anion exchanger (A) to obtain a mixed bed composed of the anion exchanger (A) and the cation exchanger.

In the method for producing a mixture of an anion exchanger and a cation exchanger according to the present invention, and the method for producing a mixed bed composed of an anion exchanger and a cation exchanger according to the present invention, the object in contact with carbon dioxide dissolved water is the anion exchanger ( B) and cation exchanger, the latter is a mixed bed composed of anion exchanger (B) and cation exchanger packed in the ion exchange tower. Although this point is different, cation exchanger and anion exchanger ( B), the carbon dioxide dissolved water is brought into contact with the anion exchanger (B), and the anion exchanger (B) is transformed into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form, It is the same at this point.

Step (1) of anion exchanger conversion is to change the anion exchanger (B) in the mixture to have a bicarbonate ion form or by bringing carbon dioxide dissolved water into contact with the mixture of anion exchanger (B) and cation exchanger. A step of anion exchanger (A) having bicarbonate ion form and carbonate ion form. In the anion exchanger conversion step (2), the anion exchanger in the mixed bed is made by dissolving carbon dioxide in contact with the mixed bed composed of the anion exchanger (B) and the cation exchanger filled in the ion exchange tower. (B) A step of converting to an anion exchanger (A). Mixture of anion exchanger (B) and cation exchanger The substance refers to a mixture of granular anion exchange resin (B) and granular cation exchange resin. In addition, a mixed bed composed of an anion exchanger (B) and a cation exchanger includes: (i) a bed formed by mixing a granular anion exchange resin (B) and a granular cation exchange resin with each other; , That is, mixed bed, and (ii) a layer formed of anion exchanger (B) such as granular anion exchange resin (B), organic porous anion exchanger (B), and the cation exchange resin in granular form A layer composed of a cation exchanger such as an organic porous cation exchanger, that is, a multilayer bed composed of an anion exchanger (B) layer and a cation exchanger layer.

The anion exchanger (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is converted into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. The former anion exchanger. If a strongly basic anion exchanger, that is, an OH ion anion exchanger (anion exchanger in which the opposite anion of the anion exchange group is an OH ion) is used to carry out the purification of crude hydrogen peroxide water, the contact with the OH ion anion exchanger Decomposition of hydrogen peroxide occurs. In addition, if a Cl ion anion exchanger (anion exchanger in which the opposite anion of the anion exchange group is Cl ion) is used to purify crude hydrogen peroxide water, Cl ion will flow out to the treatment due to the ion exchange reaction with the target ion. It cannot be purified because it is in liquid. Therefore, in the method for producing a mixture of an anion exchanger and a cation exchanger in the present invention or the method for producing a mixed bed composed of an anion exchanger and a cation exchanger in the present invention, the anion exchanger is converted into a bicarbonate ion form. Or an anion exchanger (A) having a bicarbonate ion form and a carbonate ion form.

In the anion exchanger conversion step (1), the carbon dioxide dissolved water is brought into contact with anion exchangers such as OH ion form and Cl ion form, that is, the contact is converted into a form having a bicarbonate ion or having a bicarbonate ion. A mixture of an anion exchanger (anion exchanger (B)) and a cation exchanger before the anion exchanger (A) in the sub-form and carbonate ion form, and the anion exchanger (B) in the mixture is converted into a bicarbonate ion. Anion exchanger (A) in the form or having a bicarbonate ion form and a carbonate ion form. If a bicarbonate ion form or a mixture of anion exchangers (A) and cation exchangers having a bicarbonate ion form and a carbonic acid ion form is used, the treated water (hydrogen peroxide water or other anion exchangers and cations are used). Refined water or aqueous solution), the bicarbonate ions of the anion exchanger (A) in the mixture will be exchanged for impurity anions in the treated water. Therefore, after the purification of the treated water is continued to a certain extent, the anion exchanger exchanged with the impurity anion ion can be regenerated into an anion exchanger having a bicarbonate ion form or a bicarbonate ion form and a carbonate ion form (A ). In the present invention, an anion exchanger conversion step (in order to obtain a bicarbonate ion form or an anion exchanger (A) having a bicarbonate ion form and a bicarbonate ion form, before performing the first purification of such treated water) ( In 1), the anion exchanger before conversion to the anion exchanger (A), and the purification of treated water such as hydrogen peroxide water to a certain extent, the ion exchange of impurity ions in the treated water is performed again for the anion exchanger Both of the anion exchangers in the conversion step (1) serve as anion exchangers (B) before being converted into anion exchangers (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form.

In the anion exchanger conversion step (2), the carbon dioxide dissolved water is brought into contact with anion exchangers such as OH ion form and Cl ion form which have been filled in the ion exchange tower, that is, the ion exchanger is transformed into a bicarbonate ion form or a heavy carbonate ion form. Mixed bed of anion exchanger (anion exchanger (B)) and cation exchanger before carbonate ion and carbonate ion anion exchanger (A), and the anion exchanger (B) in the mixed bed is transformed into Anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. In addition, if an anion having a bicarbonate ion form or a bicarbonate ion form and a carbonate ion form is used, The mixed bed composed of the exchanger (A) and the cation exchanger continues to refine the treated water (hydrogen peroxide water or other water or aqueous solution refined by using a mixed bed composed of the anion exchanger and the cation exchanger). The bicarbonate ions of the anion exchanger (A) in the mixed bed are exchanged for impurity anions in the treated water. Therefore, after the purification of the treated water is continued to a certain extent, the anion exchanger that has been ion-exchanged by impurities must be regenerated into a bicarbonate ion form or an anion exchanger (A) having a bicarbonate ion form and a carbonate ion form. In the present invention, an anion exchanger conversion step (2) for obtaining an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form is performed before the purification of such first treated water (2) ), The anion exchanger before conversion to the anion exchanger (A), and the ionic exchange of impurities in the treated water by refining the treated water such as hydrogen peroxide water to a certain extent, for the anion exchanger conversion step again Both of the anion exchangers of (2) serve as anion exchangers (B) before being converted into anion exchangers (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form.

The anion exchanger (A) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is an anion exchanger having a bicarbonate ion form (-HCO ₃ ) or a bicarbonate ion form (-HCO ₃₎ and the carbonate ion form (-CO ₃₎ of the anion exchanger. The ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form to the total exchange capacity of the anion exchanger (A) is not particularly limited, and is preferably 50 equivalent% or more, particularly preferably 60 equivalent% or more, and particularly preferably 70 More than equivalent%, more preferably 80 equivalent% or more, still more preferably 95 equivalent% or more, still more preferably 99 equivalent% or more, and even more preferably 100 equivalent%, in the anion exchanger (A), compared with the bicarbonate The total exchange capacity of the ionic and carbonate ion forms, and the ratio of the exchange capacity of the bicarbonate ion form is preferably 70 equivalent% or more, particularly preferably 75 equivalent% or more, and more preferably 80 equivalent% or more.

The anion exchanger (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the matrix is a resin, and the anion exchanger with an anion exchange group introduced into the resin is a styrenic condensation agent. Colloid or MR anion exchange resin, organic porous anion exchanger. Among the anion exchangers (B), as the resin to which an anion exchange group is introduced, a styrene-divinylbenzene copolymer is preferable.

Examples of the anion exchanger (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) include a fourth-order ammonium group as a functional group, and the nitrogen-bonded group of this ammonium group is only an alkyl group. Strong basic type I, with a level 4 ammonium group as a functional group, and the nitrogen atom bonded group of this ammonium group is a strong basic type II with an alkyl group and an alkanol group, and it has the first to third amine groups as a function The base is weakly basic, and among these, a strong basic type I anion exchanger is preferred. The anion exchanger (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is preferably in the OH form.

When the anion exchanger (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is a granular anion exchange resin, the average particle diameter of the anion exchange resin is preferably 0.2 to 1.0 mm, especially It is preferably 0.4 ~ 0.8mm. When the anion exchange resin (B) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is an organic porous anion exchanger, the structure of the organic porous anion exchanger: most of the bubble-like micropores Overlapping, this overlapping part becomes a structure in which open communication holes are formed in a skeleton made of resin, that is, a continuous microporous structure.

The cation exchanger in the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the matrix is a resin, and the cation exchanger into which the cation exchange group is introduced into the resin is in the form of a styrene gel or MR Cation exchanger. In the cation exchanger, the resin introduced by the cation exchange group is preferably a styrene-divinylbenzene copolymer.

In the cation exchanger of the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the cation exchange group introduced into the resin includes a sulfonic acid group.

When the cation exchanger in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is a granular cation exchange resin, the average particle diameter of the cation exchange resin is preferably 0.2 to 1.0 mm, and particularly preferably 0.4. ~ 0.8mm. When the cation exchange resin in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is an organic porous cation exchanger, the structure of the organic porous anion exchanger: most of the bubble-like micropores overlap each other. The structure where the overlapping portion becomes an open communication hole is formed in a skeleton made of resin, that is, a continuous microporous structure.

The carbon dioxide dissolved water in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is obtained by dissolving carbon dioxide gas in pure water or ultrapure water. Pure water or ultrapure water is pure water or ultrapure water obtained by processing raw water using pure water manufacturing equipment or ultrapure water manufacturing equipment that removes ionic and non-ionic substances from raw water. The resistivity is 1.0MΩ‧cm or more. Pure water is preferably ultrapure water having a resistivity of 10MΩ‧cm or more, and particularly preferably ultrapure water having a resistivity of 18MΩ‧cm or more.

The concentration of carbon dioxide gas in the carbon dioxide-dissolved water of the anion exchanger conversion step (1) or the anion-exchanger conversion step (2) may be any concentration as long as it can dissolve the carbon dioxide gas in pure water or ultrapure water, and is preferably 1 ~ 2000mg / L, particularly preferably 20 ~ 2000mg / L. The higher the dissolved concentration of carbon dioxide, the more it can be processed in a short time, and the amount of water used can also be reduced.

The method for obtaining carbon dioxide-dissolved water, that is, a method for dissolving carbon dioxide gas in pure water or ultrapure water is not particularly limited, and a method for producing functional water used for washing applications of electronic parts and components can be cited. For example: a method of dissolving carbon dioxide gas using a hollow fiber membrane, a method of directly injecting carbon dioxide gas into a pipe, a method of dissolving carbon dioxide gas by dispersing equipment such as a static mixer, and supplying ultrapure water in a gas dissolution tank A method of supplying carbon dioxide gas on the upstream side of the pump and dissolving it by stirring in the pump. In order to dissolve carbon dioxide to a saturated concentration with good efficiency, it is preferable to use a hollow fiber membrane to dissolve carbon dioxide gas. When a gas cylinder is used for supplying carbon dioxide gas, it is preferable to provide a particle removal filter for removing particles below 0.5 μm in the gas supply pipe, and a particle removal filter for removing particles below 0.2 μm is particularly preferable.

In the preparation of carbon dioxide dissolved water, the mass flow controller is used to control the supply amount of carbon dioxide gas dissolved in pure water or ultrapure water. The carbon dioxide concentration is continuously monitored by a conductivity meter.

In the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the carbon dioxide dissolved water is brought into contact with the anion exchanger (B) and the cation exchanger or a mixture of the anion exchanger (B) and the cation exchanger In a mixed bed, if the temperature is low, it can increase the solubility of carbon dioxide to some extent, so it is ideal, but from the viewpoint of energy consumption, it is preferably 5 to 40 ° C, and particularly preferably 10 to 30 ° C. And anion In the exchange body conversion step (2), when an ion exchange tower filled with a mixed bed composed of an anion exchanger (B) and a cation exchanger is introduced with carbon dioxide dissolved water, one-pass (one pass) can be used to supply carbon dioxide to the ion exchange tower. Dissolved water, but in order to reduce the amount of pure water or ultrapure water used, a circulation tank and pump can be set at the back of the ion exchange tower, and the used water can be recycled as raw water for the preparation of carbon dioxide dissolved water. In addition, when the used water is recycled, the amount of carbon dioxide gas can be reduced by feeding back the value of the conductivity meter and controlling the amount of carbon dioxide gas supplied.

In addition, by performing the anion exchanger conversion step (1), all or a part of the relative anions of the anion exchanger (B) in the mixture of the anion exchanger (B) and the cation exchanger is exchanged for a bicarbonate ion (-HCO). ₃ ) or carbonate ion (-CO ₃ ), and transform into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. Furthermore, by performing the anion exchanger conversion step (2), all or a part of the opposite anions of the anion exchanger (B) in a mixed bed composed of the anion exchanger (B) and the cation exchanger is exchanged for bicarbonate ions ( -HCO ₃ ) or carbonate ion (-CO ₃ ), and transform into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form.

The anion exchanger (A) in the anion exchanger conversion step (1) or the anion exchanger conversion step (2) is an anion exchanger having a bicarbonate ion form (-HCO ₃ ), or an anion exchanger having a bicarbonate ion form (-HCO ₃ ) ₃ ) Anion exchanger with carbonate ion form (-CO ₃ ), that is, an anion exchanger having an anion exchange group whose relative anion is a bicarbonate ion (-HCO ₃ ion), or an anion exchanger having a relative anion which is a bicarbonate ion (- HCO ₃ ion) anion exchange group and anion exchange group whose opposite anion is a carbonate ion (-CO ₃ ion). In this specification, the bicarbonate ion form (R-HCO ₃ ) and carbonate ion form (R-CO ₃ ) are described. However, in actual use, the bicarbonate ion form dissociates into R-HCO ₃ ^- and carbonate ion form dissociation. R-CO ₃ ^2- .

In addition, in the anion exchanger (A) of the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the total exchange capacity of the bicarbonate ion form and the carbonate ion form is equal to the total exchange capacity of the anion exchanger. The ratio is not particularly limited. It is preferably 50 equivalent% or more, particularly preferably 60 equivalent% or more, more preferably 70 equivalent% or more, still more preferably 80 equivalent% or more, more preferably 95 equivalent% or more, and more preferably It is 99 equivalent% or more, and even more preferably 100 equivalent%. That is, in the anion exchanger conversion step (1) or the anion exchanger conversion step (2), the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure or ultrapure water is brought into contact with the anion exchanger (B) and cation exchange Mixture or a mixed bed composed of anion exchanger (B) and cation exchanger until the total exchange capacity of the bicarbonate ion form and carbonate ion form in the anion exchanger (A) becomes larger than the total exchange capacity. It is preferably 50 equivalent% or more, particularly preferably 60 equivalent% or more, more preferably 70 equivalent% or more, still more preferably 80 equivalent% or more, more preferably 95 equivalent% or more, and still more preferably 99 equivalent% or more. More preferably, it is 100 equivalent%.

Ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger (A) of the anion exchanger conversion step (1) or the anion exchanger change step (2) It is preferably at least 70 equivalent%, particularly preferably at least 75 equivalent%, and even more preferably at least 80 equivalent%. Bicarbonate ion form has a lower selection coefficient than carbonate ion form, so it is particularly effective for improving the processing performance of anion with low selectivity and low concentration of ion exchange load. The more the proportion of bicarbonate ion form in anion exchanger, The higher the refining performance of hydrogen peroxide water and other treated water. That is, by making the exchange capacity of the bicarbonate ion form in the anion exchanger (A) relative to the bicarbonate ion form and the carbonate ion form, The ratio of the total exchange capacity is in the above range, which is ideal for improving the refining performance of hydrogen peroxide water or other treated water.

In the anion exchanger conversion step (1), for example, the mixture of the anion exchanger (B) and the cation exchanger is charged into a container provided with a carbon dioxide-dissolved water supply pipe and a discharge pipe, and the carbon dioxide-dissolved water is supplied to the container. The carbon dioxide-dissolved water can be continuously contacted with the mixture of the anion exchanger (B) and the cation exchanger by discharging the water in the container to the outside of the container. However, in this case, each of the supply pipe and the discharge pipe of the carbon dioxide-dissolved water is used. Set a conductivity meter, etc. to measure the electrical conductivity before and after the carbon dioxide dissolved water contacts the mixture of the anion exchanger (B) and the cation exchanger. The contact between the carbon dioxide dissolved water and the mixture of the anion exchanger (B) and the cation exchanger is carried out until contact. The ratio of the conductivity of carbon dioxide-dissolved water after the mixture of anion exchanger (B) and cation exchanger to the conductivity of carbon dioxide-dissolved water before contacting the mixture of anion exchanger (B) and cation exchanger ((After contact Electrical conductivity / conductivity before contact) × 100)) is 90% or more, and preferably 95% or more. By determining the change in the conductivity ratio of carbon dioxide dissolved water before and after contacting the mixture of anion exchanger (B) and cation exchanger, the carbon dioxide dissolved water is brought into contact with the mixture of anion exchanger (B) and cation exchanger, It is easy to grasp the end point of the anion exchanger conversion step (1). In the anion exchanger conversion step (1), during a period from when the carbon dioxide dissolved water comes into contact with the mixture of the anion exchanger (B) and the cation exchanger, the carbon dioxide dissolves carbon dioxide in the water (the bicarbonate ion produced by carbon dioxide dissolved in water or Most of the carbonate ion is consumed in the anion exchanger (B) ion exchange to bicarbonate ion or carbonate ion, so the concentration of bicarbonate ion or carbonate ion in carbon dioxide dissolved water becomes very low. Therefore, for a period of time after the carbon dioxide-dissolved water starts to contact the mixture of the anion exchanger (B) and the cation exchanger, the carbon dioxide dissolved after contacting the mixture of the anion exchanger (B) and the cation exchanger The conductivity of water is very low. After that, ion exchange to bicarbonate ion form or carbonate ion form is continued, and anion exchangers which are ion-exchanged into bicarbonate ion form or carbonate ion form are increased in the anion exchanger, because the ion exchange is consumed by bicarbonate ion form or carbonate ion form. The amount of carbon dioxide will gradually decrease. Therefore, the concentration of bicarbonate ions or carbonate ions in the carbon dioxide dissolving water after contacting the mixture of the anion exchanger (B) and the cation exchanger gradually increases, and the carbon dioxide dissolving water after contacting the mixture of the anion exchanger (B) and the cation exchanger. The electrical conductivity gradually increases. Electrical conductivity of carbon dioxide-dissolved water after contact with a mixture of anion exchanger (B) and cation exchanger with respect to electrical conductivity of carbon dioxide-dissolved water before contact with a mixture of anion exchanger (B) and cation exchanger ((contact After the conductivity / conductivity before contact) × 100)) becomes the above range, it can be judged that most of the anion exchange groups in the anion exchanger (B) have been converted into bicarbonate ion form or carbonate ion form, that is, An anion exchange resin (A) was obtained. In the present invention, after the carbon dioxide dissolved water contacts the mixture of the anion exchanger (B) and the cation exchanger for a certain period of time, the conductivity becomes almost constant without any change, and is defined as the carbon dioxide dissolved water in the anion exchange resin conversion step. Electrical conductivity before contacting the mixture of anion exchanger (B) and cation exchanger.

In the anion exchanger conversion step (2), a conductivity meter may be installed at the inlet and outlet of the ion exchange tower, and the carbon dioxide dissolved water is supplied to the ion exchange tower until the conductivity of the carbon dioxide dissolved water at the outlet of the ion exchange tower is relatively high. The ratio of the conductivity of carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) is 90% or more, and preferably 95% or more. By calculating the change in the conductivity ratio of carbon dioxide dissolved water at the inlet and outlet of the ion exchange tower, it is easy to grasp the end time of the anion exchanger conversion step (2) while supplying carbon dioxide dissolved water to the ion exchange tower. In the anion exchanger conversion step (2), the carbon dioxide dissolved water starts to contact the anion exchanger. Most of the carbon dioxide dissolved in water (carbonate dissolved in water to form bicarbonate ions or carbonate ions) is consumed during the period from the mixture of the body (B) and the cation exchanger to the bicarbonate ion form. Or carbonate ion ion exchange, so the concentration of bicarbonate ions or carbonate ions in carbon dioxide dissolved in water becomes very low. Therefore, for a period of time after the carbon dioxide dissolved water comes into contact with the mixture of the anion exchanger (B) and the cation exchanger, the conductivity of the carbon dioxide dissolved water at the exit of the ion exchange tower is very low. After that, ion exchange to bicarbonate ion form or carbonate ion form is continued, and anion exchangers which are ion-exchanged into bicarbonate ion form or carbonate ion form are increased in the anion exchanger, because the ion exchange is consumed by bicarbonate ion form or carbonate ion form. The amount of carbon dioxide will gradually decrease. Therefore, the concentration of bicarbonate ions or carbonate ions in the carbon dioxide dissolved water at the exit of the ion exchange tower gradually increases, and the conductivity of the carbon dioxide dissolved water at the exit of the ion exchange tower gradually increases. The ratio of the conductivity of carbon dioxide dissolved water at the outlet of the ion exchange tower to the conductivity of carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) becomes the above range At this point, it can be judged that most of the anion exchange group in the anion exchanger (B) has been converted into a bicarbonate ion form or a carbonate ion form, that is, an anion exchange resin (A) is obtained. In the present invention, after the carbon dioxide dissolved water contacts the mixed bed composed of the anion exchanger (B) and the cation exchanger for a certain period of time, there is almost no change and the conductivity becomes substantially constant, which is defined as the anion exchange resin conversion step. Electrical conductivity at the entrance of the ion exchange tower.

Carbon dioxide dissolved water is continuously contacted with a mixture of anion exchanger (B) and cation exchanger or a mixed bed composed of anion exchanger (B) and cation exchanger to convert anion exchanger (B) to anion exchanger (A) At the same time, among all the anion exchange groups present in the anion exchanger, the more the number of anion exchange groups converted into bicarbonate ion form or carbonate ion form, the higher the performance. So, will overcast When the ion exchanger (B) is transformed into an anion exchanger (A), it is preferable to dissolve carbon dioxide in contact with a mixture of the anion exchanger (B) and the cation exchanger or a mixed bed composed of the anion exchanger (B) and the cation exchanger. Until the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group becomes preferably 80 equivalent% or more, and more preferably 95 equivalent% or more.

Among all the anion exchange groups in the anion exchanger before contacting carbon dioxide to dissolve water, the exchange capacity of anion exchange groups other than bicarbonate ion or carbonate ion can be obtained by analyzing the anion exchanger before contact. If all of the supplied carbon dioxide is used for ion exchange, carbon dioxide dissolved water is supplied to the anion exchanger until the concentration of carbon dioxide in the carbon dioxide dissolved water (equivalent / l) x space velocity (SV) (l / l-anion exchanger). × liquid-passing time (h)) "(equivalent (l)-anion exchanger) calculated from the formula (formula (1)) becomes the bicarbonate ion form or carbonate ion form among all the anion exchange groups in the anion exchanger. Anion exchange group (equivalent / l-anion exchanger), anion exchange with a total exchange capacity of bicarbonate ion form and carbonate ion form relative to the total exchange capacity of the anion exchange group can be obtained body. However, in reality, because the supplied carbon dioxide is not sufficiently dissolved, does not reach a predetermined concentration, or part of the carbon dioxide dissolved water leaks out due to ion exchange balance, not all of the supplied carbon dioxide is used in ion exchange, and there must be unused ions. Instead, the carbon dioxide is emitted. Therefore, in the anion exchanger conversion step (1) or the anion exchanger conversion step (2), in order to make the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger relative to the total exchange capacity of the anion exchange group, The ratio is 80 equivalent% or more, preferably 95 equivalent% or more. It is necessary to make the supply amount of carbon dioxide dissolved water less than the value calculated by the above formula (1). The amount of carbon dioxide dissolved water supplied when the exchange capacity of the anion exchange group of bicarbonate ion or carbonate ion is larger.

However, in the middle of implementing the anion exchanger conversion step (1) or the anion exchanger conversion step (2), it is impossible to take out the anion exchanger and analyze the amount of the bicarbonate ion form and carbonate ion form, so only carbon dioxide is used to dissolve the water. If the supply amount is managed, it is impossible to determine the extent to which the excess amount of carbon dioxide dissolved water is supplied to just make the total exchange capacity of the bicarbonate ion and carbonate ion form in the anion exchanger relative to the total exchange capacity of the anion exchange group. The ratio is 80 equivalent% or more, and preferably 95 equivalent% or more. Therefore, in practice, when anion exchange group conversion is performed, a considerable excess of carbon dioxide dissolved water must be supplied in order to reliably perform the conversion of the anion exchange group, and too much amount of carbon dioxide dissolved water will be wasted.

As described above, measure the conductivity of carbon dioxide dissolved water before and after it comes into contact with the anion exchanger, find the conductivity ratio after contact with the carbon dioxide dissolved water before contact, observe the change in the conductivity ratio, and supply carbon dioxide dissolved water until this point. If the value is 90% or more, preferably 95% or more, the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group becomes 80 equivalent% or more. It is preferably at a time point of 95% by weight or more, and the amount of carbon dioxide dissolved in the water can be supplied without too much, so that the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger can be exchanged with respect to the total exchange of the anion exchange group. The ratio of the capacity becomes 80 equivalent% or more, preferably 95 equivalent% or more, which prevents waste of carbon dioxide dissolved water.

In this way, in the method for producing a mixture of an anion exchanger and a cation exchanger of the present invention, by performing the anion exchanger conversion step (1), a mixture of an anion exchanger (A) and a cation exchanger is obtained, and the present invention In the method for producing a mixed bed composed of an anion exchanger and a cation exchanger, a mixed bed composed of an anion exchanger (A) and a cation exchanger is obtained by performing anion exchanger conversion step (2). In addition, in the method for producing a mixture of an anion exchanger and a cation exchanger according to the present invention or the method for producing a mixed bed composed of an anion exchanger and a cation exchanger according to the present invention, the anion in the anion exchanger (B) The exchange group is converted into bicarbonate ion form or carbonate ion form. Instead of using carbonate or bicarbonate aqueous solution, carbon dioxide is used to dissolve the water. Therefore, the cations of the cation exchange group of the cation exchanger existing with the anion exchanger will not be exchanged. To form carbonate or bicarbonate cations.

The mixture of the anion exchanger and the cation exchanger of the present invention is a mixture of the anion exchanger (A) and the cation exchanger obtained by performing the anion exchanger conversion step (1). The mixed bed composed of anion exchanger and cation exchanger of the present invention is a mixed bed composed of anion exchanger (A) and cation exchanger obtained by performing anion exchanger conversion step (2).

The method for purifying hydrogen peroxide water according to the first aspect of the present invention includes an anion exchanger conversion step (2) and a hydrogen peroxide water purification step; the anion exchanger conversion step (2) is performed by using Carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is contacted with a mixed bed composed of anion exchanger (B) and cation exchanger filled in an ion exchange tower to convert the anion exchanger (B) into With bicarbonate ion or with There is an anion exchanger (A) in the form of bicarbonate ion and carbonate ion, and a mixed bed composed of the anion exchanger (A) and the cation exchanger is obtained; the hydrogen peroxide water purification step is performed by The ion exchange tower supplies crude hydrogen peroxide water, and the crude hydrogen peroxide water is brought into contact with a mixed bed composed of the anion exchanger (A) and the cation exchanger to obtain purified hydrogen peroxide water.

That is, in the method for purifying hydrogen peroxide water according to the first aspect of the present invention, the cation exchanger and the anion exchanger (B) are simultaneously present, and carbon dioxide dissolved water is brought into contact with the anion exchanger (B). Anion exchanger (B) is converted to an anion exchanger (A) having a bicarbonate ion form or an anion exchanger (A) having a bicarbonate ion form and a carbonate ion form, followed by supplying crude hydrogen peroxide water to the ion exchange column, and Purification of crude hydrogen peroxide water.

The anion exchanger conversion step (2) of the method for purifying hydrogen peroxide water according to the first aspect of the present invention, and the anion exchanger conversion step of the method for producing a mixed bed composed of anion exchanger and cation exchanger according to the present invention ( 2) Same. Therefore, the anion exchanger (B), anion exchanger (A), cation exchanger, pure water, ultrapure water, carbon dioxide gas, carbon dioxide dissolved water, Mixed bed composed of anion exchanger (B) and cation exchanger, mixed bed composed of anion exchanger (A) and cation exchanger, and manufacturing method of mixed bed composed of anion exchanger and cation exchanger of the present invention Anion exchanger (B), anion exchanger (A), cation exchanger, pure water, ultrapure water, carbon dioxide gas, carbon dioxide dissolved water, a mixed bed composed of anion exchanger (B) and cation exchanger, The anion exchanger (A) is the same as the mixed bed composed of the cation exchanger.

In the method for purifying hydrogen peroxide water according to the first aspect of the present invention, an anion exchanger conversion step (2) is first performed. The anion exchanger conversion step (2) is performed by contacting carbon dioxide dissolved water in a mixed bed composed of anion exchanger (B) and a cation exchanger packed in an ion exchange tower to fill the mixed bed of the ion exchange tower. The step of converting the anion exchanger (B) to the anion exchanger (A).

In the method for purifying hydrogen peroxide water according to the first aspect of the present invention, the hydrogen peroxide water purification step is performed after the anion exchanger conversion step (2). The hydrogen peroxide water refining step is to supply crude hydrogen peroxide water to an ion exchange tower filled with a mixed bed composed of anion exchanger (A) and cation exchanger, so that the crude hydrogen peroxide water contacts the anion exchanger (A). ) A mixed bed with a cation exchanger to obtain refined hydrogen peroxide.

In the hydrogen peroxide water refining step, the temperature when the crude hydrogen peroxide water is brought into contact with the mixed bed composed of the anion exchanger (A) and the cation exchanger is preferably -10 to 25 ° C, and more preferably -5 to 10 ° C. In the hydrogen peroxide water refining step, the space velocity (SV) of the crude hydrogen peroxide water supplied to the ion exchange tower is preferably 1 to 30 h ^-1 , and particularly preferably 1 to 15 h ^-1 .

In this way, in the method for purifying hydrogen peroxide water according to the first aspect of the present invention, purification of crude hydrogen peroxide water is performed.

In addition, when the hydrogen peroxide water refining step of the method for purifying hydrogen peroxide water according to the first aspect of the present invention is continuously performed, many of the relative anions of the anion exchanger (A), that is, bicarbonate ions are exchanged into crude When preparing the impurity anions in hydrogen peroxide water, the anion exchanger conversion step (2) can also be performed to fill the anion exchanger (anion) in a mixed bed composed of anion exchanger and cation exchanger in an ion exchange tower. The exchanger (B)) is converted into an anion exchanger (A), and then a hydrogen peroxide water purification step is performed. That is, in the method for purifying hydrogen peroxide water according to the first aspect of the present invention, the anion exchanger conversion step (2) and the hydrogen peroxide water purification step may be repeatedly performed alternately.

In the method for purifying hydrogen peroxide water according to the first aspect of the present invention, in the anion exchanger conversion step (2) and the anion exchanger (A), the total exchange capacity is compared with the total amount of the bicarbonate ion form and the carbonate ion form. The ratio of the exchange capacity of the bicarbonate ion form is preferably 70 equivalent% or more, more preferably 75 equivalent% or more, and even more preferably 80 equivalent% or more. In the method for purifying hydrogen peroxide water according to the first aspect of the present invention, in the anion exchanger conversion step (2), the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is brought into contact with anion exchange. The mixed bed composed of the body (B) and the cation exchanger until the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form to the total exchange capacity of the anion exchanger (A) becomes preferably 50 equivalent% or more, especially It is preferably 60 equivalent% or more, more preferably 70 equivalent% or more, still more preferably 80 equivalent% or more, still more preferably 95 equivalent% or more, even more preferably 99 equivalent% or more, and still more preferably 100 equivalent%.

In the method for purifying hydrogen peroxide water according to the first aspect of the present invention, in the anion exchanger conversion step (2), a conductivity meter may be installed at the inlet and outlet of the ion exchange tower, and carbon dioxide may be supplied to the ion exchange tower. The ratio of the conductivity of the dissolved carbon dioxide dissolved water up to the exit of the ion exchange tower to the conductivity of the dissolved carbon dioxide water at the entrance of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) is more than 90%, It is preferably at least 95%.

As described above, measure the conductivity of carbon dioxide dissolved water before and after it comes into contact with the anion exchanger, find the conductivity ratio after contact with the carbon dioxide dissolved water before contact, observe the change in the conductivity ratio, and supply carbon dioxide dissolved water until this point. If the value is 90% or more, preferably 95% or more, the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group becomes 80 equivalent% or more. It is preferably at a time point of 95% by weight or more, and the amount of carbon dioxide dissolved in the water can be supplied without too much, so that the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger is exchanged with respect to the total exchange of the anion exchange group. The ratio of the capacity becomes 80 equivalent% or more, preferably 95 equivalent% or more, which prevents waste of carbon dioxide dissolved water.

The anion exchanger of the present invention is characterized by an anion exchanger having a bicarbonate ion form (-HCO ₃ ), or an anion exchanger having a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ). Anion exchanger. That is, the anion exchanger of the present invention is the same as the aforementioned anion exchanger and cation exchanger of the present invention or the anion exchanger (A) of the mixed bed composed of the anion exchanger and the cation exchanger of the present invention. Hereinafter, the anion exchanger of the present invention will also be described as an anion exchanger (A).

The anion exchanger (anion exchanger (A)) of the present invention is an anion exchanger having a bicarbonate ion form (-HCO ₃ ) or a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ) of the anion exchanger, i.e., based anion exchanger having a counter anion-exchange groups are anionic bicarbonate ion (-HCO ₃ ions), the anion exchange or an anion having a relatively bicarbonate ion (-HCO ₃ ions) of the opposite group The anion is an anion exchanger of an anion-exchange group of a carbonate ion (-CO ₃ ion). The anion exchanger (A) is a resin whose matrix is a resin, and an anion exchanger in which an anion exchange group is introduced into the resin. The anion exchanger is a styrene gel-type or MR-type anion exchange resin and an organic porous anion exchanger. In this specification, the bicarbonate ion form (R-HCO ₃ ) and carbonate ion form (R-CO ₃ ) are described. However, in actual use, the bicarbonate ion form dissociates into R-HCO ₃ ^- and carbonate ion. The form dissociates as R-CO ₃ ^2- .

In the anion exchanger (anion exchanger (A)) of the present invention, the ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form is preferably 70 equivalent% or more, particularly preferably It is 75 equivalent% or more, and more preferably 80 equivalent% or more. By setting the ratio of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form within the above range, the purification performance of hydrogen peroxide water and other water, aqueous solution, or organic solvent purified using an anion exchanger is improved. The viewpoint is more ideal.

The anion exchanger (anion exchanger (A)) of the present invention may have a bicarbonate ion form and an ion form other than a carbonate ion form, and a bicarbonate ion in the anion exchanger if it does not adversely affect purification. The ratio of the total exchange capacity of the form and carbonate ion form to the total exchange capacity of the anion exchange group is preferably 50 equivalent% or more, particularly 60 equivalent% or more is particularly desirable, 70 equivalent% or more is more desirable, and 80 equivalent% or more is more preferable. 95% equivalent is more preferable, 99% equivalent is more preferable, and 100% equivalent is more preferable. By setting the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form to the total exchange capacity within the above range, the purification performance of hydrogen peroxide water and other water, aqueous solution, or organic solvent purified using an anion exchanger is improved. This view is ideal.

When the anion exchanger (anion exchanger (A)) of the present invention has an ion form other than a bicarbonate ion form and a carbonate ion form, examples of such an ion form include a Cl form, an OH form, and the like. In addition, if the amount of the OH form in the anion exchanger (A) is too much, the hydrogen peroxide decomposition reaction will easily proceed when the hydrogen peroxide is purified. Therefore, when the anion exchanger (A) is used in peroxidation, When purifying hydrogen, the ratio of the OH-type exchange capacity to the total exchange capacity in the anion exchanger (A) is preferably 1 equivalent% or less, particularly preferably 0.1 equivalent% or less, and even more preferably 0 equivalent%.

Among the anion exchangers (anion exchangers (A)) of the present invention, the resin to which an anion exchange group is introduced is preferably a styrene-divinylbenzene copolymer.

Examples of the anion exchanger (anion exchanger (A)) of the present invention include a strongly basic type I having a 4th-order ammonium group as a functional group, and a nitrogen atom-bonded group of the ammonium group having an alkyl group. The ammonium group is used as a functional group, and the nitrogen atom-bonded group of this ammonium group is a strong basic type II of an alkyl group and an alkanol group, and a weak basic type having a first to a third amine group as a functional group. Strongly basic type I anion exchanger is preferred.

When the anion exchanger (anion exchanger (A)) of the present invention is a granular anion exchange resin, the average particle diameter of the anion exchange resin is preferably 0.2 to 1.0 mm, particularly preferably 0.4 to 0.8 mm. In addition, when the anion exchanger (anion exchanger (A)) of the present invention is an organic porous anion exchanger, the structure of the organic porous anion exchanger: most of the bubble-like micropores overlap each other, and this overlapping portion becomes an open communication A structure in which pores are formed in a skeleton made of resin, that is, a continuous microporous structure.

The method for producing an anion exchanger of the present invention is characterized by including an anion exchanger conversion step (3), in which the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is brought into contact with the anion exchanger (B), The anion exchanger (B) is converted into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form to obtain the anion exchanger (A).

The anion exchanger conversion step (3) of the method for producing an anion exchanger of the present invention is to convert the anion exchanger (B) into a bicarbonate ion-form or A step of anion exchanger (A) having bicarbonate ion form and carbonate ion form.

The anion exchanger (B) in the anion exchanger conversion step (3) is an anion exchanger before the anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. If the purification of crude hydrogen peroxide water is carried out using a strongly basic anion exchanger, that is, an OH ion-formed anion exchanger (the opposite anion of the anion exchange group is an anion exchanger with OH ions), hydrogen peroxide will contact the OH ion form. Decomposition occurs during anion exchanger. In addition, if the purification of crude hydrogen peroxide water is to be performed using a Cl ion anion exchanger (anion exchanger in which the opposite anion of the anion exchange group is Cl ion), the Cl ion will flow out to the treatment due to the ion exchange reaction with the target ion. It cannot be purified because it is in liquid. Therefore, in the method for producing an anion exchanger of the present invention, the anion exchanger is converted into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form.

In the anion exchanger conversion step (3), carbon dioxide dissolved water is brought into contact with anion exchangers such as OH ion form, Cl ion form, etc., preferably an OH form anion exchanger, that is, converted into a bicarbonate ion form or Anion cross before anion exchanger (A) with bicarbonate ion form and carbonate ion form (Anion exchanger (B)), and the anion exchanger (B) is converted into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. In addition, if an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form is continuously used to purify the water to be treated (hydrogen peroxide water or other water or aqueous solution purified using an anion exchanger) The bicarbonate ions of the anion exchanger (A) will be exchanged for impurity anions in the treated water. Therefore, after a certain degree of refining of the treated water, the anion exchanger which is ion-exchanged by impurity anions can be regenerated into an anion exchanger having a bicarbonate ion form or a bicarbonate ion form and a carbonate ion form (A) . In the present invention, before the purification of such first treated water is performed, an anion exchanger conversion step is performed to obtain an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form. In (3), purification of the treated water such as hydrogen peroxide water is performed to some extent with the anion exchanger before being converted into the anion exchanger (A), and ion exchange is performed with impurity ions in the treated water to make the supply again. Both of the anion exchangers in the anion exchanger conversion step (3) become anion exchangers (B) before being converted into anion exchangers (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form.

The anion exchanger (A) in the anion exchanger conversion step (3), that is, the anion exchanger obtained by performing the anion exchanger conversion step (3), is an anion exchanger having a bicarbonate ion form (-HCO ₃ ), or Anion exchanger with bicarbonate ion form (-HCO ₃ ) and carbonate ion form (-CO ₃ ). The ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form of the anion exchanger (A) to the total exchange capacity of the anion exchange group is not particularly limited, and is preferably 50 equivalent% or more, particularly preferably 60 equivalent% or more. More preferably, it is 70 equivalent% or more, more preferably 80 equivalent% or more, even more preferably 95 equivalent% or more, still more preferably 99 equivalent% or more, and even more preferably 100 equivalent%, and the anion exchanger (A) The ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form is preferably 70 equivalent% or more, particularly preferably 75 equivalent% or more, and more preferably 80 equivalent% or more. .

The anion exchanger (B) in the anion exchanger conversion step (3) is based on a resin, and an anion exchanger with an anion exchange group introduced into the resin is a styrene gel or MR anion exchanger Resin, organic porous anion exchanger. Among the anion exchangers (B), a styrene-divinylbenzene copolymer is preferably used as a resin to which an anion exchange group is introduced.

Examples of the anion exchanger (B) in the anion exchanger conversion step (3) include a strong ammonium type I having a quaternary ammonium group as a functional group, and the nitrogen atom-bonded group of the ammonium group has an alkyl group. Grade 4 ammonium group is a functional group, and the nitrogen atom-bonded group of this ammonium group is a strong basic type II of an alkyl group and an alkanol group, and a weak basicity having a 1st to a 3rd amine group as a functional group. Of these, a strongly basic type I anion exchanger is preferred. The anion exchanger (B) in the anion exchanger conversion step (3) is preferably OH-shaped.

When the anion exchanger (B) in the anion exchanger conversion step (3) is a granular anion exchange resin, the average particle diameter of the anion exchange resin is preferably 0.2 to 1.0 mm, and particularly preferably 0.4 to 0.8 mm. When the anion exchange resin (B) in the anion exchanger conversion step (3) is an organic porous anion exchanger, the structure of the organic porous anion exchanger: most of the bubble-like micropores overlap each other, and this overlapping portion becomes an open communication A structure in which pores are formed in a skeleton made of resin, that is, a continuous microporous structure.

The carbon dioxide-dissolved water of the anion exchanger conversion step (3) is obtained by dissolving carbon dioxide gas in pure water or ultrapure water. Pure water or ultrapure water, which is pure by removing ionic and non-ionic substances from raw water Pure water or ultrapure water obtained by processing raw water in a water manufacturing device or ultrapure water manufacturing device. Pure water with a resistivity of 1.0MΩ‧cm or more, preferably ultrapure water with a resistivity of 10MΩ‧cm or more, particularly preferably Ultra-pure water with resistivity above 18MΩ‧cm is ideal.

The concentration of carbon dioxide gas in the carbon dioxide-dissolved water of the anion exchanger conversion step (3) may be any concentration as long as the carbon dioxide gas can be dissolved in pure or ultrapure water, preferably 1 to 2000 mg / L, and particularly preferably 20 to 2000mg / L. The higher the dissolved concentration of carbon dioxide, the more it can be processed in a short time, and the amount of water used can also be reduced.

The method for obtaining carbon dioxide-dissolved water, that is, a method for dissolving carbon dioxide gas in pure water or ultrapure water is not particularly limited, and a method for producing functional water used for washing applications of electronic parts and components can be cited. For example: a method of dissolving carbon dioxide gas using a hollow fiber membrane, a method of directly injecting carbon dioxide gas into a pipe, a method of dissolving carbon dioxide gas by dispersing equipment such as a static mixer, and supplying ultrapure water in a gas dissolution tank A method of supplying carbon dioxide gas on the upstream side of the pump and dissolving it by stirring in the pump. In order to dissolve carbon dioxide to a saturated concentration with good efficiency, it is preferable to use a hollow fiber membrane to dissolve carbon dioxide gas. When a gas cylinder is used for supplying carbon dioxide gas, it is preferable to provide a particle removal filter for removing particles below 0.5 μm in the gas supply pipe, and a particle removal filter for removing particles below 0.2 μm is particularly preferable.

In the preparation of carbon dioxide dissolved water, the mass flow controller is used to control the supply amount of carbon dioxide gas dissolved in pure water or ultrapure water. The carbon dioxide concentration is continuously monitored by a conductivity meter.

In the anion exchanger conversion step (3), the method of contacting the carbon dioxide-dissolved water with the anion exchanger (B) is not particularly limited, for example, a method of adding the anion exchanger (B) to carbon dioxide-dissolved water and stirring, and anion exchanger (B) A method of filling a contact container with a supply pipe and a discharge pipe provided with carbon dioxide dissolved water, and discharging the water in the container to the outside of the container while supplying carbon dioxide dissolved water to the container, filling the ion exchange tower, and A method for supplying carbon dioxide dissolved water to the ion exchange tower. In the anion exchanger conversion step (3), if the temperature at which the carbon dioxide dissolved water contacts the anion exchanger (B) is low, it can increase the solubility of carbon dioxide to some extent, so it is ideal, but from the viewpoint of energy consumption, it is better It is 5 to 40 ° C, particularly preferably 10 to 30 ° C. In the anion exchanger conversion step (3), when carbon dioxide dissolved water is passed through the ion exchange tower filled with the anion exchanger (B), carbon dioxide dissolved water can be supplied to the ion exchange tower by one pass, but In order to reduce the consumption of pure water or ultrapure water, a circulation tank and a pump can be provided at the back of the ion exchange tower, and the used water can be recycled as raw water for the preparation of carbon dioxide dissolved water. In addition, when the used water is recycled, the amount of carbon dioxide gas can be reduced by feeding back the value of the conductivity meter and controlling the amount of carbon dioxide gas supplied.

In addition, by performing the anion exchanger conversion step (3), all or part of the opposite anions of the anion exchanger (B) are exchanged for bicarbonate ions (-HCO ₃ ) or carbonate ions (-CO ₃ ) and converted into a heavy carbon dioxide ion (-HCO ₃ ). Carbonate ion form or anion exchanger (A) having bicarbonate ion form and carbonate ion form.

The anion exchanger (A) in the anion exchanger conversion step (3) is an anion exchanger having a bicarbonate ion form (-HCO ₃ ) or a bicarbonate ion form (-HCO ₃ ) and a carbonate ion form (-CO ₃ ) an anion exchanger, that is, an anion exchanger having an anion exchange group whose opposite anion is a bicarbonate ion (-HCO ₃ ion), or an anion exchanger having an anion exchange group whose opposite anion is a bicarbonate ion (-HCO ₃ ion), and The opposite anion is an anion exchanger of an anion exchange group of a carbonate ion (-CO ₃ ion). In this specification, the bicarbonate ion form (R-HCO ₃ ) and carbonate ion form (R-CO ₃ ) are described. However, in actual use, the bicarbonate ion form dissociates into R-HCO ₃ ^- and carbonate ion form dissociation. R-CO ₃ ^2- .

In addition, in the anion exchanger (A) of the anion exchanger conversion step (3), the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form to the total exchange capacity of the anion exchanger is not particularly limited, and is preferably Above 50 equivalent%, particularly preferably above 60 equivalent%, more preferably above 70 equivalent%, even more preferably above 80 equivalent%, even more preferably above 95 equivalent%, even more preferably above 99 equivalent%, and even more preferably It is 100 equivalent%. That is, in the anion exchanger conversion step (3), the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is brought into contact with the anion exchanger (B) until the bicarbonate in the anion exchanger (A) The ratio of the total exchange capacity of the ionic and carbonate ion forms to the total exchange capacity is preferably 50 equivalent% or more, particularly preferably 60 equivalent% or more, more preferably 70 equivalent% or more, and even more preferably 80 equivalent% or more. , More preferably 95 equivalent% or more, still more preferably 99 equivalent% or more, even more preferably 100 equivalent%.

In the anion exchanger (A) of the anion exchanger conversion step (3), the ratio of the exchange capacity of the bicarbonate ion form to the total exchange capacity of the bicarbonate ion form and the carbonate ion form is preferably 70 equivalent% or more, especially It is preferably at least 75 equivalent%, more preferably at least 80 equivalent%. Bicarbonate ion form has a lower selection coefficient than carbonate ion form, so it is particularly effective for improving the processing performance of anion with low selectivity and low concentration of ion exchange load. The more the proportion of bicarbonate ion form in anion exchanger, The higher the refining performance of hydrogen peroxide water and other treated water. That is, by decarbonating the anion exchanger (A), The ratio of the sub-form exchange capacity to the total exchange capacity of the bicarbonate ion form and the carbonate ion form is in the above range, which is ideal for improving the purification performance of hydrogen peroxide water or other treated water.

In the anion exchanger conversion step (3), for example, the anion exchanger (B) is charged into a container provided with a carbon dioxide-dissolved water supply pipe and a discharge tube. Water can be discharged to the outside of the container, or the ion exchange tower can be filled with anion exchanger (B) and the carbon dioxide can be dissolved in the ion exchange tower. Water contacts the mixture of anion exchanger (B) and cation exchanger, but in this case, the conductivity of carbon dioxide dissolved water before and after contact with anion exchanger (B) is measured to make carbon dioxide dissolve water and anion exchanger (B The ratio of the conductivity of the carbon dioxide-dissolved water after the contact is performed until the anion exchanger (B) is contacted to the conductivity of the carbon dioxide-dissolved water before the anion exchanger (B) is contacted ((conductivity after contact / conductivity before contact) The ratio) × 100)) is 90% or more, and preferably 95% or more. By determining the change in the conductivity ratio of carbon dioxide dissolved water before and after the anion exchanger (B) is contacted, it is easy to grasp the end of the anion exchanger conversion step (3) while contacting the carbon dioxide dissolved water with the anion exchanger (B). Point in time. In the anion exchanger conversion step (3), most of the carbon dioxide (the bicarbonate ion or carbonate ion generated by carbon dioxide dissolved in water) is consumed during the period from when the carbon dioxide dissolved water comes into contact with the anion exchanger (B). Since the anion exchanger (B) is ion-exchanged to a bicarbonate ion or a carbonate ion, the concentration of the bicarbonate ion or carbonate ion in the carbon dioxide dissolved water becomes very low. Therefore, for a period of time after the carbon dioxide dissolved water comes into contact with the anion exchanger (B), the conductivity of the carbon dioxide dissolved water after contacting the anion exchanger (B) is very low. After that, the ion exchange to the bicarbonate ion form or carbonate ion form is continued, and the anion exchanger is ion-exchanged into a bicarbonate ion form or a carbonate ion form, because the ion exchange is a bicarbonate ion. The amount of carbon dioxide consumed by the carbon dioxide ion or carbonate ion will gradually decrease. Therefore, the concentration of bicarbonate ions or carbonate ions in the carbon dioxide dissolved water after contacting the anion exchanger (B) gradually increases, and the conductivity of the carbon dioxide dissolved water after contact with the anion exchanger (B) gradually increases. Electrical conductivity of carbon dioxide dissolved water after contact with anion exchanger (B) relative to electrical conductivity of carbon dioxide dissolved water before contact with anion exchanger (B) ((conductivity after contact / conductivity before contact) × 100)) When the above range is reached, it can be judged that most of the anion exchange group in the anion exchanger (B) has been converted into a bicarbonate ion form or a carbonate ion form, that is, an anion exchange resin (A) is obtained. In the present invention, after the carbon dioxide dissolved water contacts the anion exchanger (B) for a certain period of time, there is almost no change and the conductivity becomes substantially constant. It is defined as the carbon dioxide dissolved water contacting the anion exchange in the anion exchange resin conversion step (3). Conductivity before body (B).

When carbon dioxide dissolved water is continuously brought into contact with the anion exchanger (B) to convert the anion exchanger (B) to the anion exchanger (A), it is the same as the anion exchanger conversion step (1) or the anion exchanger conversion step (2). Among all the anion exchange groups present in the anion exchanger, the more the number of anion exchange groups converted into bicarbonate ion form or carbonate ion form, the higher the performance. Therefore, when converting the anion exchanger (B) to the anion exchanger (A), it is preferable to contact the dissolved carbon dioxide water with the anion exchanger (B) until the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger is relatively large. The ratio of the total exchange capacity in the anion exchange group is preferably 80 equivalent% or more, and more preferably 95 equivalent% or more.

As mentioned above, among all anion exchange groups in the anion exchanger before contacting carbon dioxide to dissolve water, the exchange capacity of anion exchange groups other than bicarbonate ion or carbonate ion can be obtained by analyzing the anion exchanger before contact. If all of the supplied carbon dioxide is used for ion exchange, The carbon dioxide-dissolved water is supplied to the anion exchanger until the expression "the concentration of carbon dioxide in the carbon dioxide-dissolved water (equivalents / l) x space velocity (SV) (l / l-anion exchanger) x flow time (h))" is given by (1) The calculated amount (equivalent / l-anion exchanger) becomes the exchange capacity (equivalent / l-anion exchange) of all the anion exchangers in the anion exchanger which is not an anion exchange group that is not bicarbonate ion or carbonate ion. Anion exchangers having a total exchange capacity of bicarbonate ion form and carbonate ion form relative to the total exchange capacity of the anion exchange group of 100 equivalent% can be obtained. However, in reality, because the supplied carbon dioxide is not sufficiently dissolved, does not reach a predetermined concentration, or part of the carbon dioxide dissolved water leaks out due to ion exchange balance, not all of the supplied carbon dioxide is used in ion exchange, and there must be unused ions. Instead, the carbon dioxide is emitted. Therefore, in the anion exchanger conversion step (3), in order to make the ratio of the total exchange capacity of the bicarbonate ion form and carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group 80% or more, it is preferable. If it is 95 equivalent% or more, it is necessary to make the supply amount of carbon dioxide dissolved water more than the supply capacity of carbon dioxide dissolved water when the value calculated from the above formula (1) becomes the exchange capacity of anion exchange group which is not bicarbonate ion or carbonate ion. More excess.

However, in the middle of implementing the anion exchanger conversion step (3), it is impossible to take out the anion exchanger and analyze the amount of bicarbonate ion form and carbonate ion form. Therefore, it is impossible to manage only by the supply of carbon dioxide dissolved water. Judging to what extent, the excess amount of carbon dioxide dissolved water can just make the total exchange capacity of the bicarbonate ion form and carbonate ion form in the anion exchanger relative to the total exchange capacity of the anion exchange group to be 80 equivalent% or more, Preferably, it is above 95 equivalent%. Therefore, in practice, when anion exchange group conversion is carried out, a considerable excess of carbon dioxide must be supplied for dissolution. Water, so that the conversion of the anion exchange group can be carried out reliably, too much amount of carbon dioxide to dissolve the water will be wasted.

As described above, measure the conductivity of carbon dioxide dissolved water before and after it comes into contact with the anion exchanger, find the conductivity ratio after contact with the carbon dioxide dissolved water before contact, observe the change in the conductivity ratio, and supply carbon dioxide dissolved water until this point. If the value is 90% or more, preferably 95% or more, the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group becomes 80 equivalent% or more. It is preferably at a time point of 95% by weight or more, and the amount of carbon dioxide dissolved in the water can be supplied without too much, so that the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger can be exchanged with respect to the total exchange of the anion exchange group. The ratio of the capacity becomes 80 equivalent% or more, preferably 95 equivalent% or more, which prevents waste of carbon dioxide dissolved water.

The method for purifying hydrogen peroxide water according to the second aspect of the present invention is characterized by including an anion exchanger conversion step (4) and a hydrogen peroxide water purification step; the anion exchanger conversion step (4) is performed by using pure water Or carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in ultrapure water is contacted with anion exchanger (B) filled in an ion exchange tower to transform the anion exchanger (B) into a form having a bicarbonate ion or having a bicarbonate ion. An anion exchanger (A) in the form of a carbonate ion to obtain the anion exchanger (A); the hydrogen peroxide water refining step is to supply crude hydrogen peroxide water to the ion exchange tower to make the crude hydrogen peroxide water This anion exchanger (A) is contacted to obtain purified hydrogen peroxide water.

The anion exchanger (B), anion exchanger (A), pure water, ultrapure water, carbon dioxide gas, and carbon dioxide are dissolved in the anion exchanger conversion step (4) of the method for purifying hydrogen peroxide water according to the second aspect of the present invention. Water is the same as the anion exchanger (B), anion exchanger (A), pure water, ultrapure water, carbon dioxide gas, and carbon dioxide dissolved water in the anion exchanger conversion step (3) of the method for producing an anion exchanger of the present invention. .

In the method for purifying hydrogen peroxide water according to the second aspect of the present invention, an anion exchanger conversion step (4) is performed first. The anion exchanger conversion step (4) is to convert the anion exchanger (B) filled in the ion exchange tower into an anion exchanger (B) by contacting carbon dioxide dissolved water with the anion exchanger (B) filled in the ion exchange tower ( A). Anion exchanger conversion step (4) is a method of contacting anion exchanger (B) with carbon dioxide dissolved water in anion conversion step (3). The ion exchange column is filled with anion exchanger (B), and The ion exchange tower of the body (B) supplies carbon dioxide dissolved water to implement a method in which the carbon dioxide dissolved water contacts the anion exchanger (B).

In the method for purifying hydrogen peroxide water according to the second aspect of the present invention, the anion exchanger conversion step (4) is followed by a hydrogen peroxide water purification step. The hydrogen peroxide water refining step is to supply crude hydrogen peroxide water to an ion exchange tower filled with an anion exchanger (A), so that the crude hydrogen peroxide water contacts the anion exchanger (A) to obtain refined peroxide. Hydrogen water.

In the hydrogen peroxide water refining step, the temperature when the crude hydrogen peroxide water is brought into contact with the anion exchanger (A) is preferably -10 to 25 ° C, and particularly preferably -5 to 10 ° C. In the hydrogen peroxide water refining step, the space velocity (SV) of the crude hydrogen peroxide water supplied to the ion exchange tower is preferably 1 to 30 h ^-1 , and particularly preferably 1 to 15 h ^-1 .

In this way, in the method for purifying hydrogen peroxide water according to the second aspect of the present invention, the crude hydrogen peroxide water is purified.

In addition, since the hydrogen peroxide water purification step of the method for purifying hydrogen peroxide water according to the second aspect of the present invention is continuously carried out, many of the bicarbonate ions, which are the opposite anions of the anion exchanger (A), have been exchanged for crude peroxide. For impurity anions in hydrogen water, the anion exchanger conversion step (4) can be performed again to convert the anion exchanger (anion exchanger (B)) filled in the ion exchange tower to an anion exchanger (A), and then perform peroxidation. Hydrogen water refining step. That is, in the method for purifying hydrogen peroxide water of the present invention, the anion exchanger conversion step (4) and the hydrogen peroxide water purification step may be repeatedly performed alternately.

In the method for purifying hydrogen peroxide water according to the second aspect of the present invention, in the anion exchanger conversion step (4), the total exchange capacity for the bicarbonate ion form and the carbonate ion form in the anion exchanger (A) The ratio of the exchange capacity of the bicarbonate ion form is preferably 70 equivalent% or more, more preferably 75 equivalent% or more, and even more preferably 80 equivalent% or more. In the method for purifying hydrogen peroxide water according to the second aspect of the present invention, in the anion exchanger conversion step (4), the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water is brought into contact with anion exchange. The ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger (A) to the total exchange capacity of the anion exchange group is preferably 50 equivalent% or more, and more preferably 60 equivalent. % Or more, more preferably 70 equivalent% or more, still more preferably 80 equivalent% or more, more preferably 95 equivalent% or more, still more preferably 99 equivalent% or more, and still more preferably 100 equivalent%.

In the method for purifying hydrogen peroxide water according to the second aspect of the present invention, in the anion exchanger conversion step (4), a conductivity meter may be installed at the inlet and outlet of the ion exchange tower, and carbon dioxide may be applied to the ion exchange tower. The ratio of the conductivity of the carbon dioxide dissolved water supplied to the outlet of the ion exchange tower to the conductivity of the carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) becomes 90% The above is preferably at least 95%.

As described above, measure the conductivity of carbon dioxide dissolved water before and after it comes into contact with the anion exchanger, find the conductivity ratio after contact with the carbon dioxide dissolved water before contact, observe the change in the conductivity ratio, and supply carbon dioxide dissolved water until this point. If the value is 90% or more, preferably 95% or more, the ratio of the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger to the total exchange capacity of the anion exchange group becomes 80 equivalent% or more. It is preferably at a time point of 95% by weight or more, and the amount of carbon dioxide dissolved in the water can be supplied without too much, so that the total exchange capacity of the bicarbonate ion form and the carbonate ion form in the anion exchanger can be exchanged with respect to the total exchange of the anion exchange group. The ratio of the capacity becomes 80 equivalent% or more, preferably 95 equivalent% or more, which prevents waste of carbon dioxide dissolved water.

In the present invention, in the anion exchanger conversion step, in order to exchange the opposite anions of the anion exchanger (B) into bicarbonate ions, carbon dioxide is used to dissolve water in carbon dioxide. Since the carbon dioxide dissolved water is weakly acidic, the proportion of monovalent bicarbonate ions in the carbon dioxide dissolved water is large. Therefore, in the anion exchanger conversion step, an anion exchanger having a very high proportion of bicarbonate ion form can be obtained, that is, compared to the total exchange capacity of the bicarbonate ion form and carbonate ion form in the anion exchanger (A), The ratio of the ionic exchange capacity is 70 equivalent% or more, preferably 75 equivalent% or more, and even more preferably 80 equivalent% or more of an anion exchanger.

On the other hand, the conventional method uses a bicarbonate aqueous solution for the exchange of anions with respect to anions. The bicarbonate aqueous solution is weakly alkaline, so the proportion of divalent carbonate ions in the bicarbonate aqueous solution is large. Therefore, in the conventional method, the proportion of the bicarbonate ion form is not so high.

The bicarbonate ion form is more easily ion-exchanged than the carbonate ion form, so anion exchangers with a larger proportion of bicarbonate ion forms than hydrogen ion water or other anion exchangers with a lower proportion of heavy carbonate ion forms. Water has a high refining performance, and in particular, the effect of improving the processing performance on anion with a low selectivity and an ion exchange load with a low concentration can be expected. In this way, by implementing the anion exchanger conversion step, the present invention can obtain a total exchange capacity with respect to the bicarbonate ion form and the carbonate ion form, and the ratio of the bicarbonate ion form is 70% or more, preferably 75% or more, In particular, a very high anion exchanger (A) of 80 equivalent% or more can be used to obtain water to be treated (hydrogen peroxide water or other anion exchanger, a mixture of anion exchanger and cation exchanger, or water purified by a mixed bed, Aqueous solution or organic solvent) has high refining performance, especially for anion exchangers with low selectivity and low concentration of ion exchange load.

In this way, the amount of water to be treated until the next anion exchanger conversion step can be increased. Therefore, when the hydrogen peroxide water purification method of the present invention repeats the anion exchanger conversion step and the hydrogen peroxide water purification step, the frequency of performing the anion exchanger conversion step can be reduced, and the hydrogen peroxide water purification can be efficiently performed.

In the method for purifying hydrogen peroxide water of the present invention, the anion exchanger (A) used for the purification of crude hydrogen peroxide water is prepared by using carbon dioxide to dissolve water. For example, the salt of ammonium bicarbonate is insoluble in carbon dioxide to dissolve in water, so it is not necessary to wash the ammonium ion after converting the anion exchanger to the bicarbonate ion form as in the conventional method using an aqueous solution of ammonium bicarbonate. That is, in the method for purifying hydrogen peroxide water of the present invention, after performing the anion exchanger conversion step, the anion exchanger (A) does not need to be washed, and the hydrogen peroxide water purification step can be performed quickly. Therefore, the method for purifying hydrogen peroxide water of the present invention can efficiently implement the purification of hydrogen peroxide water.

[Example]

Hereinafter, the present invention will be described in detail according to examples. However, the present invention is not limited to the following examples.

(Example 1)

As shown in Fig. 1, an ion exchange tower made of PFA (copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether) with an inner diameter of 16 mm and a height of 30 cm is installed with a PFA net at the bottom, and 50 mL of strong alkali is filled in the tower. Mixed bed ESP-1 (mixed bed with a ratio of 1: 1, manufactured by Organo) of anion exchanger (OH form) and strongly acidic cation exchanger (H form). Next, ultra-pure water and a hollow fiber membrane for gas dissolution using a mass flow controller for gas are supplied to the carbon fiber and the carbon dioxide gas is dissolved in the ultra-pure water to obtain carbon dioxide-dissolved water. Next, the obtained carbon dioxide dissolved water was supplied into an ion exchange tower made of PFA, and passed through an ESP-1 packed layer. At this time, the flow-through flow rate of the ion exchange tower made of PFA was set to 1.5 L / hour, and the supply amount of carbon dioxide gas to the hollow fiber membrane for gas dissolution was adjusted so that the conductivity at the inlet of the tower was 38 μS / cm. Then, the carbon dioxide dissolved water was continuously passed in (about 90 minutes) until the conductivity at the outlet became equal to that at the inlet of the tower (38 μS / cm), and an anion exchanger and a cation exchanger were obtained. Mixed bed A. The change in the conductivity of the carbon dioxide dissolved water at the tower inlet and the conductivity of the carbon dioxide dissolved water at the tower outlet at this time is shown in FIG. 2. In addition, in FIG. 2, the electric conductivity of the carbon dioxide water at the inlet of the tower fluctuated slightly in a period of time after the supply of carbon dioxide dissolved water was started, but it was fixed at 38 μS / cm after about 45 minutes after the start of the supply.

Next, ultrapure water was supplied to the PFA-made ion exchange tower for 10 minutes, and the discharged water was sampled. The content of ammonium ions in the discharged water was measured. As a result, the ammonium ions did not reach 0.1 mg / L, which was the lower limit of detection.

Next, in order to find the ion conversion ratio (%) of the anion exchanger to the carbonate or bicarbonate form in the mixed bed A composed of an anion exchanger and a cation exchanger, a sodium nitrate aqueous solution is passed through the packed layer to obtain The treatment solution was neutralized and titrated using sodium hydroxide (indicator: phenolphthalein and methyl red mixed indicator). The results are shown in Table 1.

Further, in FIG. 2, the conductivity of the carbon dioxide dissolved water at the tower inlet and the conductivity of the carbon dioxide dissolved water at the tower outlet were obtained, and the conversion rate of the anion exchange resin to the bicarbonate ion form or the bicarbonate ion form and the carbonate ion form was calculated. As a result, when the conductivity of the carbon dioxide dissolved water at the tower outlet became 34 μS / cm, the conductivity of the carbon dioxide dissolved water at the tower inlet was 38 μS / cm, and the ratio of the conductivity of the tower outlet to the conductivity of the tower inlet was 90%, the conversion rate of anion exchange resin to bicarbonate ion form or bicarbonate ion form and carbonate ion form was 99.3%; when the conductivity of the carbon dioxide dissolved water at the tower outlet became 36 μS / cm, the carbon dioxide dissolved water at the tower inlet The conductivity is 38 μS / cm, the ratio of the conductivity of the tower outlet to the conductivity of the tower inlet is 95%, and the conversion rate of the anion exchange resin to the bicarbonate ion form or bicarbonate ion form and carbonate ion form is 99.9% . In addition, anion exchange resins The conversion rate of the ionic form or the bicarbonate ionic form and the carbonate ionic form was determined as follows. First, the load per unit time of carbon dioxide to anion exchange resin is calculated from the difference in conductivity between the tower inlet and the tower outlet, and the water flow time is integrated to calculate the load of carbon dioxide. Next, the total load of carbon dioxide at the time point when the electrical conductivity of the tower inlet and the tower outlet reached the same value was obtained, and was calculated using (the load of carbon dioxide / the total load of carbon dioxide) × 100 (%).

(Comparative example 1)

A PFA-made ion exchange tower with an inner diameter of 16 mm and a height of 30 cm was installed with a PFA net at the lower part, and 50 mL of a type I strong basic anion exchanger ESG4002 (OH type, manufactured by Organo) was filled in the tower. Next, ammonium bicarbonate was dissolved in ultrapure water to obtain a 5% aqueous solution of ammonium bicarbonate. Next, the obtained ammonium bicarbonate aqueous solution was supplied to an ion exchange tower made of PFA at a liquid flow rate of 0.25 L / hour, and liquid was passed through the ESG4002 layer for 3 hours to obtain an anion exchanger a.

Next, in the same manner as in Example 1, the ion conversion ratio (%) of the anion exchanger a to a carbonic acid form or a bicarbonate form was determined. The results are shown in Table 1.

(Comparative example 2)

The concentration of the ammonium bicarbonate aqueous solution was changed from 5% to 0.8%, and the liquid was passed at a flow rate of 0.25L / hour for 3 hours. The liquid was changed to a flow rate of 0.50L / hour for 6 hours. The method was performed in the same manner as in Comparative Example 1 to obtain an anion exchanger b.

Next, ultrapure water was supplied to the PFA-made ion exchange tower for 5 minutes, and the discharged water was sampled. When the ammonium ion concentration in the discharged water was measured, the ammonium ion concentration was 770 mg / L. The concentration of ammonium ions in the discharged water when the ultrapure water was supplied was also measured. As a result, it was 6.6 mg / L.

Next, in the same manner as in Example 1, the ion conversion ratio (%) of the anion exchanger b to the carbonic acid form or the bicarbonate form was determined. The results are shown in Table 1.

(Example 2)

<Refining test of hydrogen peroxide water>

Using the mixed bed A composed of the anion exchanger and the cation exchanger obtained in Example 1, a purification test of hydrogen peroxide water was performed. A 35% by weight hydrogen peroxide solution containing 10 ppb of metal was used as a sample for purification, and the hydrogen peroxide solution was allowed to flow downward for 5 hours at a temperature of 5 ° C. and 0.5 L / hour for 4 hours. The hydrogen peroxide water flowing from the lower part of the packed tower was collected, and the metal content was analyzed by ICP-MS method. The results are shown in Table 2.

(Example 3)

As shown in Figure 1, in an ion exchange tower made of PFA (copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether) with an inner diameter of 16mm and a height of 30cm, a PFA net is installed in the lower part, and 50mL of type I is filled in the tower. Strongly basic anion exchange resin ESG4002 (OH type, manufactured by Organo). Next, carbon dioxide gas is supplied to the ultra-pure water and the hollow fiber membrane for gas dissolution using a mass flow for gas, and carbon dioxide gas is dissolved in the ultrapure water to obtain carbon dioxide dissolved water. Next, the obtained carbon dioxide dissolved water was supplied into an ion exchange tower made of PFA, and passed through a packed layer of ESG4002. At this time, the liquid flow rate in the ion exchange tower made of PFA was set to 3.0 L / hour, and the supply amount of carbon dioxide gas to the hollow fiber membrane for gas dissolution was adjusted so that the conductivity at the inlet of the tower became 38 μS / cm. Then, carbon dioxide dissolved water was continuously passed in (about 90 minutes) until the conductivity at the outlet became equal to that at the inlet of the tower (38 μS / cm), and an anion exchange resin A was obtained.

Next, in order to determine the ion conversion ratio (%) of the anion exchange resin A to a carbonate or bicarbonate form, an aqueous sodium nitrate solution was passed through the filling layer, and the obtained treatment solution was sodium hydroxide (indicator: phenolphthalein and formazan Base red mixed indicator) for neutralization titration. The results are shown in Table 3.

(Example 4)

The anion exchange resin A prepared under the same conditions as in Example 3 was passed through an acetic acid aqueous solution at a rate of 1.5 L / hour using a liquid-passing pump, and the acetic acid removal performance at this time was confirmed. The TOC meter (Sievers 900, manufactured by GE) was used to measure the acetic acid concentration at the inlet and outlet. The inlet TOC concentration was fixed at 24.9 ppm. The results are shown in Fig. 3.

(Comparative example 3)

The acetic acid removal performance was confirmed under the same conditions as in Example 4 except that the anion exchange resin a prepared under the same conditions as in Comparative Example 1 was used. The results are shown in Fig. 3.

Compared with Example 4, the time until the acetic acid break is short and the processing performance is low.

(Example 5)

<Refining test of hydrogen peroxide water>

Using the anion exchange resin A obtained in Example 3, a purification test of hydrogen peroxide water was performed. Hydrogen peroxide water containing Cr and Fe 10ppb 35 wt% hydrogen peroxide water as an anion metal was used as a sample for purification, and the hydrogen peroxide water was applied to the anion exchange resin in a downward direction. The solution was passed under the conditions of 5 ° C. and 0.5 L / hour for 4 hours. The hydrogen peroxide water flowing from the lower part of the packed tower was collected, and the Cr and Fe contents were analyzed by ICP-MS method. As a result, it was confirmed that the exit concentrations of Cr and Fe did not reach 0.01 ppb.

Claims (8)

A method for producing a mixture of an anion exchanger and a cation exchanger, which is characterized by having an anion exchanger conversion step (1) by contacting carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water to anion exchange A mixture of a substance (B) and a cation exchanger to convert the anion exchanger (B) into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form to obtain the anion exchange A mixture of the body (A) and the cation exchanger. For example, the method for producing a mixture of an anion exchanger and a cation exchanger in the first patent application range, wherein the anion exchanger (A) has a bicarbonate ion with respect to the total exchange capacity of the bicarbonate ion form and the carbonate ion form. The proportion of the exchange capacity is more than 70 equivalent%. For example, the method for producing a mixture of anion exchanger and cation exchanger in the scope of application for patents 1 or 2, wherein in the anion exchanger conversion step (1), the carbon dioxide dissolved water is brought into contact with the anion exchanger (B) and The conductivity of the carbon dioxide-dissolved water after contacting the mixture of cation exchangers with the anion exchanger (B) and the cation exchanger is relative to the carbon dioxide-dissolved water before the mixture with the anion exchanger (B) and the cation exchanger. The ratio of the electrical conductivity ((conductivity after contact / conductivity before contact) × 100)) is 90% or more. A method for manufacturing a mixed bed composed of an anion exchanger and a cation exchanger, which is characterized by having an anion exchanger conversion step (2), and contacting carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water. A mixed bed composed of anion exchanger (B) and cation exchanger packed in an ion exchange tower to transform the anion exchanger (B) into an anion exchange having a bicarbonate ion form or a bicarbonate ion form and a carbonate ion form (A) to obtain a mixed bed composed of the anion exchanger (A) and the cation exchanger. For example, in the method for manufacturing a mixed bed composed of an anion exchanger and a cation exchanger in the fourth scope of the patent application, wherein the anion exchanger (A) has an exchange capacity with respect to the total amount of the bicarbonate ion form and the carbonate ion form, The ratio of the exchange capacity of the bicarbonate ion form is 70 equivalent% or more. For example, in the method for manufacturing a mixed bed composed of an anion exchanger and a cation exchanger in the scope of the patent application No. 4 or 5, wherein in the anion exchanger conversion step (2), the carbon dioxide dissolved water is supplied to the ion exchange tower, The ratio of the conductivity of the carbon dioxide dissolved water up to the outlet of the ion exchange tower to the conductivity of the carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100)) becomes 90% or more. A method for refining hydrogen peroxide water, comprising the following steps: anion exchanger conversion step (2), contacting the carbon dioxide dissolved water obtained by dissolving carbon dioxide gas in pure water or ultrapure water, and filling the ion exchange tower with A mixed bed composed of an anion exchanger (B) and a cation exchanger to transform the anion exchanger (B) into an anion exchanger (A) having a bicarbonate ion form or having a bicarbonate ion form and a carbonate ion form, A mixed bed composed of the anion exchanger (A) and the cation exchanger is obtained; in the hydrogen peroxide water refining step, a crude hydrogen peroxide water is supplied to the ion exchange tower, and the crude hydrogen peroxide water is brought into contact with the anion A mixed bed composed of the exchanger (A) and the cation exchanger to obtain refined hydrogen peroxide water. For example, the method for purifying hydrogen peroxide water according to item 7 of the application, wherein in the anion exchanger conversion step (2), the carbon dioxide dissolved water is supplied to the ion exchange tower until the carbon dioxide at the outlet of the ion exchange tower is dissolved. The ratio of the conductivity of water to the conductivity of carbon dioxide dissolved water at the inlet of the ion exchange tower ((outlet conductivity / inlet conductivity) × 100) is 90% or more.