KR102346921B1 - Mixed bed ion exchange resin comprising anion exchange resin and cation exchange resin, method for preparing the same and method for purifying hydrogen peroxide solution using the same - Google Patents

Abstract

The present invention relates to a mixed-phase ion exchange resin comprising an anion exchange resin and a cation exchange resin, a method for producing the same, and a method for purifying hydrogen peroxide water using the same, and more particularly, to an alkali metal complex of stannous oxide adsorbed, Including an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and bicarbonate ion type, and a cation exchange resin converted to a hydrogen ion type to which a chelate compound is adsorbed, the precision electronics industry among aqueous solutions of hydrogen peroxide It relates to a mixed-phase ion exchange resin capable of producing ultra-high purity hydrogen peroxide used in the field (especially for manufacturing high-density semiconductor substrates, etc.), a method for producing the same, and a method for purifying hydrogen peroxide solution using the same.

Description

Mixed-phase ion exchange resin comprising anion exchange resin and cation exchange resin, manufacturing method thereof, and purification method of hydrogen peroxide water using the same PURIFYING HYDROGEN PEROXIDE SOLUTION USING THE SAME}

The present invention relates to a mixed-phase ion exchange resin comprising an anion exchange resin and a cation exchange resin, a method for producing the same, and a method for purifying hydrogen peroxide water using the same, and more particularly, to an alkali metal complex of stannous oxide adsorbed, Including an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and bicarbonate ion type, and a cation exchange resin converted to a hydrogen ion type to which a chelate compound is adsorbed, the precision electronics industry among aqueous solutions of hydrogen peroxide It relates to a mixed-phase ion exchange resin capable of producing ultra-high purity hydrogen peroxide used in the field (especially for manufacturing high-density semiconductor substrates, etc.), a method for producing the same, and a method for purifying hydrogen peroxide solution using the same.

BACKGROUND ART Hydrogen peroxide water is used in a wide range of fields, such as being used for a bleaching process of paper and pulp, used as an industrial oxidizing agent, used as a cleaning agent for wastewater treatment, and a semiconductor manufacturing process. In particular, with the recent high integration of LSIs (High Density Integrated Circuits), the requirements for cleaning materials used in semiconductor manufacturing processes are becoming more stringent. Since dust and metals deposited on the wafer greatly affect the reliability of semiconductors and cause a decrease in yield, it is becoming important in industrially manufacturing semiconductors to reduce their adhesion as much as possible.

Hydrogen peroxide is used by mixing with aqueous ammonia, hydrochloric acid, sulfuric acid or hydrofluoric acid in a wafer cleaning process of a semiconductor manufacturing process such as LSI. It is known that metals derived from the cleaning solution do not adhere to the wafer when hydrogen peroxide solution is mixed with hydrochloric acid, sulfuric acid or hydrofluoric acid when used. It has been reported that metals such as aluminum adhere to the wafer surface. In addition, since it has been found that the presence of chlorine ions and sulfate ions adversely affect metal adhesion, hydrogen peroxide water with a reduced content of anions such as chlorine ions and sulfate ions has been demanded.

As a method for reducing impurities in hydrogen peroxide solution, an impurity removal method using an ion exchange resin and an impurity removal method using a reverse osmosis membrane have been proposed. In the case of using an ion exchange resin, if the anion exchange resin is used in the OH type state, the decomposition reaction of hydrogen peroxide proceeds to generate heat or oxygen gas is generated and there is a risk of explosion. Therefore, it is used after converting the OH of anion exchange resin into carbonate ion type or bicarbonate ion type in advance.

Japanese Patent No. 3715371 (Patent Document 1) discloses a process for removing dissociable impurities by a mixed-bed ion exchange resin apparatus, a process for removing non-dissociable impurities by an adsorbent apparatus, and a process for removing dissociable impurities by a mixed-bed ion exchange resin apparatus It is described that by using a purification method of hydrogen peroxide water composed of

In Japanese Patent Publication No. 4056695 (Patent Document 2), hydrogen peroxide water containing metal ion impurities is mixed with a hydrogen ion type (H ⁺ ) cation exchange resin, a fluorine ion type (F ⁻ ) anion exchange resin, and a carbonate ion type (CO ₃ ^2- ) or a bicarbonate ion type (HCO ₃ ⁻ ) anion exchange resin and a hydrogen ion type (H ⁺ ) cation exchange resin are brought into contact in this order, thereby purifying hydrogen peroxide water with high purity.

In Japanese Patent No. 3171058 (Patent Document 3), the ion exchange resin is previously contacted with a high-purity aqueous solution of mineral acid having each metal component concentration of 0.1 wt ppb or less, and each metal component concentration is 0.1 wt ppb or less. It is described that a high-purity hydrogen peroxide solution is obtained by contacting a pretreated ion exchange resin with a crude hydrogen peroxide solution containing an impurity metal component.

In Japanese Patent No. 3608211 (Patent Document 4), crude hydrogen peroxide solution is brought into contact with an anion exchange resin in which ammonium carbonate is used as a carbonate ion or an anion exchange resin in which ammonium bicarbonate is used as a bicarbonate ion is brought into contact. A method for producing high-purity hydrogen peroxide solution is described.

In Japanese Laid-Open Publication No. 2011-068533 (Patent Document 5), crude hydrogen peroxide solution containing a hydrophobic substance as an impurity is brought into contact with a reverse osmosis membrane made of a polyamide-based or polyvinyl alcohol-based composite membrane, characterized in that A process for the preparation of purified hydrogen peroxide water is described.

However, in Patent Documents 1 to 4, when an anion exchange resin having a bicarbonate ion type is used as an anion exchange resin, carbonate or hydrogen carbonate aqueous solution is generally used, but the metal concentration in the purified hydrogen peroxide solution is high, and the total organic carbon concentration is still high.

In addition, in Patent Documents 1 to 3, when a carbonate ion-type or bicarbonate ion-type anion exchange resin is used as the anion exchange resin, a very high concentration of carbonate or hydrogen carbonate aqueous solution having a salt concentration of 5 to 15% by weight is used. In general, despite the removal of impurities in the hydrogen peroxide solution and purification to a high concentration, an aqueous solution containing a high concentration of salt is brought into contact with the ion exchanger. It will elute from this resin.

In addition, Patent Document 5 proposes a method for producing purified hydrogen peroxide water using a reverse osmosis membrane. However, by constantly contacting the reverse osmosis membrane with a high-concentration hydrogen peroxide solution, there is a problem that the reverse osmosis membrane deteriorates and the blocking rate decreases.

Japanese Patent Publication No. 3715371 Japanese Patent Publication No. 4056695 Japanese Patent Publication No. 3171058 Japanese Patent Publication No. 3608211 Japanese Laid-Open Patent Publication No. 2011-68533

The present invention is intended to solve the problems of the prior art as described above, and an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and a bicarbonate ion type to which an alkali metal complex of stannous oxide is adsorbed And, including a cation exchange resin converted to a hydrogen ion type with a chelate compound adsorbed, ultra-high purity hydrogen peroxide used in the precision electronics industry (especially in the manufacture of high-integration semiconductor substrates, etc.) among aqueous hydrogen peroxide solutions. It is a technical task to provide a hybrid ion exchange resin, a method for producing the same, and a method for purifying hydrogen peroxide solution using the same.

In order to solve the above technical problem, the present invention provides an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and a bicarbonate ion type; and a cation exchange resin converted to a hydrogen ion type, wherein an alkali metal complex of stannous oxide is adsorbed to the anion exchange resin converted to the bicarbonate ion type or an anion exchange resin converted to carbonate ion type and bicarbonate ion type, , In which the chelate compound is adsorbed to the cation exchange resin converted to the hydrogen ion type, it provides a mixed-phase ion exchange resin.

According to another aspect of the present invention, (a) adsorbing an alkali metal complex of stannous oxide to an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and bicarbonate ion type; (b) adsorbing a chelate compound to a cation exchange resin converted into a hydrogen ion type; and (c) mixing the anion exchange resin obtained in step (a) with the cation exchange resin obtained in step (b), a method for producing a mixed-phase ion exchange resin is provided.

According to another aspect of the present invention, there is provided a method for purifying hydrogen peroxide solution comprising the step of contacting the mixed-phase ion exchange resin and crude hydrogen peroxide solution.

According to the present invention, an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and bicarbonate ion type to which an alkali metal complex of _{stannic oxide (SnO 2 ) is adsorbed, and a chelate compound is adsorbed} By purifying crude hydrogen peroxide water using a mixed-phase ion exchange resin containing a cation exchange resin converted into a hydrogen ion type, the content of metal ions, which is an impurity, is very low, and the total organic carbon content is very low, so the precision electronics industry Ultra-high purity hydrogen peroxide suitable for use in the field can be stably purified without generating excess oxygen.

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

The present invention relates to an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and a bicarbonate ion type; and a cation exchange resin converted to a hydrogen ion type, wherein the anion exchange resin converted to the bicarbonate ion type or the anion exchange resin converted to the carbonate ion type and bicarbonate ion type is an alkali metal complex of _{stannous oxide (SnO 2 )} It relates to a mixed-phase ion exchange resin in which the cation exchange resin converted to the hydrogen ion type adsorbs the chelate compound.

An anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and a bicarbonate ion type contained in the mixed-phase ion exchange resin of the present invention is a chlorine type (Cl ^- ) anion exchange resin or a hydroxyl type (OH) ^- ) converting the anion exchange resin into an anion exchange resin of a bicarbonate ion type or an anion exchange resin of a carbonate ion type and a bicarbonate ion type using an aqueous ammonium carbonate or sodium carbonate solution, or an aqueous ammonium bicarbonate or sodium bicarbonate solution; pre-treating the anion exchange resin converted to the bicarbonate ion type or the anion exchange resin converted to the carbonate ion type and the bicarbonate ion type; and washing the anion exchange resin converted into the pretreated bicarbonate ion type or the anion exchange resin converted into carbonate ion type and bicarbonate ion type with water.

Using ammonium carbonate or sodium carbonate aqueous solution, or ammonium bicarbonate or sodium bicarbonate aqueous solution, chlorine-type (Cl ^- ) anion exchange resin or hydroxyl-type (OH ^{- ) anion exchange resin} In the step of converting to the anion exchange resin of the type, any one of a strong base type and a weak base type may be used as the converted anion exchange resin.

Usually, anion exchange resin is ^{supplied as chlorine type (Cl -} ) and then as hydroxyl type (OH ^- ). Therefore, when using a new anion exchange resin, it is converted into bicarbonate ion type or carbonate ion type and bicarbonate ion type before use. do.

Examples of the conversion method include a method of suspending the anion exchange resin in an aqueous ammonium carbonate or sodium carbonate solution using a reactor, or suspending the anion exchange resin in an aqueous ammonium bicarbonate or sodium bicarbonate solution; and a method of passing an aqueous solution of ammonium carbonate or sodium carbonate or passing an aqueous solution of ammonium bicarbonate or sodium bicarbonate through the column after filling the column with an anion exchange resin, and the latter is common industrially.

The concentration of the aqueous solution of ammonium carbonate or sodium carbonate, or aqueous solution of ammonium bicarbonate or sodium bicarbonate used in the transformation may be 4% to 12%, preferably 6% to 10%. If the concentration of the aqueous solution is lower than the numerical range, the ion conversion rate of the anion exchange resin may be lowered, and thus the purification effect may be deteriorated.

In the case of a method of passing an aqueous solution of ammonium carbonate or sodium carbonate, or an aqueous solution of ammonium bicarbonate or sodium bicarbonate after filling the column with an anion exchange resin, the flow rate is 0.5 to 30 hr ^-1 day at a superficial speed (hereinafter referred to as SV) can

The amount of liquid passing through can be determined by the concentration of ammonium carbonate or sodium carbonate aqueous solution or the concentration of ammonium bicarbonate or sodium bicarbonate aqueous solution used so that carbonate ions or bicarbonate ions are twice or more in an equivalent ratio with respect to the functional group to be converted. The equivalent ratio of carbonate ions or bicarbonate ions may be 2 to 15 times, preferably 2 to 10 times.

In addition, the anion exchange resin supplied as chlorine type (Cl ^{− ) can be converted into hydroxyl type (OH −} ) and then converted into bicarbonate ion type or carbonate ion type and bicarbonate ion type, and this method is more completely It is preferable because it can be converted into an ionic form or a carbonate ion form and a bicarbonate ion form. Conversion of the chlorine type to the oxalic acid type can be carried out by passing an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or aqueous ammonia.

The used anion exchange resin is converted into a new anion exchange resin into a bicarbonate ion type or a carbonate ion type and a bicarbonate ion type. It can be regenerated by passing through it.

The anion exchange resin may have a ratio of the exchange capacity of the bicarbonate ion type to 80 equivalent% or more, preferably 90 equivalent% or more, based on 100 equivalent% of the total exchange capacity of the carbonate ion type and the bicarbonate ion type. If the ratio of the exchange capacity of the bicarbonate ion type is lower than the above numerical range, the purification effect of the hydrogen peroxide solution may be reduced.

After converting the anion exchange resin into a bicarbonate ion type or carbonate ion type and bicarbonate ion type by the above-described method, in the step of pre-treating the bicarbonate ion type anion exchange resin or carbonate ion type and bicarbonate ion type anion exchange resin, Excess ammonium carbonate or sodium carbonate, or ammonium bicarbonate or sodium bicarbonate may be removed using pretreatment, and then the pretreated anion exchange resin of bicarbonate ion type or carbonate ion type and bicarbonate ion type anion exchange resin is washed with water. In this step, residual amounts of organic matter and metal ions may be removed.

The pretreatment of the anion exchange resin converted to the bicarbonate ion type or the anion exchange resin converted to the carbonate ion type and the bicarbonate ion type is performed using a reactor or column, and the pretreatment temperature may be 30° C. to 120° C., preferably Preferably, it may be 50° C. to 100° C.

As the solution used for the pretreatment, ultrapure water may be used, or a mixture of one or two or more organic solvents and ultrapure water may be used (for example, methanol, ethanol, butanol, or a mixture thereof and ultrapure water may be used. can be used), preferably ultrapure water. When only an organic solvent is used as the pretreatment solution, even a trace amount of the organic solvent used during the pretreatment process may remain in the anion exchange resin. As a result, excess oxygen may be generated, which may result in poor stability.

Ultrapure water may be used as the solution used in the water washing step. When ultrapure water is used in the water washing step, the residual amount of organic matter and metal ions can be effectively removed.

the conversion step; pretreatment step; And the alkali metal complex of stannous oxide can be adsorbed to the anion exchange resin converted to the bicarbonate ion type or the anion exchange resin converted to the carbonate ion type and the bicarbonate ion type obtained through the water washing step.

In order to adsorb the alkali metal complex of stannous oxide to the anion exchange resin converted to the bicarbonate ion type or the anion exchange resin converted to the carbonate ion type and the bicarbonate ion type, the anion exchange resin or the carbonate ion type converted to the bicarbonate ion type and The anion exchange resin converted to the bicarbonate ion type may be brought into contact with an aqueous alkali metal solution of stannic oxide, and for this purpose, either a batch type or a column type may be used.

In one embodiment, the aqueous alkali metal solution of stannous oxide is obtained by dissolving stannous oxide in an aqueous alkali metal solution of 2 to 3 times in an equivalent ratio, and then taking the supernatant of the solution, and using it with an inorganic acid solution to pH 7 to 8, and the aqueous alkali metal solution of stannic oxide is prepared by dissolving commercially available alkali metal tin(II) acid trihydrate (eg, sodium tin(II) acid trihydrate) with pure water. can be

As the alkali metal aqueous solution used to dissolve the stannous oxide, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, or cesium hydroxide aqueous solution may be used, and the inorganic acid solution used for pH adjustment is hydrochloric acid solution, nitric acid solution, sulfuric acid solution , a hydrofluoric acid solution, a phosphinic acid solution, a phosphonic acid solution, a phosphoric acid solution, or a mixture thereof may be used. However, since the inorganic acid solution is ion-exchanged with the bicarbonate ion or carbonate ion of the anion exchange resin, the exchange capacity of the anion exchange resin is reduced, so it is preferable to use it at a minimum.

The content of the alkali metal aqueous solution of stannous oxide used in contact with the anion exchange resin is not particularly limited, but the tin element is 0.01 equivalents/L-Resin or more, 0.03 equivalents/L-Resin or more, relative to the anion exchange resin, Alternatively, it may be used in an amount that is 0.05 equivalents/L-Resin or more, 0.3 equivalents/L-Resin or less, 0.2 equivalents/L-Resin or less, or 0.1 equivalent/L-Resin or less. When the content of the alkali metal aqueous solution of the stannous oxide is less than the above level, the adsorption amount of the alkali metal complex of the stannous oxide is insignificant, so that the ion reduction effect of the metal impurities is insignificant, and the amount of oxygen generation may be relatively large.

The step of adsorbing the alkali metal complex compound of stannous oxide to the anion exchange resin converted into the bicarbonate ion type or the carbonate ion type and the anion exchange resin converted to the bicarbonate ion type is the anion exchange resin converted to the bicarbonate ion type or the carbonate ion type and The anion exchange resin converted to the bicarbonate ion type is brought into contact with an aqueous alkali metal solution of stannic oxide, and then the temperature is raised to 30-100°C, preferably 50-80°C, for 2-8 hours, preferably 3 This can be done by stirring for ~5 hours.

Thereafter, a pretreatment step may be performed on the anion exchange resin of the bicarbonate ion type or the anion exchange resin of the carbonate ion type and the bicarbonate ion type to which the alkali metal complex of stannous oxide is adsorbed.

Through the pretreatment step, unreacted aqueous alkali metal solution of stannic oxide and excess ammonium carbonate or sodium carbonate, or ammonium bicarbonate or sodium bicarbonate are removed from the anion exchange resin, and other organic substances and metal ions of the anion exchange resin can be removed. have.

The pretreatment step may be performed using a reactor or column, and the pretreatment temperature may be 30 ~ 120 ℃, preferably 50 ~ 100 ℃.

As the solution used for the pretreatment, ultrapure water may be used, or a mixture of one or two or more organic solvents and ultrapure water may be used (for example, methanol, ethanol, butanol, or a mixture thereof and ultrapure water may be used. Yes), preferably ultrapure water can be used. When only an organic solvent is used as the pretreatment solution, even a trace amount of the organic solvent used during the pretreatment process may remain in the anion exchange resin. As a result, excess oxygen may be generated, which may result in poor stability.

A trace amount of organic matter and metal impurity ions may be removed through a water washing step after the pretreatment step. For the water washing step, either a batch type or a column type may be used, and a column type may be preferable in order to sufficiently remove the remaining alkali metal. Specifically, the washing step may be performed by passing ultrapure water down-flow for 5-10 hours at ^{20 to 70 hr -1} at a superficial speed (hereinafter referred to as SV).

In this way, after converting the anion exchange resin into a bicarbonate ion type or carbonate ion type and bicarbonate ion type, and adsorbing an alkali metal complex of stannous oxide to the anion exchange resin, excess ammonium carbonate or sodium carbonate, or bicarbonate remaining In order to remove ammonium or sodium bicarbonate, and to remove the unreacted aqueous alkali metal solution of stannous oxide that has not been adsorbed to the anion exchange resin, a pretreatment step may be performed, and a trace amount of other organic matter and metal ions may be removed. , the washing step may be performed.

The alkali metal complex of stannous oxide adsorbed on the anion exchange resin converted to carbonate ion type or the anion exchange resin converted to carbonate ion type and bicarbonate ion type is a dissolved metal ion (especially a polyvalent heavy metal) having catalytic decomposition activity. ion) to suppress the catalytic decomposition activity of metal ions with respect to hydrogen peroxide, so that a high-purity hydrogen peroxide solution can be finally obtained without generating excess oxygen.

The cation exchange resin included in the mixed phase ion exchange resin of the present invention may use a strong acid type cation exchange resin having a sulfonic acid group as a functional group. The cation exchange resin is used as a ^{hydrogen ion type (H + ).} Sodium ion type (Na ⁺⁾ cation exchange resin to be supplied is converted into a hydrogen ion type (H ⁺⁾ with an acid such as hydrochloric acid or sulfuric acid. It is industrially preferable to carry out the conversion method through a reactor or a column liquid in the same way as the anion exchange resin.

That is, hydrochloric acid having a concentration of 2% to 12% can be passed through a column filled with a cationic resin at ^{SV=0.5 to 10 hr -1} by making the equivalent ratio of the acid to the functional group to be converted more than doubled.

After the cation exchange resin is converted to a hydrogen ion type by the above method, excess hydrochloric acid is removed by pretreatment, the remaining amount of organic matter and metal ions can be removed by washing with water.

The cation exchange resin that has been converted to the hydrogen ion type is subjected to pretreatment, and the pretreatment is performed using a reactor or column, and the pretreatment temperature may be 30°C to 120°C, preferably 50°C to 100°C. have.

As the solution used for the pretreatment, ultrapure water may be used, or a mixture of one or more organic solvents and ultrapure water may be used (for example, methanol, ethanol, butanol, or a mixture thereof and ultrapure water may be used. can be used), preferably ultrapure water. When only an organic solvent is used as the pretreatment solution, even a trace amount of the organic solvent used during the pretreatment process may remain in the cation exchange resin. As a result, excess oxygen may be generated, which may result in poor stability.

Ultrapure water may be used as the solution used in the water washing step. When ultrapure water is used in the water washing step, the residual amount of organic matter and metal ions can be effectively removed.

In addition, it is not a problem in practicing the present invention to repeat the passage of acid and alkali, which is usually carried out during the adjustment.

the conversion step; pretreatment step; And the chelate compound may be adsorbed to the cation exchange resin converted to the hydrogen ion type obtained through the water washing step.

In order to adsorb the chelate compound to the cation exchange resin converted to the hydrogen ion type, an aqueous solution of the chelate compound may be contacted with the cation exchange resin converted to the hydrogen ion type, and for this, either a batch type or a column type may be used. can

The content of the aqueous solution of the chelate compound used for contact with the cation exchange resin is not particularly limited, but the chelate compound is 0.05 equivalents/L-Resin or more, 0.1 equivalents/L-Resin or more, or 0.2 equivalents relative to the cation exchange resin. It can be used in an amount that becomes /L-Resin or more, and it can be used in an amount that becomes 0.5 equivalents/L-Resin or less, 0.4 equivalents/L-Resin or less, or 0.3 equivalents/L-Resin or less. When the content of the chelate aqueous solution is less than the above level, the adsorption amount of the chelate compound is insignificant, so that the effect of reducing ions of metal impurities is insignificant, and the amount of oxygen generation may be relatively large.

The step of adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type is to contact the aqueous solution of the chelate compound with the cation exchange resin converted to the hydrogen ion type, and then increase the temperature to 30 ~ 120 °C, preferably 50 ~ It can be carried out by raising the temperature to 100° C. and stirring for 2 to 8 hours, preferably for 3 to 5 hours.

Thereafter, a pretreatment step may be performed on the hydrogen ion type cation exchange resin to which the chelate compound is adsorbed.

Through the pretreatment step, the unreacted chelate compound may be removed from the cation exchange resin, and other organic substances and metal ions of the cation exchange resin may be removed.

The pretreatment step may be performed using a reactor or column, and the pretreatment temperature may be 30 ~ 120 ℃, preferably 50 ~ 100 ℃.

As the solution used for the pretreatment, ultrapure water may be used, or a mixture of one or two or more organic solvents and ultrapure water may be used (for example, methanol, ethanol, butanol, or a mixture thereof and ultrapure water may be used. Yes), preferably ultrapure water can be used. When only an organic solvent is used as the pretreatment solution, even a trace amount of the organic solvent used during the pretreatment process may remain in the anion exchange resin. As a result, excess oxygen may be generated, which may result in poor stability.

A trace amount of organic matter and metal impurity ions may be removed through a water washing step after the pretreatment step. The water washing step may use either a batch type or a column type, and a column type may be preferable in order to sufficiently remove the remaining alkali metal. Specifically, the washing step may be performed by passing ultrapure water down-flow for 5 to 10 hours at SV = 20 to 70 hr ^-1.

Examples of the chelate compound include a compound in which at least one amine group and at least one phosphonic acid group exist in one molecule; or a compound in which at least one amine group and at least one carboxylic acid group exist in one molecule; may be, for example, aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediamine tetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DTPMA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), etc. This can be preferably used.

The chelate compound adsorbed to the cation exchange resin converted to the hydrogen ion type is coordinated with a dissolved metal ion (especially a polyvalent heavy metal ion) having catalytic decomposition activity, thereby inhibiting the catalytic decomposition activity of the metal ion for hydrogen peroxide. Finally, it is possible to obtain high-purity hydrogen peroxide water without generating excess oxygen.

In this way, after converting the cation exchange resin to a hydrogen ion type, adsorbing the chelate compound to the cation exchange resin, in order to remove the unreacted chelate compound not adsorbed to the anion exchange resin, a pretreatment step may be performed. In order to remove trace amounts of other organic matter and metal ions, a water washing step may be performed.

The bicarbonate ion type anion exchange resin to which the alkali metal complex of stannous oxide obtained by the above-mentioned method is adsorbed or the carbonate ion type and bicarbonate ion type anion exchange resin and the hydrogen ion type cation exchange resin to which the chelate compound is adsorbed, By uniformly mixing in a ratio, a mixed phase type ion exchange resin can be prepared.

In the step of mixing the anion exchange resin and the cation exchange resin, the content of the hydrogen ion-type cation exchange resin to which the chelate compound is adsorbed is 1 to 20% by volume, preferably based on the total volume of the mixed-phase ion exchange resin. The cation exchange resin and the anion exchange resin may be mixed so as to be 5 to 10% by volume. When the content of the cation exchange resin is less than the above range, the effect of reducing metal ion impurities may be insignificant, and on the contrary, when the content exceeds the above range, a problem of increasing the total organic carbon elution may occur.

The present invention also provides a method for purifying hydrogen peroxide solution comprising the step of contacting the mixed-phase ion exchange resin according to the present invention and crude hydrogen peroxide solution.

As the crude hydrogen peroxide solution, an industrially used aqueous hydrogen peroxide solution produced by an anthraquinone method or the like can be used. In addition, in the case of hydrogen peroxide water used for the electronic industry, etc., it is possible to use hydrogen peroxide water having a higher purity than that for general industrial use.

The concentration of the hydrogen peroxide solution used in the semiconductor manufacturing process may be 20 to 40%. Although 20% or more is preferable, if the ion exchange resin is brought into contact with an excessively high concentration of hydrogen peroxide solution, the deterioration of the ion exchange resin may be accelerated or impurities may be eluted from the ion exchange resin. It is preferable to use aqueous hydrogen peroxide. In the case of using a lower concentration, hydrogen peroxide solution having a corresponding concentration may be used as a raw material.

In order to sufficiently reduce the impurities of anions and metals and to minimize the generation of oxygen during the purification process of the crude hydrogen peroxide solution, the crude hydrogen peroxide solution may be brought into contact with both the anion exchange resin and the cation exchange resin. Each resin may be contacted in one stage or may be contacted in multiple stages. However, at the end of the purification treatment of the hydrogen peroxide solution, the mixed-phase ion exchange resin according to the present invention and the crude hydrogen peroxide solution can be brought into contact to solve the above-mentioned problems, and the mixed-phase ion exchange resin is as described above.

As the anion exchange resin, either a strong base type or a weak base type may be used, and as the cation exchange resin, either a strong acid type or a weak acid type may be used.

For purification of hydrogen peroxide solution, the mixed-phase ion exchange resin according to the present invention may be brought into contact with crude hydrogen peroxide solution. As the contacting method, a batch method in which the mixed-phase ion exchange resin according to the present invention is put in hydrogen peroxide water and stirred can be used, but the crude hydrogen peroxide solution is passed through a column filled with the mixed-phase ion exchange resin according to the present invention The method is preferred as an industrial method.

In order to prevent leakage of metals or anions, the filling height of the mixed-phase ion exchange resin in the column is preferably 20 cm or more, but more preferably 30 cm or more.

Passing liquid rate is 0.1 to 20 hr to SV ^- may be ^1, and may be preferably from 0.5 to 10 hr ^-1.

At the time of passing the hydrogen peroxide solution in contact with the anion exchange resin, although a trace amount causes decomposition, it is preferable to carry out the passage of the hydrogen peroxide solution at a low temperature in order to make the decomposition less occur. Specifically, it is preferable to carry out the liquid passing at -10 °C to 30 °C, and it is more preferable to perform the liquid passing at -10 °C to 10 °C. By carrying out the liquid passage in the low temperature range as described above, the crude hydrogen peroxide solution as a raw material can be efficiently used, and the stability of the treatment can be improved.

[ Example ]

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

Wherein the content of metal ion impurities are of the ICP-MS method (Agilent 7500) was measured as total organic carbon (TOC) content measurement was performed using a Sievers 500RL On-Line TOC Analyzer, particularly ultrapure SV = 20 hr ^-1 It was measured as a delta value (ΔTOC) excluding a blank value from the measured value after passing the fluid at the speed for 24 hours.

The amount of oxygen gas generated was measured manually by using a burette filled with saturated saline by collecting the gas generated from the ion exchange resin tower, and analyzing the oxygen composition in the gas using gas chromatography to measure the amount of oxygen gas generated.

<Production of mixed-phase ion exchange resin>

Example A1

Preparation of anion exchange resin converted to bicarbonate ion type

Trilite AMP16 (Cl type, Amination type 1, Samyang Corporation), a strong basic anion exchange resin, was used in an ion exchange tower (column inner diameter 16 mm and height 40 cm) of PFA (tetrafluoroethylene and perfluoroalkyl vinyl ether). As an ion exchange tower prepared by coalescence), the PFA mesh is attached to the lower part of the ion exchange tower) is charged to a bed height of 30 cm, and 8 wt% of an aqueous sodium hydroxide solution is added in an amount equivalent to 10 times the functional group SV = 2 The ^{liquid was passed through at hr -1} , followed by washing with ultrapure water in an amount 10 times the amount of the strongly basic anion exchange resin. After that, 4 wt% of sodium bicarbonate aqueous solution was passed through an amount equivalent to 15 times the functional group at SV = 2 hr ^-1 , and finally by washing with ultrapure water 10 times the amount of the strong basic anion exchange resin, the anion exchange The resin was converted to the bicarbonate ionic form.

After that, the obtained bicarbonate ion-type anion exchange resin was put into the reactor (2L) together with ethanol, stirred at 70° C. for 5 hours, cooled to room temperature, and the ethanol in the bicarbonate ion-type anion exchange resin was reduced under reduced pressure. By removing it, a pretreatment step was performed.

Then, the obtained bicarbonate ion-type anion exchange resin was applied to an ion exchange tower (an ion exchange tower made of PFA having a column inner diameter of 16 mm and a height of 40 cm, with a PFA mesh attached to the bottom of the ion exchange tower) at a bed height of 30 cm. After filling, the liquid was passed through at SV = 20 hr ^-1 , followed by washing with ultrapure water 480 times the amount of the bicarbonate ion type anion exchange resin.

Thereafter, in order to measure the ion conversion rate (%) of the obtained bicarbonate ion type anion exchange resin into carbonate ion type or bicarbonate ion type, nitric acid was placed in the packed bed of the ion exchange column filled with the bicarbonate ion type anion exchange resin. The treatment solution obtained by passing a sodium aqueous solution was subjected to neutralization titration using sodium hydroxide (as an indicator, a mixed indicator of phenolphthalein and methyl red was used), and the ion conversion rate measurement results are shown in Table 1 below.

on anion exchange resin stannous oxide Adsorbs alkali metal complexes

Stirring was performed while slowly adding 133.37 g of sodium stannate trihydrate to 5 L of ultrapure water, and after further stirring at room temperature for 24 hours, the supernatant was taken to prepare an alkali metal aqueous solution of about 0.1 mol/L of stannous oxide did

The obtained bicarbonate ion type anion exchange resin and ultrapure water in an amount twice the amount of the bicarbonate ion type anion exchange resin were put into a reactor together, and the obtained alkali metal aqueous solution of stannous oxide was mixed with tin element to exchange the bicarbonate ion type anion exchange resin. With respect to the resin, it was added in an amount of 0.05 eq/L-Resin. Thereafter, the reactor was heated to 70° C., stirred for 4 hours, the supernatant was removed, and as a pretreatment step for removing unreacted aqueous alkali metal solution of stannous oxide, 10 times the amount of the bicarbonate ion-type anion exchange resin After adding ultrapure water and stirring for 30 minutes, a series of operations of removing the supernatant was repeated 5 times.

Then, the bicarbonate ion-type anion exchange resin to which the alkali metal complex of stannous oxide is adsorbed together with ultrapure water twice the amount of the bicarbonate ion-type anion exchange resin is put into the reactor, the temperature of the reactor is raised to 70° C., and then 5 hours After stirring for a while, it was cooled to room temperature, and the obtained bicarbonate ion-type anion exchange resin to which the alkali metal complex of stannous oxide was adsorbed was used in an ion exchange column (an ion exchange tower made of PFA having a column inner diameter of 16 mm and a height of 40 cm). as, by passing liquid to an ion exchange in a lower portion of the column that a PFA mesh is attached) to then filled with a floor height of 30cm, ultra-pure water of 200-fold amount of the bicarbonate ion-type anion exchange resin amount to as SV = 20 hr ^-1 downflow, was washed.

Preparation of cation exchange resin converted to hydrogen ion type

Trilite CMP28 (Na type, Samyang Corporation), a strong acid cation exchange resin, is an ion exchange tower (column inner diameter 16 mm and height 40 cm made of PFA), with a PFA mesh attached to the bottom of the ion exchange tower ) to a bed height of 30 cm, and an 8 wt% aqueous hydrochloric acid solution ^{is passed through an amount equivalent to 10 times the functional group at SV = 2 hr -1} , followed by washing with ultrapure water 10 times the amount of the strongly acidic cation exchange resin. , the cation exchange resin was converted to a hydrogen ion type.

Then, the obtained hydrogen ion type cation exchange resin was added to the reactor (2L) with ultrapure water, and then stirred at 100° C. for 10 hours and then cooled to room temperature.

Then, the obtained hydrogen ion-type cation exchange resin was applied to an ion exchange tower (an ion exchange tower made of PFA having a column inner diameter of 16 mm and a height of 40 cm, with a PFA mesh attached to the bottom of the ion exchange tower) at a bed height of 30 cm. After filling, the liquid was passed through at SV = 20 hr ^-1 , followed by washing with ultrapure water 480 times the amount of the hydrogen ion type cation exchange resin.

Adsorption of chelate compounds to cation exchange resin

The obtained hydrogen ion type cation exchange resin and ultrapure water in an amount twice the amount of the hydrogen ion type cation exchange resin were put into the reactor together, and 10 wt% of an aminotris(methylenephosphonic acid) (ATMP) aqueous solution as a chelate compound was added to the above It was added in an amount of 0.2eq/L-Resin with respect to the hydrogen ion type cation exchange resin. After raising the temperature of the reactor to 80 ℃, stirring for 6 hours, then removing the supernatant, as a pretreatment step to remove the unadsorbed ATMP, 10 times the amount of the hydrogen ion-type cation exchange resin ultrapure water was put After stirring for 30 minutes, a series of operations for removing the supernatant was repeated 5 times.

After that, the hydrogen ion type cation exchange resin to which ATMP is adsorbed together with twice the amount of the hydrogen ion type cation exchange resin is put into the reactor, the temperature of the reactor is raised to 70° C., and then stirred for 5 hours, then at room temperature was cooled, and the obtained hydrogen ion-type cation exchange resin to which ATMP was adsorbed was converted into an ion exchange tower (an ion exchange tower made of PFA having a column inner diameter of 16 mm and a height of 40 cm, and a PFA mesh was attached to the lower portion of the ion exchange tower. After filling to a bed height of 30 cm, ultrapure water 200 times the amount of the hydrogen ion type cation exchange resin ^{was passed downward at SV = 20 hr -1} to wash with water.

comprising an anion exchange resin and a cation exchange resin; mixed type Preparation of ion exchange resins

A mixed-phase ion exchange resin was prepared by uniformly mixing the obtained bicarbonate ion-type anion exchange resin to which the alkali metal complex of stannous oxide was adsorbed and the obtained hydrogen ion-type cation exchange resin to which ATMP was adsorbed, in this case Based on the total volume of the ion exchange resin, the content of the hydrogen ion-type cation exchange resin to which the ATMP was adsorbed was mixed so as to be 10% by volume.

Example A2

In the same manner as in Example A1, except that the concentration of the sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt% during the preparation of the anion exchange resin converted to the bicarbonate ion type, the mixed phase ion exchange resin was prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A3

In the same manner as in Example A1, except that in the process of preparing the anion exchange resin converted to the bicarbonate ion type, 8% by weight of an aqueous solution of ammonium bicarbonate was used instead of the aqueous solution of 4% by weight of sodium bicarbonate. An ion exchange resin was prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A4

In the same manner as in Example A1, except that, in the process of preparing the anion exchange resin converted to the bicarbonate ion type, 8% by weight of an aqueous ammonium carbonate solution was used instead of the 4% by weight of the aqueous sodium bicarbonate solution. An ion exchange resin was prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A5

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) the alkali of stannous oxide in the anion exchange resin converted to the bicarbonate ion type In the process of adsorbing the metal complex, when the alkali metal aqueous solution of stannous oxide was added so that the amount of 0.05 eq/L-Resin was 0.05 eq/L-Resin with respect to the anion exchange resin in which the tin element was converted to the bicarbonate ion type, the tin element was the bicarbonate ion Mixed-phase ions were carried out in the same manner as in Example A1, except that an aqueous alkali metal solution of stannous oxide was added in an amount of 0.01 eq/L-Resin to the converted anion exchange resin. An exchange resin was prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A6

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, changing the concentration of the sodium bicarbonate aqueous solution from 4% by weight to 8% by weight, ii) adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type In the process, 10% by weight of ATMP aqueous solution was added so that the chelate compound was in an amount of 0.2 eq/L-Resin with respect to the cation exchange resin converted to the hydrogen ion type, to the cation exchange resin converted to the hydrogen ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that 10% by weight of ATMP aqueous solution was added so as to have an amount of 0.05 eq/L-Resin. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A7

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) the alkali of stannous oxide in the anion exchange resin converted to the bicarbonate ion type In the process of adsorbing the metal complex, when an aqueous alkali metal solution of stannous tin oxide was added so that the amount of 0.05 eq/L-Resin with respect to the anion exchange resin in which the tin element was converted to the bicarbonate ion type, the tin element was converted to the bicarbonate ion type In the process of adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type, the alkali metal aqueous solution of stannous oxide is added to the anion exchange resin converted to 0.1 eq/L-Resin. , 0.5 eq with respect to the cation exchange resin converted to the hydrogen ion type from the introduction of 10 wt% of ATMP aqueous solution so that the chelate compound is in an amount of 0.2 eq/L-Resin with respect to the cation exchange resin converted to the hydrogen ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that 10 wt% of ATMP aqueous solution was added so that the amount of /L-Resin was added. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A8

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, changing the concentration of the sodium bicarbonate aqueous solution from 4% by weight to 8% by weight, ii) adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type In the process, a mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that 10 wt% of an aqueous ethylenediamine tetraacetic acid (EDTA) solution was used instead of 10 wt% of the ATMP aqueous solution as a chelate compound. prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A9

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, changing the concentration of the sodium bicarbonate aqueous solution from 4% by weight to 8% by weight, ii) adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type In the process, the cation exchange resin converted to the hydrogen ion type in place of the 10 wt % ATMP aqueous solution was added so that the chelate compound was in an amount of 0.2 eq/L-Resin with respect to the cation exchange resin converted to the hydrogen ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that 10% by weight of an EDTA aqueous solution was added in an amount of 0.5 eq/L-Resin. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A10

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of the sodium bicarbonate aqueous solution was changed from 4% by weight to 8% by weight, ii) the alkali of stannous oxide in the anion exchange resin converted to the bicarbonate ion type In the process of adsorbing the metal complex, when an aqueous alkali metal solution of stannous tin oxide was added in an amount of 0.05 eq/L-Resin with respect to the anion exchange resin in which the tin element was converted to the bicarbonate ion type, the tin element was converted to the bicarbonate ion type. In the process of adsorbing the chelate compound to the cation exchange resin converted to the hydrogen ion type, the alkali metal aqueous solution of stannous oxide is added to the anion exchange resin converted to 0.1 eq/L-Resin. , Instead of adding 10 wt% of ATMP aqueous solution so that the chelate compound is in an amount of 0.2 eq/L-Resin with respect to the cation exchange resin converted to the hydrogen ion type, the cation exchange resin converted to the hydrogen ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that 10 wt% of an EDTA aqueous solution was added in an amount of 0.5 eq/L-Resin. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin into the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

Example A11

i) In the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) hydrogen to which ATMP was adsorbed in the process of preparing the mixed-phase ion exchange resin A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that the content of the ion-type cation exchange resin was changed from 10% by volume to 20% by volume.

Example A12

i) In the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) hydrogen to which ATMP was adsorbed in the process of preparing the mixed-phase ion exchange resin A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that the content of the ion-type cation exchange resin was changed from 10% by volume to 1% by volume.

comparative example A1

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) the alkali of stannous oxide in the anion exchange resin converted to the bicarbonate ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that the metal complex was not adsorbed, and iii) the chelate compound was not adsorbed to the cation exchange resin converted to the hydrogen ion type. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin into the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

comparative example A2

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) the alkali of stannous oxide in the anion exchange resin converted to the bicarbonate ion type A mixed-phase ion exchange resin was prepared in the same manner as in Example A1, except that the metal complex was not adsorbed. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

comparative example A3

i) in the process of preparing the anion exchange resin converted to the bicarbonate ion type, the concentration of the sodium bicarbonate aqueous solution was changed from 4 wt% to 8 wt%, ii) the chelate compound was not adsorbed on the cation exchange resin converted to the hydrogen ion type Except for that, in the same manner as in Example A1, a mixed-phase ion exchange resin was prepared. In addition, the ion conversion rate (%) of the bicarbonate ion type anion exchange resin to the carbonate ion type or the bicarbonate ion type was measured in the same manner as in Example A1, and the ion conversion rate measurement results are shown in Table 1 below.

[Table 1]

As shown in Table 1, in the case of Examples 1 to 12 according to the present invention, the HCO ₃ type ion conversion rate (%) was 80% or more, and in Examples 2 and 5 to 12, the HCO ₃ type ion conversion rate (%) It can be seen that (%) is very high as 90% or more.

It can be seen from Examples 1 and 3 that sodium bicarbonate has better conversion efficiency than ammonium bicarbonate, and the sodium carbonate or ammonium carbonate aqueous solution used from Examples 1, 2, 3, and 4; Alternatively, it can be seen that the higher the concentration of sodium bicarbonate or ammonium bicarbonate aqueous solution, the higher the conversion rate.

<Purification of hydrogen peroxide solution>

Example B1 to B12 and comparative example B1 to B3

Each of the mixed-phase ion exchange resins obtained in Examples A1 to A12 and Comparative Examples A1 to A3 was charged in a column to perform purification of crude hydrogen peroxide solution. As a raw material to be purified, 35 wt% hydrogen peroxide solution containing 10 wt ppb of metals was used, and the hydrogen peroxide solution was poured downward into the mixed bed column containing the mixed-phase ion exchange resin at a temperature of 5 ° C and 0.5 L /hour, allowed to flow for 4 hours. The hydrogen peroxide solution flowing out from the lower part of the mixed-bed column was collected, the content of metals was measured by ICP-MS method, and the results are shown in Table 2 below.

[Table 2]

As shown in Table 2 above, in the case of Examples B1 to B12 according to the present invention, the anion exchange resin converted to the bicarbonate ion type to which the alkali metal complex of stannous oxide was adsorbed and the chelate compound was converted to the adsorbed hydrogen ion type Since crude hydrogen peroxide was purified by using the mixed-phase ion exchange resin according to the present invention including a cation exchange resin, it can be seen that the ion concentration of the metal impurities is very low and the amount of oxygen gas generation is remarkably low. In addition, it can be seen from Examples B5 to B7 according to the present invention that as the adsorption amount of the alkali metal complex of stannous oxide and the adsorption amount of the chelate compound increase, the ion concentration of the metal impurity further decreases and the amount of oxygen generation further decreases.

However, in Comparative Example B1, the alkali metal complex of stannous oxide is not adsorbed to the anion exchange resin converted to the bicarbonate ion type, and the chelate compound is not adsorbed to the anion exchange resin converted to the hydrogen ion type, A very large amount of metal impurity ions were eluted, and an excessive amount of oxygen was generated, which made it unstable. In Comparative Example B2, since the alkali metal complex of stannous oxide was not adsorbed to the anion exchange resin converted to the bicarbonate ion type, a relatively large amount of ions of the metal impurity were eluted, and a relatively large amount of oxygen was generated. In the case of Example B3, since the chelate compound was not adsorbed to the cation exchange resin converted to the hydrogen ion type, a relatively large amount of ions of the metal impurity were eluted, and a relatively large amount of oxygen was generated.

Claims (16)

an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and a bicarbonate ion type; and a cation exchange resin converted to a hydrogen ion type,
An alkali metal complex compound of stannous oxide is adsorbed to the anion exchange resin converted to the bicarbonate ion type or to the anion exchange resin converted to the carbonate ion type and bicarbonate ion type,
The chelate compound is adsorbed to the cation exchange resin converted to the hydrogen ion type,
Mixed-phase ion exchange resin. According to claim 1, wherein the content of the cation exchange resin is 1 to 20% by volume, based on the total volume of the mixed-phase ion exchange resin, the mixed-phase ion exchange resin. The mixed-phase ion exchange resin according to claim 1, wherein an alkali metal complex of stannous oxide is adsorbed to the anion exchange resin in an amount such that the element tin is 0.01 to 0.3 equivalents/L-Resin with respect to the anion exchange resin. . The mixed-phase ion exchange resin according to claim 1, wherein the chelate compound is adsorbed to the cation exchange resin in an amount of 0.05 to 0.5 equivalents/L-Resin relative to the cation exchange resin. According to claim 1, wherein the chelate compound,
a compound in which at least one amine group and at least one phosphonic acid group exist in one molecule; Or a compound in which at least one amine group and a carboxylic acid group exist in one molecule,
Mixed-phase ion exchange resin. The method according to claim 1, wherein the chelating compound is aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) , Diethylenetriaminepenta(methylenephosphonic acid) (DTPMA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), or a mixture thereof is selected from the group consisting of a mixture thereof. (a) adsorbing an alkali metal complex compound of stannous oxide to the anion exchange resin converted to the bicarbonate ion type or to the anion exchange resin converted to the carbonate ion type and the bicarbonate ion type;
(b) adsorbing a chelate compound to a cation exchange resin converted into a hydrogen ion type; and
(c) mixing the anion exchange resin obtained in step (a) with the cation exchange resin obtained in step (b),
A method for producing a mixed-phase ion exchange resin. 8. The method of claim 7, wherein step (a) comprises contacting an aqueous alkali metal solution of stannous oxide with an anion exchange resin converted to a bicarbonate ion type or an anion exchange resin converted to a carbonate ion type and bicarbonate ion type, A method for producing a mixed-phase ion exchange resin. The anion exchange resin according to claim 8, wherein in step (a), the tin element is converted into a bicarbonate ion type in an amount of 0.01 to 0.3 equivalents/L-Resin with respect to the anion exchange resin, or carbonate ion type and bicarbonate ion type A method for producing a mixed-phase ion exchange resin, comprising the step of contacting an aqueous alkali metal solution of stannous oxide with an anion exchange resin converted into a . The method of claim 7, wherein step (b) comprises contacting an aqueous solution of a chelate compound with a cation exchange resin converted into a hydrogen ion type. According to claim 7, (b) step is the chelate compound in an amount of 0.05 to 0.5 equivalents / L-Resin with respect to the cation exchange resin, contacting the aqueous solution of the chelate compound with the cation exchange resin converted into a hydrogen ion type A method for producing a mixed-phase ion exchange resin, comprising the steps. The method according to claim 7, wherein in step (c), the cation exchange resin and the anion exchange resin are mixed so that the content of the cation exchange resin is 1 to 20% by volume based on the total volume of the mixed-phase ion exchange resin. A method for producing a mixed-phase ion exchange resin. The method of claim 8, wherein the aqueous alkali metal solution of stannous oxide is prepared by dissolving stannous oxide in an aqueous alkali metal solution. The method of claim 13, wherein the alkali metal aqueous solution is selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, or a mixture thereof. The method of claim 8, wherein the aqueous alkali metal solution of stannic oxide is prepared by dissolving tin(II) acid alkali metal trihydrate in pure water. A method for purifying hydrogen peroxide water comprising the step of contacting the mixed-phase ion exchange resin of any one of claims 1 to 6 with crude hydrogen peroxide water.