KR20190089877A - Operation method of ultrapure water producing apparatus and ultrapure water producing apparatus - Google Patents

Abstract

The ultrapure water producing apparatus 1 includes a pretreatment apparatus 2, a primary pure water producing apparatus 3, and a subsystem 4. The primary pure water producing apparatus 3 has a tank 5, an ultraviolet oxidation apparatus 6, a platinum group metal catalyst resin column 7, a regenerative ion exchange apparatus 8 and a film degassing apparatus 9. The subsystem 4 includes a sub tank 11 and an ultraviolet oxidation apparatus 12 for treating primary pure water fed from the sub tank 11, a platinum group metal catalyst resin tower 13 and a film degassing apparatus 14, Regeneration type ion exchange apparatus 15, and an ultrafiltration (UF) membrane 16. The platinum group metal catalyst resin is obtained by supporting a platinum group metal on the support resin, and it is particularly preferable that the support resin contains particles of a nano-order metal of a platinum group metal. According to such an ultrapure water producing apparatus 1, by having the ultraviolet oxidation apparatus 12 and the platinum group metal catalyst resin tower 13 in the subsystem 4, it is possible to suppress the deterioration of the hydrogen peroxide removal capability.

Description

Operation method of ultrapure water producing apparatus and ultrapure water producing apparatus

The present invention relates to an ultrapure water producing apparatus having a primary pure water apparatus and a subsystem and a method of operating the ultrapure water producing apparatus, and more particularly, to an ultrapure water producing apparatus having an ultraviolet oxidation apparatus and a platinum group metal catalyst resin tower in a subsystem, And a method of operating the apparatus.

Ultrapure water conventionally used in the electronics industry such as semiconductors is manufactured by treating raw water with an ultrapure water producing apparatus composed of a pretreatment system, a primary pure water apparatus and a subsystem for treating primary pure water.

2, the conventional ultrapure water producing apparatus 21 generally has three stages, such as a pretreatment device 22, a primary pure water producing device 23, and a secondary pure water producing device (subsystem) . In the pretreatment device 22 of the ultrapure water producing device 21, the raw water W is subjected to pretreatment by filtration, coagulation sedimentation, a microfiltration membrane, and the like, and mainly suspended substances are removed.

The primary pure water producing apparatus 23 includes a tank 25 of the pretreated water W1, an ultraviolet (UV) oxidizing apparatus 26, a regenerative ion exchange apparatus (mixed-phase or four-phase five- A membrane deaerator 28, and, if necessary, a RO membrane separator, an electric deionizer, and the like. At this point, most of the electrolytes, fine particles, live bacteria and the like in the pretreated water W1 are removed and organic substances are decomposed.

The subsystem 24 includes a sub tank 31 for storing the primary pure water W2 produced by the above described primary pure water producing device 23 and a sub tank 31 for supplying the purified water from the sub tank 31 through a pump An ultraviolet oxidation apparatus 32 for treating the primary pure water W2, a platinum group metal catalyst resin tower 33, a membrane degasser 34, a non-regenerative mixed-bed ion exchange apparatus 35 and an ultrafiltration (UF) film 36 and, if necessary, a RO membrane separator or the like may be formed. In this subsystem 24, the ultraviolet oxidation apparatus 32 oxidizes and decomposes a trace amount of organic matter (TOC component) contained in the primary pure water W2 by ultraviolet rays. The hydrogen peroxide generated by the irradiation of the ultraviolet ray is called a platinum group metal And the dissolved gas such as DO (dissolved oxygen) mixed in the subsequent membrane deaerator 34 is removed. Subsequently, the remaining carbonate ions, organic acids, anionic substances, and further metal ions or cationic substances are removed by ion exchange by treating with the non-regenerative mixed ion exchange apparatus 35. The fine particles are removed by the ultrafiltration (UF) membrane 36 to obtain ultrapure water W3. This ultrafiltration water is supplied to the use point 37, and the unused ultrapure water returns to the sub tank 31. [

In the conventional ultrapure water producing apparatus 21 as described above, the oxidative decomposition mechanism of the TOC component in the ultraviolet oxidation apparatus 32 is to oxidize and decompose water to generate OH radicals, and the TOC component The ultraviolet ray in the ultraviolet ray oxidation apparatus 32 is usually irradiated with an excessive amount capable of sufficiently oxidatively decomposing TOC in water. When the ultraviolet ray irradiation amount of the ultraviolet ray oxidation apparatus 32 is high, the OH radicals generated by the decomposition of water are excessive, so that excess OH radicals are associated with each other to form hydrogen peroxide. The generated hydrogen peroxide decomposes by contacting with the platinum group metal catalyst resin tower 33 at the downstream stage.

However, as a result of the studies conducted by the present inventors, it has been found that the ultraviolet oxidation apparatus 32 of the subsystem 24 may degrade the hydrogen peroxide removal capability by decomposing the hydrogen peroxide for a long period of time. As a result, if hydrogen peroxide remains in the ultra-pure water W3, it may cause deterioration of the water quality and also deteriorate the non-regenerative mixed ion exchange apparatus 35 and the ultrafiltration (UF) membrane 36 at the downstream end . In addition, when hydrogen peroxide decomposes, oxygen is generated, which causes DO in the water to increase.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide an ultrapure water producing apparatus having a primary pure water apparatus and a subsystem, and having an ultraviolet oxidation apparatus and a platinum group metal catalyst resin tower, And an object of the present invention is to provide an apparatus for producing ultrapure water suppressing deterioration of the hydrogen peroxide removing ability and a method of operating the ultrapure water producing apparatus.

The present invention firstly relates to a process for the preparation of a process for the preparation of a polymer electrolyte membrane, which comprises a primary pure water apparatus having an ultraviolet oxidation apparatus, a regenerative mixed ion exchange column or an electrodeionization apparatus and a membrane degassing apparatus, a ultraviolet oxidation apparatus, And a subsystem for processing primary pure water obtained from the primary pure water apparatus, characterized in that the ultrapure water producing apparatus has a platinum group metal catalyst resin tower formed at the downstream end of the ultraviolet oxidation apparatus of the primary pure water apparatus (Invention 1).

According to the present invention (Invention 1), by forming the platinum group metal catalyst resin column at the rear end of the ultraviolet oxidation apparatus of the primary pure water apparatus, it is possible to reduce the hydrogen peroxide removal ability of the platinum group metal catalyst resin column at the downstream of the ultraviolet oxidation apparatus of the subsystem . This is for the following reasons. That is, it is considered that the decrease in the hydrogen peroxide removal capability of the platinum group metal catalyst resin tower at the downstream of the ultraviolet oxidation apparatus of the subsystem is due to hydrogen being less than the equivalent amount of hydrogen peroxide in the water to be treated and the oxidation of the platinum group metal catalyst. Next, as a result of investigation by the present inventors of the reason for the lack of hydrogen to hydrogen peroxide, it has been found that in the ultraviolet oxidation apparatus of the primary pure water apparatus, hydrogen peroxide and hydrogen are generated with decomposition of organic matter, and hydrogen is removed by a film degassing apparatus On the other hand, it was found that the hydrogen peroxide is caused by the inflow into the subsystem. Thus, when a platinum group metal catalyst resin tower is formed at the downstream of the ultraviolet oxidation unit of the primary pure water unit to decompose the hydrogen peroxide generated in the ultraviolet oxidation unit of the primary pure water unit, The hydrogen peroxide in the water decreases and the hydrogen becomes close to the equivalent amount with respect to the hydrogen peroxide, so that deterioration of the platinum group metal catalyst can be prevented.

In the above invention (Invention 1), it is preferable that the subsystem further has a non-regenerative mixed-bed ion exchange column (invention 2).

According to the invention (invention 2), a trace amount of organic matter contained in the for-treatment water is decomposed by the ultraviolet oxidation apparatus, and the residual carbonic ion, organic acid, anionic substance, Can be removed by ion exchange.

In the invention (Invention 1 or 2), it is preferable that the platinum group metal in the platinum group metal catalyst catalyst resin column of the primary pure water unit and the platinum group metal catalyst resin column of the subsystem is platinum, palladium or platinum / palladium alloy (Invention 3).

According to the invention (invention 3), hydrogen peroxide contained in the treated water can be efficiently decomposed and removed.

In the above inventions (Inventions 1 to 3), it is preferable that the platinum group metal is particles of a platinum group metal having an average particle diameter of 1 to 50 nm (Invention 4).

According to the invention (invention 4), hydrogen peroxide contained in the treated water can be decomposed and removed particularly efficiently.

The present invention secondly relates to a method for producing a platinum group metal catalyst, which comprises a first pure water apparatus having an ultraviolet oxidation apparatus, a platinum group metal catalyst resin tower, a regenerative mixed ion exchange tower or an electric deionization apparatus, and a film deaerator, 1. A method of operating an ultrapure water producing system having a top and a membrane degassing apparatus and a subsystem for treating primary pure water obtained from the primary pure water apparatus, Thereby producing ultrapure water, and a method of operating the ultrapure water producing apparatus (Invention 5).

According to the invention (invention 5), since the hydrogen peroxide generated in the ultraviolet oxidation apparatus of the primary pure water apparatus can be decomposed by forming the platinum group metal catalyst resin tower at the downstream end of the ultraviolet oxidation apparatus of the primary pure water apparatus, The hydrogen peroxide in the water to be treated at the downstream end of the ultraviolet oxidation apparatus of the ultraviolet oxidation apparatus is reduced and the hydrogen becomes close to the equivalent amount to the hydrogen peroxide, so that the ultrapure water can be produced while preventing deterioration of the platinum group metal catalyst.

In the invention (Invention 5), it is preferable that the platinum group metal in the platinum group metal catalyst catalyst resin column of the primary pure water unit and the platinum group metal catalyst resin column of the subsystem is platinum, palladium or platinum / palladium alloy 6).

According to the invention (invention 6), a very small amount of hydrogen peroxide contained in the treated water can be efficiently decomposed and removed.

In the invention (Invention 5 or 6), it is preferable that the platinum group metal is particles of a platinum group metal having an average particle diameter of 1 to 50 nm (invention 7).

According to the invention (invention 7), hydrogen peroxide contained in the treated water can be decomposed and removed particularly efficiently.

In the above inventions (Invention 5 to 7), it is preferable that the H ₂ O ₂ concentration of the treated water of the ultraviolet oxidation apparatus of the subsystem is 10 to 100 쨉 g / l, the H of the treated water of the platinum group metal catalyst- ₂ O ₂ concentration of 0.1 to 10 占 퐂 / liter (invention 8).

According to the invention (invention 8), the treatment conditions in the ultraviolet oxidation apparatus and the platinum group metal catalyst resin tower are controlled so that the H ₂ O ₂ concentration of the treated water of the ultraviolet oxidation apparatus and the platinum group metal catalyst resin tower of the sub- Adverse effects on the film-type degassing apparatus and the like at the rear end of the platinum group metal catalyst resin tower can be suppressed to the minimum, and the hydrogen peroxide concentration and dissolved oxygen concentration of the obtained ultrapure water can be set to a very low level.

According to the present invention, since the primary pure water obtained by decomposing hydrogen peroxide generated in the ultraviolet oxidation apparatus is supplied to the subsystem and the amount of accompanying hydrogen peroxide is small, the concentration of hydrogen peroxide in the treated water at the downstream of the ultraviolet oxidation apparatus of the subsystem is And relatively hydrogen is close to an equivalent amount to hydrogen peroxide, ultrapure water can be produced while preventing deterioration of the platinum group metal catalyst.

1 is a flowchart showing an ultrapure water producing apparatus according to an embodiment of the present invention.
2 is a flowchart showing a conventional ultrapure water producing apparatus.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an ultrapure water producing apparatus and a method for operating the same according to an embodiment of the present invention will be described in detail with reference to Fig.

1, the ultrapure water producing apparatus 1 includes a pretreatment apparatus 2, a primary pure water producing apparatus 3 and a secondary pure water producing apparatus 3, The pretreatment apparatus 2 is constituted by a raw water W such as a water source, a well water and a city water, Filtration, coagulation sedimentation, microfiltration membrane, and the like.

The primary pure water producing apparatus 3 includes a tank 5 of pretreatment water W1 as a to-be-treated water, a ultraviolet (UV) oxidizing apparatus 6, a platinum group metal catalyst resin tower 7, A four-phase five-column type or the like) 8 and a film deaerator 9 are provided.

The subsystem 4 includes a sub tank 11 for storing the primary pure water W2 produced by the primary pure water producing device 3 described above and a sub tank 11 for processing the primary pure water fed from the sub tank 11 The ultrafiltration (UF) membrane 16 as the membrane filtration device and the ultraviolet oxidation device 12, the platinum group metal catalyst resin column 13, the membrane degasser 14, the non-regenerative mixed ion exchange device 15, And ultrapure water W3 that has passed through the ultrafiltration (UF) membrane 16 is supplied to the use point 17 and then the unused ultrapure water W3 is returned to the sub tank 11. [

In the ultrapure water producing apparatus 1 as described above, the platinum group metal catalyst resin packed in the platinum group metal catalyst resin column 7 and the platinum group metal catalyst resin column 13 is a platinum group metal supported on the support resin.

As the carrier resin for supporting the platinum group metal, an ion exchange resin can be used, and particularly an anion exchange resin can be preferably used. The anion exchange resin used in the present embodiment is preferably a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a matrix, and is preferably a gel-type resin. Since the platinum group metal is negatively charged, the platinum group metal is stably supported on the anion exchange resin and is not easily peeled off. The exchanger of the anion exchange resin is preferably of the OH type. The OH type anion exchange resin promotes the decomposition of hydrogen peroxide by making the resin surface alkaline.

Since the supported platinum group metal has low elution with respect to ultrapure water and has a high catalytic activity, it can flow at a high water flow rate, so that even if any elution occurs, the concentration of the eluent can be suppressed and deterioration of early water quality can be suppressed . Examples of the platinum group metals include ruthenium, rhodium, palladium, osmium, iridium and platinum. These platinum group metals may be used singly or in combination of two or more kinds. Alternatively, they may be used as two or more kinds of alloys. Alternatively, a purified product of a naturally occurring mixture may be separated into a single substance It can also be used without. Of these, platinum, palladium, platinum / palladium alloy alone or a mixture of two or more of them is particularly preferably used because of its high catalytic activity.

Particularly, as the platinum group metal catalyst resin, it is preferable to use a carrier resin in which particles of a nano-order metal of platinum group are carried on the above-mentioned carrier resin.

The method for producing the metal nanoparticles of the platinum group is not particularly limited, and examples thereof include a metal salt reduction reaction method and a combustion method. Among them, the metal salt reduction reaction method can be preferably used because it is easy to produce, and metal nanoparticles of stable quality can be obtained. In the metal salt reduction method, a reducing agent such as alcohol, citric acid or its salt, formic acid, acetone or acetaldehyde is added to an aqueous solution of 0.1 to 0.4 mmol / liter of a chloride, nitrate, sulfate, metal complex or the like such as platinum 4 to 20 equivalents are added, and the mixture is stirred for 1 to 3 hours, whereby metal nanoparticles can be produced. Further, for example, 1 to 2 mmol / L of hexachloroplatinic acid, potassium hexachloroplatinate and the like are dissolved in an aqueous solution of polyvinylpyrrolidone, a reducing agent such as ethanol is added, and the mixture is refluxed for 2 to 3 hours under nitrogen atmosphere Whereby platinum nanocolloidal particles can be produced.

The average particle diameter of the metal nanoparticles of the platinum group is preferably 1 to 50 nm, more preferably 1.2 to 20 nm, and still more preferably 1.4 to 5 nm. If the average particle diameter of the metal nanoparticles exceeds 50 nm, the specific surface area of the nanoparticles becomes small, and the catalytic activity for decomposition and removal of hydrogen peroxide may be lowered. On the other hand, if the average particle diameter of the metal nanoparticles is less than 1 nm, the catalytic activity for decomposition and removal of hydrogen peroxide may be lowered.

The supported amount of the platinum group metal nano-particles to the anion exchange resin as described above is preferably 0.01 to 0.2% by weight, more preferably 0.04 to 0.1% by weight. If the loading amount of the metal nanoparticles is less than 0.01% by weight, the catalytic activity for decomposition and removal of hydrogen peroxide may be insufficient. When the loading amount of the metal nanoparticles is 0.2 wt% or less, sufficient catalytic activity is exhibited for the decomposition and removal of hydrogen peroxide, and it is not necessarily economical to carry metal nanoparticles of more than 0.2 wt%. In addition, when the amount of metal nanoparticles to be loaded increases, there is also a concern of elution of metal into water.

Next, a method of operating the ultrapure water producing apparatus 1 of the present embodiment having the above-described structure will be described.

First, the raw water W is mainly removed by the pretreatment device 2 by coagulation sedimentation, coagulation filtration, coagulation pressurization, or the like to remove the contaminants mainly in the raw water W. The pretreated water W1 is once stored in the tank 5 and fed to the primary pure water device 3 by a pump not shown.

In the primary pure water unit 3, the organic matter (TOC) in the pretreated water W1 is oxidized by the ultraviolet (UV) oxidizing unit 6 to become an organic acid and further carbon dioxide. In addition, OH radicals and hydrogen are generated by the decomposition of water in the pretreated water W1 by ultraviolet rays irradiated excessively to the ultraviolet oxidation processor 6, and surplus OH radicals are associated with each other to become hydrogen peroxide. As a result, the concentration of H ₂ O _{2 in} the treated water of the ultraviolet oxidation apparatus 6 is 10 to 100 μg / l. Further, the hydrogen is removed by a film degassing apparatus 9 described later. As a result, conventionally, the treated water with a high hydrogen peroxide concentration and reduced hydrogen is supplied to the subsystem 4 as the primary pure water, which causes the function of the platinum group metal catalyst resin tower 13 on the subsystem side to deteriorate there was.

Thus, in the present embodiment, the hydrogen peroxide generated is decomposed by forming the platinum group metal catalyst resin column 7 at the downstream end of the ultraviolet oxidation unit 6. The concentration of H ₂ O ₂ is about 0.1 to 10 μg / liter. Especially when the platinum group metal nanoparticles are used, the concentration of H ₂ O ₂ is about 0.1 to 1 μg / . Most of the electrolytes (ionic components) in the pretreated water W1 are removed by a regenerative ion exchanger (mixed-phase type or four-phase five-column type or the like) 8, dissolved oxygen (TOC) of 2 ppb or less and a H ₂ O ₂ concentration of 0.1 to 10 μg / l to obtain primary pure water (W2). The primary pure water W2 is once stored in the sub tank 11 and then sent to the subsystem 4 by a pump not shown.

Next, in the subsystem 4, a trace amount of organic matter remaining in the primary pure water W2 in the ultraviolet (UV) oxidizing apparatus 12 is oxidized to become an organic acid, and furthermore, it becomes carbon dioxide. At this time, ultraviolet rays are excessively irradiated in the ultraviolet oxidation apparatus 12 in order to remove the organic matter to the limit, so that the OH radicals generated by the decomposition of the water of the primary pure water W2 become excessive, Hydrogen peroxide is generated by association. Thus, the concentration of H ₂ O ₂ in the primary pure water (W ₂ ) is about 0.1 to 10 μg / L to about 10 to 100 μg / L, which is higher than the primary pure water (W 2).

The generated hydrogen peroxide is decomposed in the platinum group metal catalyst resin column 13 at the downstream end, and the concentration of H ₂ O ₂ is about 10 μg / liter or less. In particular, when the platinum group metal nanoparticles are used, the H ₂ O ₂ concentration is 5 Ug / liter or less, particularly 1 占 퐂 / liter or less, lower than the treated water of the ultraviolet oxidation apparatus (12).

On the other hand, oxygen is also generated by the decomposition of hydrogen peroxide, and dissolved oxygen is increased due to this, so that dissolved oxygen is removed by the film degasser 14 formed at the subsequent stage. Then, a metal ion or a cationic substance flowing in from a trace amount of carbonate ions, organic acids, an anionic substance, or shear is removed by a non-regenerative mixed ion exchange apparatus 15, and further, an ultrafiltration (UF) Ultrapure water (W3) can be produced by removing the fine particles with the aid of the impregnation step (16). The ultrapure water W3 is supplied to the use point 17 and the unused ultrapure water W3 is returned to the sub tank 11. [

The ultrapure water W3 in the present embodiment has a resistivity of 18.1 M? 占 ㎝ m or more, a fine particle diameter of 50 nm or more and 1000 pieces / Organic Carbon: not more than 1 / / ℓ, total silica not more than 0.1 ㎍ / ℓ, metals: not more than 1 ng / ℓ, and ionic species: not more than 10 ng / ℓ.

Particularly, when the platinum group metal catalyst resin of the platinum group metal catalyst resin bed 13 is supported on the anion exchange resin with the metal nano particles of the platinum group, the anion exchange resin carrying the metal nano particles of the platinum group has a specific surface area Because of this large size, the reaction rate of hydrogen peroxide decomposition is very fast and the water flow rate can be increased. Since the flow rate is larger than the amount of the catalyst, the influence of the metal eluted from the catalyst in the treated water can be made very small. In addition, since hydrogen peroxide in water is rapidly decomposed in contact with the metal nano-colloid particles of the platinum group carried on the anion exchange resin and does not act on the anion exchange resin, the anion exchange resin is impregnated with hydrogen peroxide, (TOC) is not likely to be eluted.

Although the present invention has been described with reference to the accompanying drawings, it is to be understood that the present invention is not limited to the above-described embodiment, and that the ultraviolet (UV) oxidation device 6 of the primary pure water device 3, It is only necessary to form the metal catalyst resin column 7, and various modifications can be made. For example, as the platinum group metal catalyst resin of the platinum group metal catalyst resin column 13 of the subsystem 4, it is preferable to use an anion exchange resin carrying platinum group metal nanoparticles. In this case, As the platinum group metal catalyst resin column 7 at the rear stage of the ultraviolet (UV) oxidation apparatus 6 of the apparatus 3, an anion exchange resin carrying metal nano particles of the platinum group may be used. Alternatively, The platinum group metal catalyst resin may be used, and the two may be different. If necessary, desalination means such as an RO membrane separation device or an electric deionization device or various other elements may be formed in the primary pure water device 3 and the subsystem 4, The pure water producing apparatus may be formed so that the pure water producing apparatus has a three-stage structure.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]

Platinum nanocolloidal particles having an average particle diameter of 3.5 nm were supported on a strongly basic gel type anion exchange resin with a loading amount of 0.07 wt% to prepare an anion exchange resin carrying platinum group metal nanoparticles as a platinum group metal catalyst resin.

The ultrapure water W3 is produced by constituting the platinum group metal catalyst resin beds 7 and 13 by using the platinum group metal catalyst resin described above in the ultrapure water producing apparatus 1 of the apparatus configuration shown in FIG. (Initial) of the inlet and outlet water of the platinum group metal catalyst resin column 13 of the catalyst layer 4 were measured. The results are shown in Table 1. The hydrogen peroxide concentration (end stage) at the outlet water of the platinum group metal catalyst resin column 13 after the operation of the ultrapure water production apparatus 1 for a long period of time was measured. The results are shown together in Table 1. The concentration of hydrogen peroxide is adjusted to 10 g by adding sodium sulfate (anhydrous) to 4.8 mg of phenolphthalein, 8 mg of copper sulfate (anhydrous) and 48 mg of sodium hydroxide to prepare a reagent for quantitatively determining a trace amount of hydrogen peroxide. 0.5 g of the reagent was added to and dissolved in 10 ml of the test water, and the solution was allowed to stand at room temperature for 10 minutes, and was calculated based on the measured value of absorbance at 552 nm.

[Comparative Example 1]

Except that the platinum group metal catalyst resin column 7 was not formed on the downstream side of the ultraviolet oxidation unit 6 of the primary pure water unit 3 in Example 1 to constitute the ultrapure water producing unit, And the hydrogen peroxide concentration (initial value) of the inlet and outlet water of the platinum group metal catalyst resin tower 13 of the subsystem 4 was measured. The results are shown in Table 1. The hydrogen peroxide concentration (end stage) at the outlet water of the platinum group metal catalyst resin column 13 after the operation of the ultrapure water production apparatus 1 for a long period of time was measured. The results are shown together in Table 1.

As is apparent from Table 1, in Comparative Example 1 in which the platinum group metal catalyst resin column 7 was not provided at the downstream end of the ultraviolet oxidation unit 6 of the primary pure water unit 3, the hydrogen peroxide concentration of ultrapure water (W3) The rise was remarkable, but there was almost no change in Example 1.

[Comparative Examples 2 and 3 and Reference Example]

In the comparative example 1, the resin of the platinum group metal catalyst resin column 13 after long-term operation was separated into three regions of the surface layer portion, the middle portion and the lower portion and taken out. The surface layer portion and the middle portion resin were filled in the respective test columns, Of a platinum group metal catalyst resin bed. As a reference example, a new resin was similarly charged in a test column to obtain a platinum group metal catalyst resin bed.

Deionized water (hydrogen peroxide 1 ㎍ / ℓ less) water flow velocity (SV) of hydrogen peroxide in the test column, respectively 300 ㎍ / ℓ and 1000 ㎍ / ℓ was added to, and preparing a number of test inlet, described above this number test inlet to 300 hr ^{- 1} , the concentration of hydrogen peroxide at the outlet water was measured. The results are shown in Table 2.

As is apparent from Table 2, in Comparative Example 2 in which the column surface layer resin of the platinum group metal catalyst resin column 13 after long-term operation was packed in the column, the concentration of hydrogen peroxide in the treated water Respectively. As a result, it can be seen that the degradation of the hydrogen peroxide decomposition ability is large in the middle resin. When passing through the platinum group metal catalyst resin tower 13 in the downflow direction, the hydrogen peroxide concentration decreases as the surface layer portion goes downward, while the dissolved hydrogen concentration is lowered. It is presumed that this is caused by oxidation deterioration caused by the oxidation.

1: Ultrapure water producing device
3: Primary pure water production equipment
4: Subsystem (Secondary pure water manufacturing device)
6: ultraviolet oxidation apparatus
7: Platinum group metal catalyst resin tower
8: Regenerative ion exchanger
9: Membrane degasser
12: Ultraviolet oxidation apparatus
13: Platinum group metal catalytic resin tower
14: Membrane degasser
15: Non-regenerative mixed-bed ion exchange apparatus
W: enemies
W1: preprocessing number
W2: Primary pure water
W3: Ultrapure water (secondary pure water)

Claims (8)

A primary pure water device having an ultraviolet oxidation device, a regenerative mixed-bed ion exchange column or an electric deionization device and a film degassing device, an ultraviolet oxidation device, a platinum group metal catalyst resin bed and a film degassing device, In an ultrapure water producing apparatus provided with a subsystem for processing the obtained primary pure water,
Wherein a platinum group metal catalyst resin tower is formed on the downstream side of the ultraviolet oxidation unit of the primary pure water unit. The method according to claim 1,
Wherein the subsystem further has a non-regenerative mixed-phase ion exchange column. 3. The method according to claim 1 or 2,
Wherein the platinum group metal catalyst resin bed of the primary pure water unit and the platinum group metal in the platinum group metal catalyst bed of the subsystem are platinum, palladium or platinum / palladium alloy. 4. The method according to any one of claims 1 to 3,
Wherein the platinum group metal is particles of a platinum group metal having an average particle diameter of 1 to 50 nm. A primary pure water unit having a ultraviolet oxidation unit, a platinum group metal catalyst resin tower, a regenerative mixed-bed ion exchange column or an electric deionization unit, and a film deaerator, an ultraviolet oxidation unit, a platinum group metal catalyst resin tower, and a film degasser And a sub-system for processing primary pure water obtained from the primary pure water system, the method comprising:
And the water to be treated is continuously passed through the primary pure water device and the subsystem to produce ultrapure water. 6. The method of claim 5,
Wherein the platinum group metal catalyst resin bed of the primary pure water unit and the platinum group metal in the platinum group metal catalyst bed of the subsystem are platinum, palladium or platinum / palladium alloy. The method according to claim 5 or 6,
Wherein the platinum group metal is particles of a platinum group metal having an average particle size of 1 to 50 nm. 8. The method according to any one of claims 5 to 7,
H ₂ O ₂ concentration of the treated water of the ultraviolet oxidation device of the subsystem, and 10 ~ 100 ㎍ / ℓ, the platinum group H ₂ O ₂ concentration in the treated metal catalyst resin column of the sub-system 0.1 ~ 10 ㎍ / ℓ The operation method of the ultrapure water producing apparatus.

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