CN110678420A - Ultrapure water production system and ultrapure water production method - Google Patents
Ultrapure water production system and ultrapure water production method Download PDFInfo
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- CN110678420A CN110678420A CN201880027433.2A CN201880027433A CN110678420A CN 110678420 A CN110678420 A CN 110678420A CN 201880027433 A CN201880027433 A CN 201880027433A CN 110678420 A CN110678420 A CN 110678420A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
Abstract
The invention providesProvided is an ultrapure water production system which is provided with a boron adsorption resin mixed with an ion exchange resin and which can obtain ultrapure water having high water quality and a low boron concentration and a low TOC concentration for a long time. An ultrapure water production system for producing ultrapure water by treating water to be treated containing a boron component and a total organic carbon component, the ultrapure water production system comprising, in order: the treated water is treated at a rate of 0.05kWh/m3～0.2kWh/m3The 1 st ultraviolet oxidation device for irradiating ultraviolet rays with the ultraviolet irradiation amount of (1); a boron-adsorbing resin mixed ion exchange device having a boron-adsorbing anion exchange mixed bed resin obtained by mixing a boron-adsorbing resin and an anion exchange resin; 2, ultraviolet oxidation device; and a non-regenerative mixed bed ion exchange resin apparatus.
Description
Technical Field
The present invention relates to an ultrapure water production system and an ultrapure water production method.
Background
Ultrapure water used in a semiconductor manufacturing process has been conventionally manufactured using an ultrapure water manufacturing system. The ultrapure water production system is composed of, for example, a pretreatment apparatus for removing suspended substances in raw water, a primary pure water system for removing Total Organic Carbon (TOC) components or ionic components in the pretreatment water using a reverse osmosis membrane apparatus or an ion exchange apparatus, and a secondary pure water system for removing trace impurities in the primary pure water. As the raw water, used ultrapure water (hereinafter, referred to as "recovered water") recovered at a Point Of Use (POU) may be used in addition to city water, well water, underground water, industrial water, and the like.
With respect to ultrapure water, demand for high purity has been increasing year by year, and removal to the ng/L (ppt) level, for example, has been demanded for various impurity concentrations. Therefore, for example, for the purpose of reducing TOC, a combination of an ultraviolet oxidation apparatus (TOC-UV) for decomposing TOC components and a mixed bed type ion exchange resin apparatus for adsorbing and removing low molecular weight organic acids or carbon dioxide remaining in the treated water of the ultraviolet oxidation apparatus are provided in the primary and secondary pure water systems, respectively (for example, see patent document 1).
Further, as an extremely small amount of impurities, for example, boron is required to be reduced. Therefore, for the purpose of improving the boron removal ability, an ultrapure water production system using an ion exchange resin column in which a boron selective ion exchange resin and a mixed bed type ion exchange resin are stacked or mixed and filled has been proposed (for example, see patent document 2).
In addition, low molecular weight organic acids and the like contained in the treated water of the ultraviolet oxidation apparatus inhibit adsorption of boron in the boron selective ion exchange resin, and the boron removal ability is reduced at an early stage. For the purpose of preventing such a problem and maintaining excellent boron removal ability for a long time, an ultrapure water production system using a mixed bed type ion exchange resin (hereinafter, also referred to as "boron adsorption resin mixed ion exchange resin") in which a boron selective ion exchange resin and an anion exchange resin are mixed has been proposed (for example, see patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-025184
Patent document 2: japanese laid-open patent publication No. 8-84986
Patent document 3: japanese patent laid-open publication No. 2016 & 047496
Disclosure of Invention
Problems to be solved by the invention
However, the inventors have found through their studies that when the boron adsorbent resin mixed ion exchange resin is disposed at the rear stage of the ultraviolet oxidation apparatus, hydrogen peroxide generated by excessive ultraviolet irradiation in the ultraviolet oxidation apparatus decomposes the boron adsorbent resin mixed ion exchange resin, thereby dissolving a large amount of low-molecular-weight organic substances, and the TOC removal load in the downstream water treatment apparatus becomes high. Further, it has been found that, in this case, deterioration of the non-regenerative mixed bed type ion exchange resin provided downstream of the boron adsorption resin mixed ion exchange resin proceeds at an early stage, and long-term production of ultrapure water becomes difficult.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an ultrapure water production system and an ultrapure water production method, the ultrapure water production system including a boron adsorption resin mixed ion exchange resin, which can obtain ultrapure water having high water quality for a long time.
Means for solving the problems
An ultrapure water production system according to the present invention is an ultrapure water production system for producing ultrapure water by treating water to be treated containing a boron component and a total organic carbon component, the ultrapure water production system comprising, in order: the treated water was treated at a rate of 0.05kWh/m3～0.2kWh/m3The 1 st ultraviolet oxidation device for irradiating ultraviolet rays with the ultraviolet irradiation amount of (1); a boron-adsorbing resin mixed ion exchange unit which has a boron-adsorbing anion-exchange mixed bed resin obtained by mixing a boron-adsorbing resin and an anion-exchange resin, and which treats the water to be treated which has been irradiated with ultraviolet light by the ultraviolet ray oxidation unit 1; a 2 nd ultraviolet ray oxidation unit for irradiating the water to be treated by the boron-adsorbing resin mixed ion exchange unit with ultraviolet rays; and a non-regenerative mixed bed ion exchange resin unit for treating the water to be treated which has been irradiated with ultraviolet light by the 2 nd ultraviolet oxidation unit.
In the ultrapure water production system of the present invention, regarding the mixing ratio of the boron adsorption resin and the anion exchange resin in the boron adsorption anion exchange mixed bed resin, the exchange capacity of the anion exchange resin is represented by "CA", the exchange capacity of the boron adsorption resin is" CB”，CA/CBPreferably 0.2 to 5.
In the ultrapure water production system of the present invention, the boron-adsorbing-resin mixed ion exchange device preferably comprises a boron-adsorbing cation-exchange mixed bed resin obtained by further mixing a cation-exchange resin with the boron-adsorbing anion-exchange mixed bed resin.
In the ultrapure water production system of the present invention, regarding the mixing ratio of the boron adsorption resin, the anion exchange resin and the cation exchange resin in the boron adsorption cation exchange mixed bed resin, the exchange capacity of the anion exchange resin is represented by "CA", the exchange capacity of the boron adsorption resin is" CB", the exchange capacity of the cation exchange resin is setIs "CC”，CC/(CA+CB) Preferably 0.3 to 1.3.
In the ultrapure water production system of the present invention, it is preferable that a reverse osmosis membrane apparatus and an electrodeionization apparatus are provided in this order upstream of the 1 st ultraviolet oxidation apparatus.
In the ultrapure water production system of the present invention, the electric current value per 1 unit of the treatment flow rate in the above-mentioned electrodeionization device is preferably 30A/(m)3H) above.
In the ultrapure water production system of the present invention, the membrane resistance of the reverse osmosis membrane device is preferably 45MPa/(m/h) or more.
In the ultrapure water production system of the present invention, the total organic carbon concentration in the treated water of the boron-adsorbing resin mixed ion exchange device is preferably 5 μ g/L (as C) or less.
In the ultrapure water production system of the present invention, it is preferable that: the total organic carbon concentration in the treated water of the non-regenerative mixed bed ion exchange resin device is less than 0.5 [ mu ] g/L (as C), and the boron concentration is less than 0.5 ng/L.
The ultrapure water production method of the present invention is an ultrapure water production method for producing ultrapure water by treating water to be treated containing a boron component and a total organic carbon component, comprising the steps of: the ultraviolet ray irradiation amount was set to 0.05kWh/m by the 1 st ultraviolet ray oxidation apparatus3～0.2kWh/m3A step of treating the water to be treated; treating the treated water of the 1 st ultraviolet oxidation apparatus with a boron-adsorbing resin-mixed ion exchange apparatus having a boron-adsorbing anion exchange mixed bed resin obtained by mixing a boron-adsorbing resin and an anion exchange resin; treating the treated water of the boron adsorption resin mixed ion exchange device by a 2 nd ultraviolet oxidation device; and a step of treating the treated water of the 2 nd ultraviolet oxidation apparatus by a non-regenerative mixed bed ion exchange resin apparatus.
Effects of the invention
According to the ultrapure water production system and the ultrapure water production method of the present invention, in an ultrapure water production system provided with a boron-adsorbing resin-mixed ion exchange resin, ultrapure water having high water quality and low boron concentration and TOC concentration can be produced for a long time.
Drawings
FIG. 1 is a block diagram showing an ultrapure water production system according to embodiment 1.
FIG. 2 is a block diagram showing an ultrapure water production system according to embodiment 2.
FIG. 3 is a graph showing the relationship between the water passage time and the TOC concentration of treated water when hydrogen peroxide is passed through various ion exchange resins.
FIG. 4 is a graph showing the relationship between the amount of ultraviolet light irradiated and the terminal TOC concentration in the 1 st ultraviolet oxidation apparatus after 1 year of water passage in the ultrapure water production system of the example.
FIG. 5 is a graph showing the relationship between the amount of ultraviolet light irradiated and the terminal TOC concentration in the 1 st ultraviolet oxidation apparatus after 1 month of water passage in the ultrapure water production system of the example.
Fig. 6 is a graph showing the relationship between the amount of ultraviolet irradiation and the amount of hydrogen peroxide generated in the 1 st ultraviolet oxidation apparatus.
Detailed Description
Hereinafter, embodiments will be described in detail with reference to the drawings.
(embodiment 1)
As shown in fig. 1, the ultrapure water production system 1 of embodiment 1 is configured by connecting a pretreatment apparatus 11, a1 st ultraviolet ray oxidation apparatus (TOC-UV1)12, a boron adsorption resin-mixed ion exchange apparatus 13, a 2 nd ultraviolet ray oxidation apparatus (TOC-UV2)14, and a non-regenerative mixed bed type ion exchange resin apparatus (Polisher)15 in this order. In the ultrapure water production system 1, raw water is treated by passing through the pretreatment apparatus 11, the 1 st ultraviolet oxidation apparatus 12, the boron adsorption resin mixed ion exchange apparatus 13, the 2 nd ultraviolet oxidation apparatus 14, and the non-regenerative mixed bed ion exchange resin apparatus 15, and treated water (end water) of the non-regenerative mixed bed ion exchange resin apparatus 15 is supplied to a point of use (POU) 16. In the ultrapure water production system 1, the ultraviolet ray irradiation amount in the 1 st ultraviolet ray oxidation apparatus 12 is 0.05 to 0.2kWh/m3。
In the ultrapure water production system 1, raw water may be city water, well water, industrial water, or the like. The raw water contains about 5 to 100 [ mu ] g/L of boron (B). The pretreatment device 11 has a function of removing suspended matter in raw water to treat the raw water to a water quality suitable for supply to the boron adsorption resin mixed ion exchange device 13. Among boron in the raw water, boron which is not removed by the pretreatment device 11 remains in the water.
The pretreatment device 11 is configured by appropriately selecting, for example, a sand filter device, a microfiltration device, and the like for removing suspended substances in raw water, and further includes a heat exchanger and the like for adjusting the temperature of water to be treated as necessary. The pretreatment device 11 may be omitted depending on the quality of the raw water.
The 1 st ultraviolet oxidation apparatus (TOC-UV1)12 has an ultraviolet lamp capable of irradiating ultraviolet rays having a wavelength of about 185nm, and oxidizes and decomposes TOC in water to be treated by irradiating the water to be treated with ultraviolet rays by the ultraviolet lamp. The ultraviolet lamp used in the 1 st ultraviolet oxidation apparatus 12 may be, for example, a low-pressure mercury lamp that emits ultraviolet rays around 254nm together with 185 nm. Commercially available products of such low-pressure mercury lamps are preferably, for example, JPW-2, AUV-8000TOC, SUV-TOC series (all manufactured by PHOTOSCIENCE JAPAN CORP.).
The 1 st ultraviolet oxidation apparatus 12 has the following functions: ultraviolet rays having a wavelength of about 185nm decompose water to generate OH radicals, which oxidize and decompose organic substances contained in the water to be treated. When excessive ultraviolet irradiation is performed in the 1 st ultraviolet oxidation apparatus 12, OH radicals that do not contribute to oxidative decomposition of organic substances react with each other to generate hydrogen peroxide. The generated hydrogen peroxide may decompose the resin in the ion exchange resin column provided downstream.
In order to reduce the hydrogen peroxide and inhibit the decomposition of the downstream boron adsorption resin mixed ion exchange resin, the ultraviolet ray irradiation amount in the 1 st ultraviolet ray oxidation device 12 is 0.05 to 0.2kWh/m3。
Wherein the ultraviolet irradiation amount is an ultraviolet oxidation deviceThe power consumption (kW) per 1 light source (UV lamp) x the number (number) of UV lamps in the system is divided by the treatment flow rate (m)3H) calculated value. In the 1 st ultraviolet oxidation apparatus, it is preferable that a stirring plate or the like is provided in a chamber through which water to be treated flows, and the water to be treated is stirred by the stirring plate. This can suppress the influence of the difference in the ultraviolet irradiation amount due to the difference in the distance from the light source on the water to be treated in the ultraviolet oxidation apparatus.
Further, when carbon dioxide or a carboxylic acid compound is contained in the water to be treated in the boron adsorbent resin mixed ion exchange device 13 at the subsequent stage, the adsorption capacity of boron of the boron adsorbent resin may be lowered due to the adsorption of the carbon dioxide or the carboxylic acid compound to the boron adsorbent resin.
The carboxylic acid compound is, for example, an aliphatic carboxylic acid having 1 or 2 or more carboxyl groups in the molecule and having 0 or 1 or more carbon atoms, and typically an aliphatic carboxylic acid having 0to 5 carbon atoms. Specific examples of the carboxylic acid compound include formic acid, acetic acid, and oxalic acid.
The ultraviolet ray irradiation amount in the 1 st ultraviolet ray oxidation device 12 is 0.05 to 0.2kWh/m3Carbon dioxide and carboxylic acid compounds in the treated water can be reduced. Further, the ultraviolet irradiation amount was set to 0.05kWh/m3Above and below 0.1kWh/m3Further, it is more preferable to suppress the power consumption of the ultraviolet irradiation device. Within the above range, the boron adsorption capacity improvement effect in the boron adsorption resin mixed ion exchange device 13 can be obtained. The total concentration of carbon dioxide and carboxylic acid compounds in the water after passing through the 1 st ultraviolet oxidation device 12 is preferably 1 to 20 μ g/L (in terms of C), for example, in terms of TOC.
In the ultrapure water production system 1, the boron-adsorbing-resin mixed ion exchange device 13 includes, as the boron-adsorbing-resin mixed ion exchange resin, a boron-adsorbing anion-exchange mixed bed resin in which a boron-adsorbing resin and an anion exchange resin are mixed.
The boron-adsorbing resin mixed ion exchanger 13 has a function of capturing and removing boron in the water flowing through the 1 st ultraviolet oxidation apparatus 12. The boron-adsorbing resin-mixed ion exchanger 13 is configured by filling a mixture of a boron-adsorbing resin and an anion-exchange resin in a cylindrical resin column, for example.
Regarding the mixing ratio of the boron adsorption resin and the anion exchange resin in the boron adsorption anion exchange mixed bed resin containing the mixture of the boron adsorption resin and the anion exchange resin, the exchange capacity of the boron adsorption resin is CBAnd the exchange capacity of the anion exchange resin is CA，CA/CBPreferably 0.2 to 5, and more preferably 1 to 5. Through CA/CBA boron adsorption capacity of 5 or less can be sufficiently exhibited by the boron adsorption resin. Through CA/CBThe content of 0.2 or more can suppress the influence of the organic acid which inhibits the boron adsorption ability of the boron adsorption resin, and therefore the boron adsorption ability of the boron adsorption resin can be sufficiently exhibited.
As the boron-adsorbing resin in the boron-adsorbing anion-exchange mixed-bed resin, a resin obtained by adding a functional group having a polyol group as a boron-adsorbing group to a polystyrene resin or a phenol resin can be used. As the boron adsorption resin, an ion exchange resin containing an N-methylglucamine group having a high boron adsorption capacity is particularly preferable. Further, the exchange capacity of the boron adsorption resin is preferably 0.15 to 1.5meq/mL in view of boron removal ability. The specific gravity of the boron adsorption resin is preferably 1.05-1.15 g/cm3。
Examples of commercially available products of boron-adsorbing resins include Amberlite (registered trademark, manufactured by Rohm and Haas company), IRA-743T, DIAION CRB02, DIAION CRB03 (both manufactured by Mitsubishi chemical corporation), and the like.
The boron-adsorbing resin mixed ion exchange device 13 may be provided with a boron-adsorbing cation-exchange mixed bed resin in which a cation-exchange resin is mixed in addition to the above-described boron-adsorbing resin and anion-exchange resin.
In this case, the desorbed groups in the boron-adsorbing cation-exchange anion-exchange mixed-bed resin can be suppressed from leaking out as organic substances.
For boron adsorption of cation exchange anionsThe mixing ratio of the boron adsorption resin, the cation exchange resin and the anion exchange resin in the mixed exchange bed resin is such that the exchange capacity of the boron adsorption resin is CBThe exchange capacity of the cation exchange resin is represented by CCThe exchange capacity of the anion exchange resin is represented by CAExchange capacity ratio in the presentation, CC/(CA+CB) Preferably 0.3 to 1.3, and more preferably 0.4 to 1.0.
If CC/(CA+CB) When the amount is 1.3 or less, the boron-adsorbing cation-exchange anion-exchange mixed bed resin is less likely to have an acidic atmosphere therein, and the boron-adsorbing ability can be sufficiently exhibited. Through CC/(CA+CB) The amount of the organic solvent is 0.3 or more, and the effect as a mixed bed type ion exchange resin using the mixed cation exchange resin and anion exchange resin can be sufficiently exhibited, thereby improving the purity of the treated water.
The anion exchange resin is preferably a strongly basic anion exchange resin, and a styrene resin having a quaternary ammonium group as an ion exchange group is preferred because the hydrolysis of the anion exchange resin is small and the elution of the organic anion component into ultrapure water is small. As the strongly basic anion exchange resin, a resin having an exchange capacity of preferably 0.7 to 1.5meq/mL, more preferably 1 to 1.5meq/mL is preferable.
Further, since an anion component having low ion selectivity can be removed, the anion exchange resin is preferably in an OH type. As the OH form conversion rate, an anion exchange resin of 99.95% or more is suitably used. The specific gravity of the anion exchange resin is preferably 1.0-1.1 g/cm3。
Commercially available strongly basic anion exchange resins include Duolite AGP (manufactured by Rohm and Haas company), DIAION SAT20L (manufactured by Mitsubishi chemical corporation), and the like.
The cation exchange resin is preferably a strongly acidic cation exchange resin, and a styrene-based resin having a sulfonic acid group as an ion exchange group is preferable because hydrolysis of the cation exchange resin is small and elution of an organic cation component into ultrapure water is small. The strongly acidic cation exchange resin is preferably a resin having an exchange capacity of preferably 1.5 to 2.5meq/mL, more preferably 2 to 2.5 meq/mL.
The cation exchange resin is preferably an H-type resin because it can remove a cation component having low ion selectivity. As the H-type conversion ratio, a cation exchange resin of 99.95% or more is suitably used. The specific gravity of the cation exchange resin is preferably 1.2-1.3 g/cm3。
Commercially available products of strongly acidic cation exchange resins include Duolite CGP (manufactured by Rohm and Haas company), DIAION SKT20L (manufactured by Mitsubishi chemical Co., Ltd.), and the like.
The water flow rate in the boron-adsorbing resin mixed ion exchanger 13 is preferably 1 to 100(1/h), and particularly preferably 3 to 50(1/h), from the viewpoint of highly removing boron for a long period of time. When the water flow rate is not more than the above upper limit, the boron removal rate can be improved. On the other hand, when the amount is equal to or more than the above lower limit, elution of organic substances and the like in the mixed bed resin can be suppressed, and the TOC concentration of the treated water can be further reduced.
The boron removal rate in the boron adsorption resin mixed ion exchange device 13 can be, for example, 97% or more, and when the raw water of the above-described water quality is used, treated water having a boron concentration of 1ng/L or less can be obtained. The TOC concentration in the treated water of the boron-adsorbing resin mixed ion exchange device 13 is preferably maintained at 5. mu.g/L (expressed as C) or less, more preferably at 3. mu.g/L (expressed as C) or less, and still more preferably at 1. mu.g/L (expressed as C) or less.
The 2 nd ultraviolet oxidation apparatus (TOC-UV2)14 irradiates the treated water in the boron adsorption resin mixed ion exchange apparatus 13 with ultraviolet rays to decompose the TOC component in the water. The TOC component in the treated water of the boron adsorbent resin mixed ion exchange device 13 is mainly an organic component generated by decomposition of the mixed bed resin in the boron adsorbent resin mixed ion exchange device 13, an organic component derived from a trace amount of residual raw water, an organic component derived from a pipe or the like, and the like. In the 2 nd ultraviolet oxidation apparatus 14, by decomposing such organic matter components, ultrapure water having a lower TOC concentration can be obtained at the end.
As 2 nd ultraviolet rayThe oxidation apparatus 14 may be the same as the ultraviolet oxidation apparatus 12 of item 1. The ultraviolet ray irradiation amount in the 2 nd ultraviolet ray oxidation device 14 is preferably 0.1 to 0.5kWh/m3. By providing the 2 nd ultraviolet oxidation device 14 in this manner, the total of the power consumed by the 1 st ultraviolet oxidation device 12 and the 2 nd ultraviolet oxidation device 14 can be reduced. In addition, since the power consumption in the 1 st ultraviolet oxidation apparatus 12 and the 2 nd ultraviolet oxidation apparatus 14 is reduced, the amount of hydrogen peroxide generated is reduced. Therefore, the decomposition of the ion exchange resin, particularly the boron adsorption resin, in the boron adsorption resin mixed ion exchange device 13 or the non-regenerative mixed bed ion exchange device 15 can be suppressed.
The non-regenerative mixed bed ion exchange resin apparatus (Polisher)15 is constituted by filling a mixed cation exchange and anion exchange bed resin obtained by mixing a cation exchange resin and an anion exchange resin in accordance with respective exchange capacities in an apparatus such as a resin column.
The non-regenerative mixed bed ion exchange resin apparatus 15 is provided at the end of the ultrapure water production system 1, in the vicinity of the point of use (POU) 16. The non-regenerative mixed bed ion exchange resin apparatus 15 mainly removes a trace amount of organic acid components generated by decomposition of organic matter components in water in the 2 nd ultraviolet oxidation apparatus 14, and reduces the TOC concentration.
When the cation exchange anion exchange mixed bed resin packed inside is deteriorated or broken, the non-regenerative mixed bed ion exchange resin apparatus 15 is replaced together with the apparatus, or the resin packed inside is taken out and replaced with a new resin. Here, if the amount of the TOC component in the water supplied to the 2 nd ultraviolet oxidation apparatus 14 is large, the amount of the organic acid generated by decomposition increases, the load on the non-regenerative mixed bed ion exchange resin apparatus 15 increases, and the replacement frequency increases.
In the ultrapure water production system 1 of the present embodiment, decomposition of the resin in the boron-adsorbing resin mixed ion exchange unit 13 is suppressed by setting the ultraviolet irradiation amount of the 1 st ultraviolet oxidation unit 12 to the above range. Therefore, leakage of the organic matter component in the boron adsorption resin mixed ion exchange device 13 is suppressed, and the load on the non-regenerative mixed bed ion exchange resin device 15 is extremely reduced. This makes it possible to produce ultrapure water having extremely low boron concentration and extremely low TOC concentration for a long period of time without replacement by the non-regenerative mixed bed ion exchange resin apparatus 15.
In addition to the above, the ultrapure water production system 1 may be provided with a reverse osmosis membrane apparatus or an electrodeionization apparatus for removing ionic components, a vacuum degassing apparatus or a membrane degassing apparatus for removing dissolved gas, an ultrafiltration apparatus (UF) or a microfiltration apparatus (MF) for removing fine particles or nonionic components, and the like.
As described above, the present inventors have found that, when a boron-adsorbing anion-exchange mixed bed resin is disposed at the rear stage of an ultraviolet oxidation apparatus, hydrogen peroxide generated by excessive ultraviolet irradiation in the ultraviolet oxidation apparatus decomposes the boron-adsorbing anion-exchange mixed bed resin, whereby a large amount of low-molecular-weight organic matter is eluted, and the TOC removal load in the downstream water treatment apparatus is increased by the low-molecular-weight organic matter. The reason for this is estimated as follows.
When water containing hydrogen peroxide is brought into contact with the boron adsorbent resin having a polyol group as a functional group as described above, the boron adsorbent resin may be decomposed. Hereinafter, the decomposition of the boron-adsorbing resin will be described by taking a boron-adsorbing resin having an N-methylglucamine group as an ion-exchange group in the resin skeleton as an example, with reference to the following formula (I).
As shown in the above formula (I), in the case of the boron adsorption resin having N-methylglucamine groups, the bond is cleaved by hydrogen peroxide in the following 4 cases: (1) a case where a bond between a hydrocarbon chain constituting a resin skeleton such as a polystyrene resin or a phenol resin and a benzene ring is cleaved; (2) the case where N-methylglucamine group is eliminated; (3) a case where a methyl group bonded to a nitrogen atom of the N-methylglucamine group is detached; (4) the polyol group bonded to the nitrogen atom of the N-methylglucamine group is eliminated. In addition, when (4) the polyol group bonded to the nitrogen atom of the N-methylglucamine group is eliminated, it is also considered that a plurality of carbon-carbon bonds included in the polyol are cleaved.
Here, in the case where the bond is cut in any one of (1) to (4) in the boron-adsorbing anion-exchange mixed-bed resin, the desorbed organic component leaks out of the ion-exchange resin layer. The leaked organic matter component can be removed by decomposing the organic acid by ultraviolet irradiation in an ultraviolet oxidation apparatus, and then trapping the organic acid by a non-regenerative mixed bed ion exchange resin.
However, in the case of the organic component produced by cleavage in the above (4), formic acid can be produced in an amount of 5 times the equivalent weight of the desorbed polyol group by irradiation with ultraviolet light in an ultraviolet oxidation apparatus at the maximum. Therefore, it is considered that the load of the non-regenerative mixed bed ion exchange resin apparatus disposed on the downstream side is increased accordingly, and the non-regenerative mixed bed ion exchange resin is extremely deteriorated at an early stage.
In addition, in the boron-adsorbing cation-exchange anion-exchange mixed bed resin, the leaving group generated by the removal of the above (1) and (2) in the boron-adsorbing resin has a nitrogen atom (N) having a + charge+) Therefore, the desorbed organic component is ion-exchanged by the cation exchange resin contained in the boron-adsorbing cation-exchanging anion-exchanging mixed bed resin, and does not leak out of the ion-exchange resin layer. On the other hand, when the bonds are cleaved as in (3) and (4) above, the desorbed organic component is not ion-exchanged by the boron-adsorbing cation-exchanging anion-exchange mixed bed resin, and leaks out of the ion-exchange resin layer.
In addition to the boron adsorption resin, the anion exchange resin may be decomposed by hydrogen peroxide, and for example, in the anion exchange resin having an ion exchange group such as a primary amino group, a secondary amino group, or a tertiary amino group, the organic component may be desorbed. When the decomposition of the anion exchange resin occurs in the boron-adsorbing anion exchange mixed bed resin, the organic component generated by the desorption leaks directly from the ion exchange resin.
However, even when the organic components generated by the decomposition of the anion exchange resin in the boron-adsorbing anion exchange mixed bed resin leak from the ion exchange resin layer, the influence of the leaking organic components on the non-regenerative mixed bed type ion exchange resin in the subsequent stage is extremely small. This is because the molecular weight of the ion exchange groups of the anion exchange resin is smaller than the molecular weight of the ion exchange groups of the boron adsorption resin, and the number of carbon-carbon bonds is also small, and therefore, it is considered that the equivalent of the organic component generated by the decomposition of these is considerably smaller than the equivalent of the organic component generated by the decomposition of the boron adsorption resin.
On the other hand, when the decomposition of the anion exchange resin occurs in the boron-adsorbing cation-exchange anion-exchange mixed bed resin, most of the organic components are nitrogen atoms (N) having a charge of + since the ion exchange groups are directly released+) The component (b) is captured by the cation exchange resin in the ion exchange resin layer, and hardly leaks from the ion exchange resin layer. When decomposition of the cation exchange resin occurs in the boron-adsorbing cation-exchanging anion-exchanging mixed-bed resin, since the ion-exchange groups are directly released and most of the organic components are components having (negative) charges, the boron-adsorbing cation-exchanging mixed-bed resin is captured by the anion exchange resin in the ion-exchange resin layer and hardly leaks out of the ion-exchange resin layer.
From the above-described presumptions, the inventors have found that ultrapure water having a significantly reduced boron concentration and TOC concentration can be produced for a long period of time by controlling the amount of hydrogen peroxide generated in the 1 st ultraviolet oxidation apparatus 12 by adjusting the amount of ultraviolet irradiation in the 1 st ultraviolet oxidation apparatus 12, thereby realizing a high boron removal rate in the boron-adsorbing anion-exchange mixed bed resin and efficiently reducing the load on the non-regenerative mixed bed ion-exchange resin apparatus 15 provided on the downstream side.
(embodiment 2)
Next, referring to fig. 2, the ultrapure water production system 2 of embodiment 2 will be described. The ultrapure water production system 2 is configured to include a reverse osmosis membrane device (RO)21 and an Electrodeionization Device (EDI)22 on the upstream side of the 1 st ultraviolet oxidation device (TOC-UV1) in the ultrapure water production system 1 according to the above-described embodiment 1. In fig. 2, the same reference numerals are given to the components having the same functions as those of the ultrapure water production system 1 shown in fig. 1, and redundant description is omitted.
The reverse osmosis membrane apparatus (RO)21 removes salts, ionic and colloidal organic substances, and the like in the pretreatment water to produce concentrated water and permeated water. As the reverse osmosis membrane device 21, a membrane module made of a sheet-like flat membrane, a spiral membrane, a tubular membrane, or a hollow fiber membrane using a cellulose triacetate asymmetric membrane or a polyamide composite membrane can be used. Among these, a polyamide composite membrane is preferable in terms of improving the removal rate of impurities, and a spiral membrane is preferable in membrane shape.
The water recovery rate of the reverse osmosis membrane device 21 is preferably 50 to 95%, more preferably 60 to 90%, and still more preferably 65 to 85%. The boron removal rate of the reverse osmosis membrane apparatus 21 is preferably 85% or more, and more preferably 90% or more, from the viewpoint of obtaining ultrapure water having an extremely low boron concentration over a long period of time.
The membrane resistance of the reverse osmosis membrane device 21 is preferably 45MPa/(m/h) or more, more preferably 53MPa/(m/h) or more, and still more preferably 60MPa/(m/h) or more. When the membrane resistance of the reverse osmosis membrane apparatus 21 is 45MPa/(m/h) or more, the boron concentration can be maintained at the end for a longer period of time. The film resistance is preferably 200MPa/(m/h) or less. If the membrane resistance is 200MPa/(m/h) or less, the number of reverse osmosis membrane modules included in the reverse osmosis membrane device 21 does not become too large, and the operation can be performed appropriately. Here, the membrane resistance is a value (pressure/flux) of a predetermined supply pressure of pure water with respect to a flux when the pure water is passed through the reverse osmosis membrane device 21. The flux is a value measured by passing pure water at normal temperature (20 ℃. + -. 5 ℃) at a pressure not lower than the designed maximum operating pressure of the reverse osmosis membrane module and not lower than 1/4 which is the designed operating pressure of the reverse osmosis membrane module.
Examples of such a reverse osmosis membrane device 21 include TM820K (film resistance of 120MPa/(m/h)), TM820M (film resistance of 94MPa/(m/h)), TM820V (film resistance of 65MPa/(m/h)), TM820 (film resistance of 55MPa/(m/h)), SU720RB (film resistance of 50MPa/(m/h)) (all manufactured by ori corporation), and SWC4 MAX (film resistance of 72MPa/(m/h), manufactured by nippon electric corporation).
The reverse osmosis membrane apparatus 21 may be configured in a multistage manner by connecting 2 or more reverse osmosis membrane apparatuses in series. In this case, the salt rejection in the reverse osmosis membrane apparatus 21 is increased, and as a result, in the boron-adsorbing resin mixed ion exchange apparatus 13, the load on the boron-adsorbing anion-exchange mixed bed resin or the boron-adsorbing cation-exchange mixed bed resin can be reduced, and therefore, the boron removal capacity can be improved. When the reverse osmosis membrane apparatus 21 is configured in multiple stages, it is preferable to use a 2-stage reverse osmosis membrane apparatus.
An Electrodeionization (EDI) unit 22 performs ion exchange treatment on the permeate water from the reverse osmosis membrane unit 21 to remove ionic components in the water. The electrodeionization device 22 is configured to fill a gap formed by the anion exchange membrane and the cation exchange membrane with an ion exchanger to form a desalting chamber and a concentrating chamber, and to apply a direct current to remove ions in the water to be treated. As the electrodeionization device 22, commercially available products such as MK-3 series (manufactured by E-Cell) and VNX series (manufactured by IONPURE) can be used. The water recovery rate of the electrodeionization device 22 is preferably 80 to 98%. The number of the electrodeionization devices 22 may be 1 for a single stage, or 2 or more may be connected in series and used in multiple stages.
In the ultrapure water production system 2 of the present embodiment, the end water quality can be improved by adjusting the current value in the Electrodeionization Device (EDI) 22. The current value (A value) per 1 unit of the treatment flow rate in the electrodeionization device 22 is preferably 30A/(m)3H) or more, more preferably 40A/(m)3H) or more, and more preferably 60A/(m)3H) above. The current value for the treatment flow rate per 1 unit in the electrodeionization device 22 was 30A/(m)3H) or more, a low boron concentration can be maintained at the end for a longer time. The value of A is preferably 300A/(m) from the viewpoint that the power consumption does not become excessive3H) below. It should be noted that 1 unit pair process flow is per unitThe treatment flow rate of 1 cell pair is the supply flow rate (m) at which the water to be treated can be supplied to the electrodeionization device 223And/h) is obtained by dividing by the number (number of cells) of combinations (pairs) of anion-exchange membranes and cation-exchange membranes included in the electrodeionization device 22.
The boron removal rate in the electrodeionization device 22 is preferably 90% or more, and more preferably 95% or more, from the viewpoint of obtaining ultrapure water having an extremely low boron concentration over a long period of time.
In this manner, the water treated by the reverse osmosis membrane apparatus 21 and the electrodeionization apparatus 22 is passed through the boron-adsorbing resin mixed ion exchange apparatus 13, the 2 nd ultraviolet oxidation apparatus 14, and the non-regenerative mixed bed ion exchange resin apparatus 15 in this order, and boron and TOC components remaining in the water are removed. The preferred embodiments and water passing conditions of the boron-adsorbing resin mixed ion exchange device 13, the 2 nd ultraviolet oxidation device 14, and the non-regenerative mixed bed ion exchange resin device 15 are the same as those of the above-described embodiment 1.
In the ultrapure water production system 2, the water passing through the reverse osmosis membrane apparatus 21 and the electrodeionization apparatus 22 is subjected to a1 st ultraviolet oxidation apparatus at a rate of 0.05 to 0.2kWh/m3Since ultraviolet rays are irradiated, decomposition of the mixed bed resin packed in the boron adsorbent resin mixed ion exchanger 13 is suppressed, and the TOC concentration in the treated water of the boron adsorbent resin mixed ion exchanger 13 can be, for example, 0.6. mu.g/L (expressed as C) or less. As a result, ultrapure water having a TOC concentration of 0.5. mu.g/L (as C) or less and a boron concentration of 1ng/L or less can be produced as the treated water of the non-regenerative mixed bed ion exchange resin apparatus 15 over a long period of time of, for example, 1 month, preferably 1 year. Ultrapure water having a TOC concentration of preferably 0.4. mu.g/L (expressed as C) or less, more preferably 0.2. mu.g/L (expressed as C) or less can be produced over a long period of time. Further, ultrapure water having a boron concentration of preferably 0.7ng/L or less, more preferably 0.5ng/L or less can be produced over a long period of time.
Examples
Next, examples will be described.
(Experimental example)
Differences in load on the non-regenerative mixed bed ion exchange resin apparatus in the subsequent stage due to the leakage of TOC components were observed for the boron adsorption resin (B), the anion exchange resin (a), the cation exchange anion exchange mixed bed resin (MB), and the boron adsorption cation exchange anion exchange mixed bed resin (BMB).
An ultraviolet oxidation apparatus (TOC-UV) and a non-regenerative mixed bed ion exchange resin apparatus (Polisher) were disposed in this order on the downstream side of the apparatus packed with the boron adsorption resin, and as an acceleration test, test water having a hydrogen peroxide concentration of 200. mu.g/L was supplied to the boron adsorption resin at a space velocity SV of 13 (1/h). Test water was prepared by adding hydrogen peroxide to pure water.
The change with time of the TOC concentration (terminal TOC concentration) of the treated water in the non-regenerative mixed bed ion exchange resin apparatus after the test water was passed was examined. The results are shown in fig. 3.
In the case where the boron adsorption resin was changed to an anion exchange resin, a cation exchange anion exchange mixed bed resin, or a boron adsorption cation exchange anion exchange mixed bed resin, test water was passed through the apparatus in the same manner as described above, and the change with time in the TOC concentration (end TOC concentration) of the treated water in the non-regenerative mixed bed ion exchange resin apparatus was examined. The results are shown in fig. 3.
The specifications and water passing conditions of the respective apparatuses (resins) used in the present experimental example are as follows.
Boron adsorption resin (B): using DIAION CRB03, Mitsubishi chemical (K.K.), exchange Capacity: 3.8L at 0.8eq/L, space velocity SV 13.2(1/h), flow rate 50L/h.
Anion exchange resin (a): 2.8L of strongly basic anion exchange resin (Duolite AGP, manufactured by Rohm and Haas company, exchange capacity: 1.1eq/L), SV 18(1/h), and 50L/h of flow rate were used.
Cation exchange anion exchange mixed bed resin (MB): a mixture of 0.8L of a strongly acidic cation exchange resin (Duolite CGP, manufactured by Rohm and Haas Company, exchange capacity: 2.0eq/L) and 2.8L of a strongly basic anion exchange resin (Duolite AGP, manufactured by Rohm and Haas Company, exchange capacity: 1.1eq/L) was used, and the space velocity SV was 14(1/h) and the flow rate was 50L/h.
Boron adsorption cation exchange anion exchange mixed bed resin (BMB): the boron adsorption resin, the strongly basic anion exchange resin and the strongly basic anion exchange resin are used in an exchange capacity ratio (C) expressed by the boron adsorption resin/the strongly basic anion exchange resinC/CA/CB) The resin obtained by mixing 5.6/10.6/3.0 was 16.2L, the space velocity SV was 3.2(1/h), and the flow rate was 50L/h.
Non-regenerative mixed bed ion exchange resin apparatus: resins obtained by mixing Duolite CGP, manufactured by Rohm and Haas Company, Duolite AGP, manufactured by Rohm and Haas Company, in equal amounts in terms of exchange capacity, were used, and the resin amount was 1L, the space velocity SV was 50(1/h), and the flow rate was 50L/h.
As shown in fig. 3, it is known that: when test water containing hydrogen peroxide is passed through the boron adsorption resin, the deterioration of the non-regenerative mixed bed ion exchange resin apparatus on the downstream side proceeds earlier than with the anion exchange resin or the cation exchange anion exchange mixed bed resin.
(examples 1 to 6)
In examples 1 to 6, the relationship between the amount of ultraviolet irradiation and the terminal TOC concentration in the 1 st ultraviolet oxidation apparatus (TOC-UV1) was examined using the same configuration as that shown in FIG. 1. Examples 2 to 5 are examples, and examples 1 and 6 are comparative examples.
A1 st ultraviolet oxidation apparatus, a boron adsorption cation exchange anion exchange mixed bed resin apparatus, a 2 nd ultraviolet oxidation apparatus, and a non-regenerative mixed bed ion exchange resin apparatus were disposed in this order. The following devices were used for each device.
Boron adsorption cation exchange anion exchange mixed bed resin device: a resin 25L obtained by mixing the same resins as those used in the above experimental examples at the same ratio was packed in a resin column, and SV was 30 (1/h).
The 1 st ultraviolet oxidation apparatus and the 2 nd ultraviolet oxidation apparatus: PHOTOSCIENCE JAPAN CORP, JPW-2.
Non-regenerative mixed bed ion exchange resin apparatus: in the same apparatus as in the above experimental example, SV is 30 (1/h).
The TOC concentration (end TOC concentration) of the treated water in the non-regenerative mixed bed ion exchange resin apparatus was examined by changing the amount of ultraviolet irradiation in the 1 st ultraviolet oxidation apparatus as shown in Table 1 and passing the treated water for 1 year. The results are shown in table 1 and fig. 4. The water quality of the water to be treated was such that the TOC concentration was 100. mu.g/L (as C), the boron concentration was 60. mu.g/L, and the conductivity was 70. mu.S/cm.
In the same manner as described above, the TOC concentration (end TOC concentration) of the treated water in the non-regenerative mixed bed ion exchange resin apparatus was examined when the treated water was passed through the apparatus for 1 month. The results are shown in table 1 and fig. 5.
Further, the hydrogen peroxide concentration of the treated water of the 1 st ultraviolet oxidation apparatus at the beginning of water passage was measured, and the relationship between the ultraviolet irradiation amount and the hydrogen peroxide generation amount in the 1 st ultraviolet oxidation apparatus was examined. The results are shown in table 1 and fig. 6.
[ Table 1]
Examples 7 to 16 (examples)
In examples 7 to 16, the relationship between the treatment conditions in the reverse osmosis membrane apparatus (RO) and the electrodeionization apparatus (EDI) and the quality of the treated water (end water quality) in the non-regenerative mixed bed ion exchange resin apparatus was examined using the same configuration as that shown in fig. 2. On the upstream side of the 1 st ultraviolet oxidation apparatus having the configuration used in the above example, a reverse osmosis membrane apparatus and an electrodeionization apparatus were disposed in this order. The raw water had a TOC concentration of 200. mu.g/L (as C), a boron concentration of 100. mu.g/L and an electric conductivity of 150. mu.S/cm.
The ultraviolet ray irradiation amount in the 1 st ultraviolet ray oxidation apparatus (TOC-UV1) was set to 0.09 kW.h/m3The water to be treated was supplied to a reverse osmosis membrane apparatus (TM820K, manufactured by toray corporation). The permeate water of the reverse osmosis membrane apparatus was passed through an electrodeionization apparatus (manufactured by VNX, ion pure), a boron adsorption resin mixed ion exchange apparatus, and a non-regenerative mixed bed ion exchange resin apparatus in this order.
As boronAdsorbent resin hybrid ion exchange apparatus 30L of the same boron adsorbent resin, strongly basic anion exchange resin and strongly acidic cation exchange resin as used in the above experimental examples were packed in a resin column at an exchange capacity ratio CC/CA/CB＝5.6/10.6/3.0(CC/(CA+CB) 0.41) was mixed and the obtained boron was used while adsorbing a cation-exchange anion-exchange mixed bed resin.
At this time, the current supplied to the electrodeionization device was changed, the value of a was adjusted as shown in table 2, and the treated water was passed through each of the devices, and the TOC concentration and the boron (B) concentration of the treated water in the non-regenerative mixed bed ion exchange resin device after 1 month and 1 year were examined. The results are shown in table 2.
Further, the hydrogen peroxide concentration of the treated water in the 1 st ultraviolet oxidation apparatus at the beginning of the water passage of the treated water, the membrane resistance and the boron (B) removal rate in the reverse osmosis membrane apparatus, and the boron (B) removal rate in the electrodeionization apparatus were measured. The boron (B) removal rate is a value calculated by {1- (boron concentration in permeated water/boron concentration in supplied water) } × 100 (%). The results are shown in table 2.
Next, the ultraviolet irradiation amount in the 1 st ultraviolet oxidation apparatus was set to 0.09 kW.h/m3The A value of the electrodeionization device was set to 80A/(m)3And/h) supplying the water to be treated to the reverse osmosis membrane apparatus in the same manner as described above.
As the reverse osmosis membrane apparatus, apparatuses having different membrane resistances were used, and the TOC concentration and the boron (B) concentration of the treated water in the non-regenerative mixed bed ion exchange resin apparatus after 1 month and after 1 year were examined. The results are shown in table 3.
The results of measuring the hydrogen peroxide concentration of the treated water in the 1 st ultraviolet oxidation apparatus, the membrane resistance and the boron (B) removal rate in the reverse osmosis membrane apparatus, and the boron (B) removal rate in the electrodeionization apparatus, at the beginning of the water passage of the treated water, are shown in table 3.
The reverse osmosis membrane apparatus used is as follows.
TM820K (film resistance 120MPa/(m/h)), TM820M (film resistance 94MPa/(m/h)), TM820V (film resistance 65MPa/(m/h)), TM820 (film resistance 55MPa/(m/h)), SU720RB (film resistance 50MPa/(m/h)), SUL-G20P (film resistance 40MPa/(m/h)) (all manufactured by Toray corporation), SWC4 MAX (film resistance 72MPa/(m/h), manufactured by Rido electrician)
In each example, the TOC concentration was measured by a TOC concentration meter (manufactured by Anatel corporation, Anatel a1000 XP), the boron concentration was measured by an inductively coupled plasma mass spectrometer (ICP-MS) apparatus, and the hydrogen peroxide concentration was measured by Noxia (manufactured by Nomura Micro Science co.
[ Table 2]
[ Table 3]
Description of the symbols
1.2 ultrapure water production system, 11 pretreatment apparatus, 12 st ultraviolet oxidation apparatus (TOC-UV1), 13 boron adsorption resin mixed ion exchange apparatus, 14 nd ultraviolet oxidation apparatus (TOC-UV1), 15 non-regenerative mixed bed type ion exchange resin apparatus (Polisher), 16 point of use (POU), 21 reverse osmosis membrane apparatus (RO), 22 electrodeionization apparatus (EDI).
Claims (10)
1. An ultrapure water production system for producing ultrapure water by treating water to be treated containing a boron component and a total organic carbon component, comprising in this order:
the treated water was treated at 0.05kWh/m3～0.2kWh/m3The 1 st ultraviolet oxidation device for irradiating ultraviolet rays with the ultraviolet irradiation amount of (1);
a boron-adsorbing resin mixed ion exchange unit which has a boron-adsorbing anion-exchange mixed bed resin obtained by mixing a boron-adsorbing resin and an anion-exchange resin, and which treats the water to be treated which has been irradiated with ultraviolet light by the ultraviolet ray oxidation unit 1;
a 2 nd ultraviolet ray oxidation device for irradiating the water to be treated by the boron adsorption resin mixed ion exchange device with ultraviolet rays; and
a non-regenerative mixed bed ion exchange resin apparatus for treating the water to be treated which has been irradiated with ultraviolet rays by the 2 nd ultraviolet ray oxidation apparatus.
2. The system for producing ultrapure water according to claim 1, wherein regarding the mixing ratio of the boron adsorption resin and the anion exchange resin in the boron adsorption anion exchange mixed bed resin, the exchange capacity of the anion exchange resin is set to "CA", wherein the exchange capacity of the boron-adsorbing resin is" CB”，CA/CB0.2 to 5.
3. The system for producing ultrapure water according to claim 1 or 2, wherein the boron-adsorbing-resin mixed ion exchange device comprises a boron-adsorbing cation-exchange mixed bed resin obtained by further mixing a cation-exchange resin with the boron-adsorbing anion-exchange mixed bed resin.
4. The ultrapure water production system according to claim 3, wherein regarding the mixing ratio of the boron adsorption resin, the anion exchange resin and the cation exchange resin in the boron adsorption cation exchange mixed bed resin, the exchange capacity of the anion exchange resin is set to "CA", wherein the exchange capacity of the boron-adsorbing resin is" CB", wherein the exchange capacity of the cation exchange resin is" CC”，CC/(CA+CB) 0.3 to 1.3.
5. The system for producing ultrapure water according to any one of claims 1 to 4, wherein a reverse osmosis membrane device and an electrodeionization device are provided in this order on the upstream side of the 1 st ultraviolet oxidation device.
6. The ultrapure water production system according to claim 5, wherein the electric current value per 1 unit of the treatment flow rate in the electrodeionization device is 30A/(m)3H) above.
7. The system for producing ultrapure water according to claim 5 or 6, wherein the membrane resistance in the reverse osmosis membrane device is 45MPa/(m/h) or more.
8. The system for producing ultrapure water according to any one of claims 1 to 7, wherein the total organic carbon concentration in the treated water of the boron-adsorbing resin mixed ion exchange device is 5 μ g/L or less in terms of C.
9. The system for producing ultrapure water according to any one of claims 1 to 8, wherein the total organic carbon concentration in the treated water of the non-regenerative mixed bed type ion exchange resin apparatus is less than 0.5 μ g/L in terms of C and the boron concentration is less than 0.5 ng/L.
10. A method for producing ultrapure water, which comprises treating water to be treated containing a boron component and a total organic carbon component to produce ultrapure water, comprising:
the ultraviolet ray irradiation amount was set to 0.05kWh/m by the 1 st ultraviolet ray oxidation apparatus3～0.2kWh/m3Treating the water to be treated;
a step of treating the treated water of the 1 st ultraviolet oxidation apparatus by a boron adsorption resin mixed ion exchange apparatus having a boron adsorption anion exchange mixed bed resin obtained by mixing a boron adsorption resin and an anion exchange resin;
treating the treated water of the boron adsorption resin mixed ion exchange device by a 2 nd ultraviolet oxidation device; and
and (3) treating the treated water of the 2 nd ultraviolet oxidation apparatus by a non-regenerative mixed bed ion exchange resin apparatus.
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| JP2017-088793 | 2017-04-27 | ||
| JP2017088793A JP2018183761A (en) | 2017-04-27 | 2017-04-27 | Ultrapure water production system and method |
| PCT/JP2018/014702 WO2018198723A1 (en) | 2017-04-27 | 2018-04-06 | Ultrapure water production system and ultrapure water production method |
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| CN112759031A (en) * | 2020-12-17 | 2021-05-07 | 苏州业华环境科技有限公司 | Ultrapure water treatment process and system |
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| JP7289206B2 (en) * | 2019-03-13 | 2023-06-09 | オルガノ株式会社 | Boron removal device, boron removal method, pure water production device, and pure water production method |
| JP6806202B1 (en) * | 2019-08-15 | 2021-01-06 | 栗田工業株式会社 | Prediction method of fine particle breakage time of non-renewable ion exchange resin device and management method of non-regenerative ion exchange resin device |
| JP7368310B2 (en) * | 2020-05-20 | 2023-10-24 | オルガノ株式会社 | Boron removal equipment and boron removal method, and pure water production equipment and pure water production method |
| JP2022026049A (en) * | 2020-07-30 | 2022-02-10 | オルガノ株式会社 | Pure water producing apparatus and ultrapure water producing apparatus, and pure water producing method and ultrapure water producing method |
| CN112279435A (en) * | 2020-10-29 | 2021-01-29 | 天津城建大学 | Combined device and method for producing high-quality condensed water |
| CN112657560B (en) * | 2020-12-11 | 2021-12-28 | 安徽三星树脂科技有限公司 | Efficient and environment-friendly polishing cation resin production system and production process |
| JP2023127080A (en) * | 2022-03-01 | 2023-09-13 | オルガノ株式会社 | Ultrapure water production system and ultrapure water production method |
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| JP6029948B2 (en) * | 2012-11-21 | 2016-11-24 | 野村マイクロ・サイエンス株式会社 | Pure water production method and pure water production system |
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| JP2002263643A (en) * | 2001-03-12 | 2002-09-17 | Kurita Water Ind Ltd | Apparatus for manufacturing ultra pure water |
| JP2004025184A (en) * | 2003-10-06 | 2004-01-29 | Nomura Micro Sci Co Ltd | Ultra-pure water making apparatus |
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| CN112759031A (en) * | 2020-12-17 | 2021-05-07 | 苏州业华环境科技有限公司 | Ultrapure water treatment process and system |
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| JP2018183761A (en) | 2018-11-22 |
| WO2018198723A1 (en) | 2018-11-01 |
| TW202200508A (en) | 2022-01-01 |
| TW201841837A (en) | 2018-12-01 |
| KR20190141208A (en) | 2019-12-23 |
| TWI754042B (en) | 2022-02-01 |
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