CN109906206B - Water treatment method and apparatus - Google Patents
Water treatment method and apparatus Download PDFInfo
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- CN109906206B CN109906206B CN201780067211.9A CN201780067211A CN109906206B CN 109906206 B CN109906206 B CN 109906206B CN 201780067211 A CN201780067211 A CN 201780067211A CN 109906206 B CN109906206 B CN 109906206B
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
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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
- C02F1/30—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
-
- 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
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/22—O2
Abstract
A water treatment apparatus for performing decomposition treatment of organic substances contained in water to be treated, which apparatus is provided with: a hydrogen peroxide adding device for adding hydrogen peroxide to water to be treated; an ultraviolet irradiation device for irradiating the water to be treated added with hydrogen peroxide with ultraviolet rays; a dissolved oxygen measuring unit that measures a dissolved oxygen concentration of outlet water of the ultraviolet irradiation device; and a control unit that controls the amount of hydrogen peroxide added according to the dissolved oxygen concentration measured by the dissolved oxygen measurement unit.
Description
Technical Field
The present invention relates to a water treatment method and apparatus for decomposing organic substances contained in water to be treated, which is water to be treated.
Background
Conventionally, pure water such as ultrapure water from which organic substances, ionic components, fine particles, bacteria, and the like have been highly removed has been used as cleaning water and the like used in a process for manufacturing a semiconductor device or a process for manufacturing a liquid crystal display device. In particular, in the production of electronic parts including semiconductor devices, a large amount of pure water is used in the cleaning process, and the demand for water quality is increasing year by year. Pure water used in a cleaning process or the like for electronic component production is required to have a very low Total Organic Carbon (TOC) concentration, which is one of water quality control items, in order to prevent carbonization of Organic substances contained in the pure water in a subsequent heat treatment process and the like, which may cause insulation failure or the like.
With the high demand for pure water quality becoming apparent, various methods for decomposing and removing trace organic substances (TOC components) contained in pure water have been studied in recent years. As a representative method of such a method, an organic substance decomposition and removal step by ultraviolet ray oxidation treatment is used.
In general, when organic substances are decomposed and removed by ultraviolet ray oxidation treatment, for example, water to be treated is introduced into a reaction tank and ultraviolet rays are irradiated to the water to be treated using an ultraviolet ray oxidation apparatus including a stainless steel reaction tank and a tubular ultraviolet lamp provided in the reaction tank. As the ultraviolet lamp, for example, a low-pressure ultraviolet lamp which generates ultraviolet rays having respective wavelengths of 254nm and 185nm is used. When the water to be treated is irradiated with ultraviolet rays having a wavelength of 185nm, oxidizing species such as hydroxyl radicals (. OH) are generated in the water to be treated, and the oxidizing ability of the oxidizing species causes a trace amount of organic substances in the water to be treated to be decomposed into carbon dioxide and organic acids. The treated water obtained by subjecting the water to be treated to the ultraviolet oxidation treatment as described above is then sent to an ion exchange device disposed at a subsequent stage, and carbon dioxide and organic acids are removed.
However, in the oxidation and decomposition method of TOC in a general ultraviolet oxidation apparatus, an ultraviolet lamp is used, but the ultraviolet lamp is very expensive, and the ultraviolet intensity is reduced with the lapse of a usage period, and thus, for example, replacement of about 1 time per 1 year is required. Therefore, in the TOC oxidative decomposition treatment using the ultraviolet oxidation apparatus, there is a problem of suppressing the running cost such as reduction of the replacement cost of the ultraviolet lamp and reduction of the energy consumption amount.
In order to improve the TOC decomposition efficiency, for example, patent document 1 proposes a water treatment apparatus in which a dissolved oxygen concentration adjustment step of adding oxygen to water to be treated is provided in a stage preceding a low-pressure ultraviolet oxidation apparatus as a water treatment apparatus for removing TOC in water to be treated using the low-pressure ultraviolet oxidation apparatus. The low-pressure ultraviolet oxidation apparatus is an oxidation apparatus using a low-pressure ultraviolet lamp. Further, patent document 2 proposes adding a predetermined amount of hydrogen peroxide (H) to the water to be treated in a stage preceding the low-pressure ultraviolet oxidation apparatus2O2) The scheme (2).
However, in recent years, water saving is strongly desired also in semiconductor factories and the like that use large amounts of ultrapure water in order to cope with depletion and deterioration of water resources. In order to achieve water saving, it is effective to recover and reuse water once used, and in order to improve the water recovery rate, for example, a technique of treating and then recovering wastewater having a high TOC concentration after use at a point of use has been studied. Such a technique is also generally called a wastewater treatment technique, a wastewater recovery treatment technique, or the like. In order to recover and reuse the wastewater having a high TOC concentration as raw water for producing ultrapure water, it is necessary to reduce the TOC concentration to a level at which the quality of the ultrapure water at the end is not deteriorated without increasing energy costs. As a technique for treating water to be treated having a high TOC concentration, there is a technique of adding hydrogen peroxide or ozone (O) to the water to be treated3) Oxidizing agent, etc., and oxidizing and decomposing TOC by ultraviolet irradiation. In this case, the TOC concentration of the water to be treated is assumed to be of the order of mg/L, and the water to be treated which originally contains a large amount of various impurities is targeted, and therefore, for example, ultraviolet irradiation is performed using a reaction vessel of an open system. Further, as the ultraviolet source, a low-pressure ultraviolet lamp or a high-pressure ultraviolet lamp which generates a wavelength of 254nm is generally used.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-
Patent document 2: japanese patent laid-open publication No. 2011-
Patent document 3: japanese laid-open patent publication No. 5-305297
Disclosure of Invention
Problems to be solved by the invention
In order to decompose and remove TOC components in water to be treated, it is common to perform a treatment of irradiating ultraviolet rays to oxidize TOC components, but it cannot be said that the technology used up to now is always optimal from the viewpoint of removing a large amount of TOC in water to be treated. In particular, as shown in patent document 2, when the ultraviolet oxidation treatment is performed after hydrogen peroxide is added, it cannot be said that sufficient studies have been made on the influence of factors other than the amount or concentration of hydrogen peroxide on the TOC removal rate. Therefore, when attempting to increase the TOC removal rate of the water to be treated, the ultraviolet irradiation amount is excessively increased, and there are problems that the required power amount becomes large, the energy cost rises, and the apparatus scale also becomes large.
An object of the present invention is to provide a water treatment method and apparatus which can reduce the size of the apparatus, suppress the running cost including the energy cost, and improve the decomposition efficiency of organic substances.
Means for solving the problems
The present inventors have found that, when decomposition treatment of organic substances in water to be treated is performed by ultraviolet irradiation with hydrogen peroxide added thereto, there is a correlation between the dissolved oxygen concentration after the ultraviolet oxidation treatment and the TOC removal rate and the amount of hydrogen peroxide added, and that the amount of hydrogen peroxide added can be controlled to an optimum relationship, thereby completing the present invention. That is, the water treatment method of the present invention is a water treatment method for decomposing organic substances contained in water to be treated, including: a hydrogen peroxide addition step of adding hydrogen peroxide to the water to be treated; an ultraviolet irradiation step of irradiating the water to be treated to which hydrogen peroxide is added with ultraviolet rays; and a step of measuring the dissolved oxygen concentration of the outlet water from the ultraviolet irradiation step, wherein the amount of hydrogen peroxide added in the hydrogen peroxide addition step is controlled according to the measured dissolved oxygen concentration.
The water treatment apparatus of the present invention is a water treatment apparatus for decomposing organic substances contained in water to be treated, and includes: a hydrogen peroxide adding device for adding hydrogen peroxide to water to be treated; an ultraviolet irradiation device that irradiates water to be treated, to which hydrogen peroxide is added, with ultraviolet rays; a dissolved oxygen measuring unit that measures a dissolved oxygen concentration of outlet water of the ultraviolet irradiation device; and a control unit that controls the amount of hydrogen peroxide added in the hydrogen peroxide addition device in accordance with the dissolved oxygen concentration measured by the dissolved oxygen measurement unit.
Effects of the invention
According to the present invention, the decomposition efficiency of organic matter in water to be treated can be improved to realize a high TOC removal rate, thereby achieving a reduction in the size of the apparatus and a reduction in the running cost.
Drawings
Fig. 1 is a diagram showing a basic configuration of a water treatment apparatus according to the present invention.
Fig. 2 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 3 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 4 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 5 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 6 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 7 is a diagram showing another configuration example of the water treatment apparatus.
Fig. 8 is a diagram showing an application example of the water treatment apparatus according to the present invention.
Fig. 9 is a diagram showing the structure of the apparatus used in the example.
Detailed Description
Next, preferred embodiments of the present invention will be described with reference to the drawings.
Fig. 1 is a diagram showing a basic structure of a water treatment apparatus according to the present invention. The water treatment apparatus shown in fig. 1 includes: a hydrogen peroxide adding device 20 for adding hydrogen peroxide (H) to the water to be treated2O2) (ii) a An ultraviolet irradiation device 30 connected to an outlet of the hydrogen peroxide addition device 20, for irradiating the water to be treated to which hydrogen peroxide is added with ultraviolet rays; a dissolved oxygen meter (DO meter) 41 which is a dissolved oxygen measuring means for measuring the dissolved oxygen concentration of the outlet water of the ultraviolet irradiation device 30; and a control device 40 for controlling H to the water to be treated based on the dissolved oxygen concentration measured by the DO meter 412O2A control means for controlling the amount of addition of (1). The hydrogen peroxide adding device 20 is provided with a storage H2O2The storage tank 21 and the pulse control type pump 22 connected to the outlet of the storage tank 21, wherein the pulse of the pump 22 is controlled by a signal from the control device 40, and H is mixed with the water to be treated2O2. The controller 40 receives the measurement result of the dissolved oxygen from the DO meter 41, and based on the measurement result, sends a signal for controlling the pulse of the pump 22 in the hydrogen peroxide adding apparatus 20, and outputs the signal to the hydrogen peroxide adding apparatus 20.
As shown in the examples described later, the inventors of the present invention have found that: in pair adding H2O2When the water to be treated is subjected to the ultraviolet oxidation treatment, the TOC removal rate is affected by the concentration of dissolved oxygen in the water; and the concentration of dissolved oxygen and TOC removal rate after the ultraviolet ray oxidation treatment, H2O2There is a correlation between the amounts of addition of (c). In particular, it was found that: in the presence of H2O2However, when the amount added is small, H is not particularly limited2O2The amount of (c) is so large that the dissolved oxygen concentration after the ultraviolet oxidation treatment is kept small; and in increasing H2O2When the amount of (3) is added, the TOC removal rate is not always increased when the dissolved oxygen concentration after the ultraviolet ray oxidation treatment exceeds a certain value. Therefore, the control device 40 preferably controls the hydrogen peroxide adding device 20 so that H is added to the water to be treated in a range where the concentration of dissolved oxygen in the outlet water of the ultraviolet irradiation device 30 does not exceed, for example, 0.1mg/L2O2。
The ultraviolet irradiation device 30 is preferably an ultraviolet oxidation device that performs ultraviolet oxidation by irradiating ultraviolet rays containing components having wavelengths of 185nm or less. In the water treatment apparatus shown in fig. 1, the outlet water from the ultraviolet irradiation device 30 is treated by the water treatment apparatus and supplied to the outside.
In the presence of H2O2In a conventional water treatment apparatus for performing an ultraviolet irradiation treatment, a germicidal lamp or a high-pressure mercury lamp that emits ultraviolet rays having a wavelength of 254nm is generally used as an ultraviolet irradiation apparatus for the ultraviolet irradiation treatment. The system described in patent document 2 is a system for producing ultrapure water by a cyclic purification treatment in which H is added to water to be treated using a low-pressure ultraviolet oxidation apparatus that generates ultraviolet rays containing a component having a wavelength of 185nm2O2Then, ultraviolet ray oxidation treatment is performed. Ultraviolet radiation having a wavelength of 185nm is generally generated by a low pressure mercury lamp, which also generates ultraviolet radiation having a wavelength of 254 nm. The ratio is about 1: 9 in terms of intensity ratio, and the intensity of one of the components having a wavelength of 254nm is greater. Ultraviolet rays having a wavelength of 185nm have an advantage of being able to directly decompose organic substances, although they have low intensity. On the other hand, ultraviolet rays having a wavelength of 254nm and H2O2The reaction generates hydroxyl radicals (. OH), thereby decomposing the organic substances. In the ultraviolet irradiation device used in the water treatment apparatus according to the present invention, a mercury lamp that generates two types of ultraviolet rays having a wavelength of 185nm and a wavelength of 254nm is used as the ultraviolet source, for example, but other ultraviolet sources, such as an ultraviolet LED (light emitting diode), may be used.
However, when the dissolved oxygen concentration of the water to be treated is high, if the dissolved oxygen concentration in the outlet water of the ultraviolet irradiation device 30 is desired to be, for example, 0.1mg/L or less, a sufficient amount of H required for the decomposition of organic substances cannot be added2O2As a result, the TOC removal rate may not be increased. In this case, it is preferable to provide a deoxidation apparatus for reducing the dissolved oxygen concentration of the water to be treated in a stage before the hydrogen peroxide addition apparatus 20. The water treatment apparatus shown in FIG. 2 is the water treatment apparatus shown in FIG. 1, wherein an ultraviolet ray oxidation apparatus 31 for generating ultraviolet rays containing a component having a wavelength of 185nm is used as an ultraviolet ray irradiation apparatus 30 for performing ultraviolet ray oxidation treatment, and a hydrogen oxide adding apparatusThe device of the deoxidation device 20 is arranged at the front stage of the device 20. The deoxidation apparatus 10 is only required to remove oxygen (O) dissolved in water2) Any apparatus may be used, and for example, any of a vacuum degasser, a membrane degasser, and a nitrogen degasser may be used. The vacuum degasifier, the membrane degasifier, and the nitrogen degasifier are preferable in that the dissolved oxygen concentration in water can be reduced and the concentration in water can be reduced by removing volatile organic compounds, carbonic acid, and the like in a gas phase. As another deoxidation apparatus, hydrogen (H) added may be used2) And then removing oxygen by reacting oxygen with hydrogen over a palladium (Pd) catalyst to form water.
The concentration of dissolved oxygen in water is about 7-8 mg/L when saturated under atmospheric pressure. Even if ultrapure water has a low dissolved oxygen concentration, oxygen is immediately dissolved when exposed to the atmosphere, and the dissolved oxygen concentration rises. Therefore, the dissolved oxygen concentration in the effluent discharged from the various steps is generally more than 1mg/L, and in many cases, is a value close to the saturation level under atmospheric pressure. According to the findings of the present inventors, if the dissolved oxygen concentration exceeds 1mg/L, H is added even if2O2The TOC removal rate was not necessarily improved by the ultraviolet oxidation treatment. Therefore, in the water treatment apparatus according to the present invention, when the deoxidation apparatus 10 is provided, the dissolved oxygen concentration of the outlet water of the deoxidation apparatus 10 is preferably 1mg/L or less. Since dissolved oxygen absorbs ultraviolet rays, when the dissolved oxygen concentration is high, the amount of ultraviolet rays that should be originally used for the decomposition reaction of organic substances is reduced, and it is difficult to advance the decomposition of organic substances. On the other hand, by removing dissolved oxygen to some extent, the influence of ultraviolet absorption can be reduced. As a result, the ultraviolet rays efficiently react with the organic substances, and the TOC removal rate is improved. In addition, by ultraviolet rays and H2O2The reaction is efficiently carried out to generate hydroxyl radicals, so that the hydroxyl radicals react with organic matters, and the TOC removal rate is improved. Therefore, the dissolved oxygen concentration of the outlet water of the deoxidation apparatus 10 is set to 1mg/L or less, and the saturation amount under atmospheric pressure is set to 1/10 or less as a referenceThe effects of the present invention are more remarkably exhibited. More preferably, the dissolved oxygen concentration of the outlet water of the deoxidation apparatus 10 is set to 0.5mg/L or less, and still more preferably 0.1mg/L or less. Although it is also possible to reduce the dissolved oxygen to an extremely low concentration, for example, μ g/L, even if the deoxidation treatment is performed to a high degree, on the order of μ g/L, the TOC removal performance obtained does not vary greatly. In view of cost efficiency including the cost required for the deoxidation treatment and the TOC removal rate, it is preferable that the dissolved oxygen concentration of the outlet water of the deoxidation apparatus 10 is 0.05mg/L or more and 1mg/L or less.
Fig. 3 shows another configuration example of the water treatment apparatus according to the present invention. The water treatment apparatus according to the present invention is an apparatus for decomposing TOC components in water to be treated by ultraviolet oxidation treatment to remove TOC, but in the case where the TOC concentration in the water to be treated is high, the load of the ultraviolet oxidation treatment becomes excessive, and therefore it is preferable to add H before the ultraviolet oxidation treatment, specifically, before the ultraviolet oxidation treatment is performed2O2Previously, the TOC of treated water was reduced. Water treatment apparatus shown in fig. 3 in the water treatment apparatus shown in fig. 2, a reverse osmosis apparatus 15 is provided in a stage preceding the deoxidation apparatus 10. The treated water is first fed to the reverse osmosis unit 15, where TOC is reduced, and then to the deoxygenator unit 10. As a result, the water treatment apparatus shown in fig. 3 can reduce the load of TOC removal in the ultraviolet oxidation apparatus 31. As the reverse osmosis apparatus 15, a multistage treatment apparatus provided with reverse osmosis membranes in multiple stages is preferably used. By using a reverse osmosis membrane provided in multiple stages, TOC can be further eliminated, and the load of ultraviolet oxidation treatment can be reduced.
As the reverse osmosis membrane provided in the reverse osmosis apparatus 15, a reverse osmosis membrane having high TOC removal ability and high rejection rate used for desalination of seawater or the like is preferably used. In particular, it is characterized by a permeation flux of 0.5m per 1MPa of effective pressure3/m2And/d is as follows. Examples of the reverse osmosis membrane that can be used in the water treatment apparatus according to the present invention include SWC membranes manufactured by Hydranautics, TM800 membranes manufactured by Toray, SW30 membranes manufactured by DOW, and HR-RO membranes manufactured by Takeda industriesSeries of films, etc. More specifically, as the reverse osmosis membrane, SWC5MAX (0.32 m) manufactured by Hydranautics corporation can be used3/m2(d) SWC6MAX (0.43 m) manufactured by Hydranautics3/m2SW30ULE (0.39 m) manufactured by DOW3/m2SW30HRLE (0.25 m) manufactured by DOW3/m2(d), TM820V (0.32 m) manufactured by Toray corporation3/m2(d), TM820K (0.20 m) manufactured by Toray corporation3/m2HR-RO (0.36 m) manufactured by Takeda industries, Ltd3/m2And/d) and the like. Here, the numerical value in parentheses is the permeation flux per 1MPa effective pressure of the reverse osmosis membrane.
The permeate flux was obtained by dividing the permeate water amount by the membrane area. The "effective pressure" is a pressure in JIS K3802: 2015 "membrane terminology" the effective pressure acting on the membrane after subtracting the osmotic pressure difference and the secondary pressure from the average operating pressure. The average operating pressure is an average value of the operating pressure, which is the pressure of the membrane feed water on the primary side of the membrane, and the concentrate outlet pressure, which is the pressure of the concentrate, and can be expressed by the following equation.
Average operating pressure (operating pressure + outlet pressure of concentrated water)/2
The permeate flux per 1MPa effective pressure can be calculated from information described in the catalog of the membrane manufacturer, for example, permeate water amount, membrane area, recovery rate at the time of evaluation, NaCl concentration, and the like. In addition, in the case where one or more pressure vessels are filled with a plurality of membranes having the same permeation flux, the permeation flux of the filled membranes can be calculated from information such as the average operating pressure/secondary pressure of the pressure vessel, the raw water quality, the amount of permeated water, the number of membranes, and the like.
The membrane shape of the reverse osmosis membrane is not particularly limited, and examples thereof include a circular type, a flat membrane type, a spiral type, a hollow fiber type, and the like, and the spiral type may be any of a 4-inch type, an 8-inch type, a 16-inch type, and the like.
In the water treatment apparatus shown in fig. 3, the reverse osmosis apparatus 15 is provided in the stage preceding the deoxidation apparatus 10, but the position of the reverse osmosis apparatus 15 for reducing the load of the ultraviolet oxidation treatment may be any position as long as it is on the inlet side of the hydrogen peroxide addition apparatus 20. Therefore, as shown in fig. 4, the positions of the deoxidation apparatus 10 and the reverse osmosis apparatus 15 may be switched, the water to be treated may be first supplied to the deoxidation apparatus 10, and the outlet water of the deoxidation apparatus 10 may be supplied to the hydrogen peroxide addition apparatus 20 via the reverse osmosis apparatus 15. Further, even in a structure in which the deoxidation apparatus 10 is not provided, it is effective to provide the reverse osmosis apparatus 15. Fig. 5 shows a water treatment device in which: the reverse osmosis apparatus 15 is connected to the inlet of the hydrogen peroxide addition apparatus 20 without providing the deoxidation apparatus 10, so that the water to be treated having TOC reduced by the reverse osmosis apparatus 15 is supplied to the water treatment apparatus of the hydrogen peroxide addition apparatus 20.
In the present invention, an ion exchange device for removing decomposition products in the ultraviolet ray oxidation treatment or ionic impurities derived from the water to be treated may be provided on the outlet side of the ultraviolet ray irradiation device. The water treatment apparatus shown in fig. 6 is further provided with an ion exchange device 35 to which outlet water of the ultraviolet oxidation device 31 is supplied, as compared with the water treatment apparatus shown in fig. 3. The outlet water from the ion exchange device 35 is treated by the water treatment device and then supplied to the outside.
Although the organic substances contained in the water to be treated also contain substances that are ionic from the stage before the water is subjected to the ultraviolet oxidation treatment, H is added2O2The ultraviolet oxidation treatment is performed to generate various organic acids or carbonic acid plasma substances. The ion exchange device 35 removes these ionic species. The ion exchange device 35 is constituted by, for example, an ion exchange column packed with an ion exchange resin. When the concentration of ionic impurities in the outlet water of the ultraviolet oxidation device 31 is high, it is preferable to use a regenerative ion exchange device. Since the organic acid or carbonic acid, which is a reaction product of the ultraviolet oxidation treatment, is in the form of anions in water, the ion exchange resin used in the ion exchange device 35 is at least an anion exchange resin. Since organic acids and carbonic acid are weak acids, it is preferable to use strongly basic anion exchange resins as the anion exchange resins in order to reliably remove them. Furthermore, by using the vaginaA mixed resin of an ion exchange resin and a cation exchange resin is used as the ion exchange resin, or a mixed bed type ion exchange column packed with the mixed resin is used as the ion exchange column, whereby treated water of high purity can be obtained.
However, the excess H contained in the outlet water of the ultraviolet oxidation device 312O2There is a possibility that the ion exchange resin in the ion exchange device 35 is oxidatively deteriorated. Therefore, it is preferable to remove H at the front stage of the ion exchange apparatus 352O2. The water treatment apparatus shown in FIG. 7 is the water treatment apparatus shown in FIG. 6, in which H in the decomposed water is provided between the ultraviolet oxidation apparatus 31 and the ion exchange apparatus 352O2The hydrogen peroxide decomposing device 37. The outlet water of the ultraviolet oxidation apparatus 31 is passed through a hydrogen peroxide decomposition apparatus 37 to remove hydrogen peroxide, and then supplied to an ion exchange apparatus 35. The hydrogen peroxide decomposition device 35 is, for example, a decomposition tower filled with activated carbon. As a means capable of decomposing H efficiently at low cost2O2The substance (2) is preferably activated carbon. Alternatively, the hydrogen peroxide decomposition device 37 may decompose H using a palladium (Pd) catalyst2O2。
While various configuration examples have been described above with respect to the water treatment apparatus according to the present invention, these water treatment apparatuses can be used for decomposition treatment of organic substances in water to be treated having a TOC concentration of 0.1mg/L or more and a dissolved oxygen concentration of more than 1mg/L, for example. According to the present invention, it is clear from the examples described later that the water to be treated containing TOC in the order of mg/L can be treated at a high TOC removal rate.
In the present invention, the water to be treated is, for example, process wastewater. The water treatment method of the present invention is used for recovering process wastewater, particularly wastewater discharged from a process using ultrapure water such as a semiconductor production process, and the like, and treating the wastewater. The water treated by the water treatment method of the present invention can be used as raw water for producing ultrapure water. Therefore, the water treatment method of the present invention can be used for recovering and treating wastewater from a process using ultrapure water, and ultrapure water is produced for recycling.
Fig. 8 shows an application example of the water treatment apparatus according to the present invention. The water treatment apparatus 81 according to the present invention treats recovered water recovered from an ultrapure water use process 83, which is a process using ultrapure water, as water to be treated, and generates recovered water with reduced organic matters. The ultrapure water used in the ultrapure water use process 83 is produced by the ultrapure water production apparatus 82 to which the primary pure water is supplied, but the recovered water from the water treatment apparatus 81 in which the organic matter is reduced is mixed with the primary pure water and supplied to the ultrapure water production apparatus 82. In the system shown in FIG. 8, the recovery and reuse of ultrapure water is realized by the water treatment apparatus 81, and only the amount of primary pure water corresponding to the amount of ultrapure water consumed by the ultrapure water use process 83 and not recovered can be supplied to the ultrapure water production apparatus 82, so that a significant water saving can be realized.
[ examples ] A method for producing a compound
Next, the present invention will be described in further detail by explaining the results of experiments performed by the inventors of the present invention to complete the present invention.
[ Experimental example 1]
The device of the structure shown in fig. 7 was assembled. In this apparatus, isopropyl alcohol (CH) is added after pure water is subjected to deoxidation treatment by membrane degassing3CH(OH)CH3(ii) a IPA) and then H is added2O2For addition of IPA and H2O2The water is subjected to ultraviolet oxidation treatment. The water quality of the pure water used here is: resistivity of 1M omega cm or more, TOC of 3 μ g/L or less, dissolved oxygen concentration of 7.8mg/L, and H2O2The concentration is 1. mu.g/L or less. This apparatus is an apparatus for decomposing organic substances contained in water to be treated, using pure water containing IPA as organic substances (TOC component), and it can be said that a deoxidation treatment by membrane degassing before adding IPA is a treatment for reducing the dissolved oxygen concentration of water to be treated. Considering that IPA in water is not generally removed by membrane degassing, the apparatus shown in FIG. 9 is used to supply IPA-containing water to be treated to a deoxidation apparatus for deoxidation treatment, and then H is added2O2The same result was obtained in the case of performing the ultraviolet ray oxidation treatment.
At the position of FIG. 7In the illustrated apparatus, pure water is supplied to a membrane degassing unit 11 as a deoxidation apparatus. As the membrane degassing unit 11, "liquid-CellG 284" manufactured by Celgard corporation was used, and the gas phase side of the membrane degassing unit 11 was depressurized by a pump 12 to perform a degassing treatment so that the dissolved oxygen concentration became a predetermined concentration. A predetermined amount of IPA is added as a TOC component to the water having a reduced dissolved oxygen concentration through the membrane degassing unit 11 via the storage tank 51 and the pump 52. This produces water to be treated having a reduced dissolved oxygen concentration. Then, a predetermined amount of H2O2 was added to the water to be treated via the storage tank 21 and the pump 22. Will be added with H2O2A part of the water to be treated was branched, and the dissolved oxygen concentration and the TOC concentration thereof were measured on-line with a dissolved oxygen meter (DO meter) 56 and a TOC meter 57, respectively. DO-30A manufactured by TOA electronics is used as the DO meter 56, and SIEVERS900 TOC meter manufactured by Sievers is used as the TOC meter 57. The dissolved oxygen concentration at the DO meter 56 becomes the dissolved oxygen concentration in the outlet water of the membrane degassing unit 11, that is, the dissolved oxygen concentration at the inlet of the ultraviolet oxidation device 31. The TOC measurement at TOC meter 57, TOC0, becomes the TOC concentration of the water being treated.
Will be added with H2O2The water not branched in the water to be treated is supplied to the ultraviolet oxidizer 31. As the ultraviolet ray oxidation apparatus 31, JPW-2 manufactured by Photoscience, Japan was used, and 4 low-pressure ultraviolet ray lamps (165W ultraviolet ray lamps AZ-9000W manufactured by Photoscience, Japan) for generating two kinds of light of 254nm wavelength and 185nm wavelength were disposed as ultraviolet ray lamps in the ultraviolet ray oxidation apparatus 31. The dissolved oxygen concentration of the outlet water of the ultraviolet oxidation apparatus 31 was measured by the DO meter 41, a part of the outlet water of the ultraviolet oxidation apparatus 31 was branched and passed through the ion exchange apparatus 35, and the TOC concentration TOC1 of the outlet water from the ion exchange apparatus 35, that is, the treated water in the water treatment apparatus was measured by the TOC meter 58. DO-30A manufactured by TOA electronics is used as the DO meter 41, and SIEVERS900 TOC meter manufactured by Sievers is used as the TOC meter 58.
As the ion exchanger 35, a mixed bed type ion exchanger is used. The mixed bed type ion exchanger had a cylindrical container (inner diameter: 25mm, height: 1000mm) made of an acrylic resin, and 300mL of a mixed bed ion exchange resin (EG-5A: manufactured by Organo) was charged into the container. At this time, the height of the ion exchange resin layer was about 600 mm.
The TOC removal rate in the water treatment device is defined by the following calculation formula:
TOC removal rate (%) ((TOC0-TOC1)/TOC0) × 100
As described above, the TOC0 is the TOC concentration of the water to be treated, i.e., the TOC concentration measured by the TOC meter 57, and the TOC1 is the TOC concentration of the water to be treated from the ion exchange device 35, i.e., the TOC concentration measured by the TOC meter 58.
H is added in a state where the TOC concentration of the water to be treated, that is, the TOC concentration at the inlet of the ultraviolet oxidation apparatus 31 is adjusted to 500. mu.g/L by adjusting the dissolved oxygen concentration at the inlet of the ultraviolet oxidation apparatus 31 to 50. mu.g/L and the amount of IPA to be added by the membrane degassing unit 112O2The amounts of addition of (A) were adjusted to 0mg/L, 2.5mg/L, 5.0mg/L and 10.0mg/L, and the TOC removal rate and the dissolved oxygen concentration at the outlet of the ultraviolet oxidation apparatus 31, that is, the dissolved oxygen concentration measured by the DO meter 41 were measured for each case. The results are shown in table 1. The amount of water supplied to the ultraviolet oxidizer 31 was 800L/hr. From the results, it was found that addition of H2O2Thereby improving the TOC removal rate, and if the TOC concentration of the liquid to be treated and the dissolved oxygen concentration at the inlet of the ultraviolet oxidation device 31 are constant, H is excessively added2O2In this case, the TOC removal rate is rather decreased, and the dissolved oxygen concentration at the outlet of the ultraviolet oxidation device 31 is increased. From this, it was found that H can be converted by measuring the dissolved oxygen concentration at the outlet of the ultraviolet oxidation apparatus 312O2The amount of the additive (B) is controlled to be optimum.
Further, the dissolved oxygen concentration was adjusted to 7.8mg/L by bypassing the membrane degassing unit 11, and H was added2O2The TOC removal rate and the dissolved oxygen concentration at the outlet of the ultraviolet oxidation apparatus 31 were measured with the addition amount of (2) being 0 mg/L. The results are also shown in table 1. The TOC removal rate in this case was 82%, and it was found that the concentration of dissolved oxygen in the water to be treated was reduced and that the TOC removal rate was increasedH2O2The TOC removal rate is improved by irradiating the water to be treated with ultraviolet rays.
[ TABLE 1]
[ Experimental example 2]
In addition to the TOC concentration of the treated water, that is, the TOC concentration at the inlet of the ultraviolet oxidation apparatus 31, set to 1000. mu.g/L, H is added2O2An experiment was carried out under the same conditions as in example 1 except that the amount of addition was 20.0 mg/L. The results are shown in table 2. Thereby, the concentration of dissolved oxygen in the water to be treated can be reduced and H can be added2O2And thus increased TOC removal.
Further, H was adjusted so that the dissolved oxygen concentration was 7.8mg/L by bypassing the membrane degassing unit 112O2The TOC removal rate was measured with the addition amounts of (2) and (2.5) mg/L. These results are also shown in table 2. By-passing the membrane degassing module 11, it is meant that the dissolved oxygen concentration is not lowered but is maintained at a saturation level substantially at atmospheric pressure, but it is understood that even when H is added to the liquid to be treated in the case where the dissolved oxygen concentration is high as described above2O2The TOC removal rate in the ultraviolet ray oxidation treatment was not increased.
[ TABLE 2]
[ Experimental example 3]
Except that the dissolved oxygen concentration at the inlet of the ultraviolet ray oxidation apparatus 31 was set to 500. mu.g/L, and H was added2O2The experiment was carried out under the same conditions as in Experimental example 1 except that the amounts of addition were 0mg/L, 1.5mg/L, 2.5mg/L and 5.0 mg/L. The results are shown in Table 3.
[ TABLE 3]
[ Experimental example 4]
Except that the dissolved oxygen concentration at the inlet of the ultraviolet oxidation device 31 was set to 1000. mu.g/L, and H was added2O2The experiment was carried out under the same conditions as in Experimental example 1 except that the amounts of addition were 0mg/L, 1.5mg/L, 2.0mg/L and 2.5 mg/L. The results are shown in Table 4.
[ TABLE 4]
[ Experimental example 5]
The concentration of dissolved oxygen at the inlet of the ultraviolet oxidation apparatus 31 was adjusted to 50. mu.g/L by the membrane degassing unit 11, and the amount of IPA added was adjusted so that the TOC concentration of the water to be treated (TOC concentration at the inlet of the ultraviolet oxidation apparatus 31) became 100. mu.g/L. In this state, H is introduced2O2The amounts of (A) were adjusted to 0mg/L, 0.2mg/L and 0.4mg/L, and TOC removal rates were measured for each case. The amount of water supplied to the ultraviolet oxidizer 31 was 2000L/hr. Otherwise, the experiment was performed under the same conditions as in experimental example 1. The results are shown in table 5.
[ TABLE 5]
Description of the symbols
10 deoxidation device
15 reverse osmosis device
20 hydrogen peroxide adding device
30 ultraviolet irradiation device
31 ultraviolet ray oxidation device
40 control device
41. 56 Dissolved Oxygen (DO) meter.
Claims (16)
1. A water treatment method for decomposing organic substances contained in water to be treated, comprising:
a hydrogen peroxide addition step of adding hydrogen peroxide to the water to be treated;
an ultraviolet irradiation step of irradiating the water to be treated to which hydrogen peroxide is added with ultraviolet rays; and
a stage of measuring the dissolved oxygen concentration of the outlet water from the ultraviolet irradiation stage,
controlling the amount of hydrogen peroxide added in the hydrogen peroxide addition stage according to the measured dissolved oxygen concentration.
2. The water treatment method according to claim 1,
the amount of hydrogen peroxide added is controlled so that the dissolved oxygen concentration of the outlet water from the ultraviolet irradiation stage becomes 0.1mg/L or less.
3. The water treatment method according to claim 1 or 2,
in the ultraviolet irradiation step, ultraviolet rays containing components having a wavelength of 185nm or less are irradiated.
4. The water treatment method according to claim 1 or 2,
the water treatment method further comprises a step of reducing organic substances contained in the water to be treated by reverse osmosis treatment before the hydrogen peroxide addition step.
5. The water treatment method according to claim 4,
the reverse osmosis membrane used in the reverse osmosis treatment had a permeation flux of 0.5m per 1MPa of effective pressure3/m2And/d is as follows.
6. The water treatment method according to claim 1 or 2,
the total organic carbon concentration of the water to be treated before the treatment by the water treatment method is 0.1mg/L or more, and the dissolved oxygen concentration exceeds 1 mg/L.
7. The water treatment method according to claim 1 or 2,
the treated water is drained from the process.
8. The water treatment method according to claim 7,
the process wastewater is water discharged from a process using ultrapure water, and the water treated by the water treatment method is used as raw water for generating ultrapure water used in the process.
9. The water treatment method according to claim 1,
there is also a stage of reducing the dissolved oxygen concentration of the water being treated prior to the hydrogen peroxide addition stage.
10. A water treatment apparatus for decomposing organic substances contained in water to be treated, comprising:
a hydrogen peroxide adding device that adds hydrogen peroxide to the water to be treated;
an ultraviolet irradiation device that irradiates the water to be treated to which the hydrogen peroxide is added with ultraviolet rays;
a dissolved oxygen measuring unit that measures a dissolved oxygen concentration of outlet water of the ultraviolet irradiation device; and
and a control unit that controls the amount of hydrogen peroxide added in the hydrogen peroxide addition device in accordance with the dissolved oxygen concentration measured by the dissolved oxygen measurement unit.
11. The water treatment apparatus according to claim 10,
the control means controls the amount of hydrogen peroxide added so that the dissolved oxygen concentration of the outlet water from the ultraviolet irradiation device becomes 0.1mg/L or less.
12. The water treatment apparatus according to claim 10 or 11,
the ultraviolet irradiation device is an ultraviolet oxidation device which irradiates ultraviolet rays containing components with the wavelength of 185nm or less.
13. The water treatment apparatus according to claim 10 or 11,
the hydrogen peroxide adding apparatus is provided with a reverse osmosis apparatus on the inlet side thereof, and the reverse osmosis apparatus has a reverse osmosis membrane and reduces organic matter contained in the water to be treated.
14. The water treatment apparatus according to claim 13,
the permeation flux of the reverse osmosis membrane per 1MPa of effective pressure is 0.5m3/m2And/d is as follows.
15. The water treatment apparatus according to claim 10 or 11,
the water to be treated supplied to the water treatment apparatus has a total organic carbon concentration of 0.1mg/L or more and a dissolved oxygen concentration exceeding 1 mg/L.
16. The water treatment apparatus according to claim 10,
a deoxidation device for reducing the dissolved oxygen concentration of the water to be treated is provided in a stage preceding the hydrogen peroxide addition device.
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Also Published As
| Publication number | Publication date |
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| WO2018092832A1 (en) | 2018-05-24 |
| KR20190066059A (en) | 2019-06-12 |
| CN109906206A (en) | 2019-06-18 |
| TW201821371A (en) | 2018-06-16 |
| JP6752693B2 (en) | 2020-09-09 |
| KR102233505B1 (en) | 2021-03-29 |
| JP2018079448A (en) | 2018-05-24 |
| TWI732970B (en) | 2021-07-11 |
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