The present application is based on, and claims priority from, JP2019-193568, filed on Oct. 24, 2019, and the disclosure of which is hereby incorporated by reference herein in its entirety.
The present invention relates to a water treatment system, an ultrapure water producing system and a water treatment method.
Conventionally, in the processes of manufacturing semiconductor devices and liquid crystal devices, pure water (including ultrapure water) from which organic materials, ion components, fine particles, bacteria and so on are substantially removed is used as washing water. In particular, regarding pure water that is used in the processes of washing electronic components including semiconductor devices, the requirements for water quality have been raised year by year. As a part of this, reduction of boron has recently been required. It is known that boron, which is a weak acid, can be removed by means of a reverse-osmosis membrane apparatus (hereinafter, referred to as an RO apparatus) or an electrodeionization apparatus (hereinafter, referred to as an EDI) (JP4045658). In order to substantially remove boron, boron-selective ion exchange resin may also be used.
The above-mentioned method needs a system for selectively removing boron and thus results in an increase in initial cost.
The present invention aims at providing a water treatment system and a water treatment method with a simple arrangement to make it possible to enhance the boron removal efficiency of an EDI.
According to an aspect, a water treatment system comprises:
an electrodeionization apparatus having a deionization chamber that deionizes water to be treated that contains boron and a concentration chamber in which concentrated water flows; and
cooling means to cool the water to be treated supplied to the deionization chamber or the concentrated water supplied to the concentration chamber.
According to another aspect, a water treatment system comprises:
an electrodeionization apparatus having a deionization chamber that deionizes water to be treated that contains boron, a concentration chamber in which concentrated water flows, and an electrode chamber in which electrode water flows;
cooling means that adjusts temperature of the water to be treated or temperature of the concentrated water supplied to the concentration chamber; and
control means that controls the cooling means such that the cooling means adjusts the temperature of the water to be treated supplied to the deionization chamber or the temperature of the concentrated water supplied to the concentration chamber within a range of 10 to 23° C., based on the temperature of the water to be treated, temperature of treated water of the electrodeionization apparatus, the temperature of the concentrated water, or temperature of the electrode water.
According to jet another aspect, in a water treatment method using an electrodeionization apparatus comprising a deionization chamber that deionizes water to be treated that contains boron and a concentration chamber in which concentrated water flows, the water treatment method comprises:
cooling the water to be treated or the concentrated water supplied to the concentration chamber by cooling means; and
supplying the water to be treated or the concentrated water to the electrodeionization apparatus after being cooled and deionizing the water to be treated in the deionization chamber.
According to the present invention, it is possible to provide a water treatment system and a water treatment method with a simple arrangement to make it possible to enhance the boron removal efficiency of an EDI.
The above and other objects, features and advantages of the present invention will become apparent from the following description with reference to the accompanying drawings which illustrate examples of the present invention.
With reference to the drawings, descriptions will now be given of some embodiments of the present invention.
In water treatment system 2, first heat exchanger 21, a first reverse-osmosis membrane apparatus (hereinafter, referred to as first RO apparatus 22A), a second reverse-osmosis membrane apparatus (hereinafter, referred to as second RO apparatus 22B), first membrane-degassing apparatus 23, second heat exchanger 24 (means for adjusting water temperature) and an electrodeionization apparatus (hereinafter, referred to as EDI 25) are arranged in a series in the order listed above along first line L1 in which the water to be treated flows and in the direction in which the water to be treated flows from upstream to downstream. Second RO apparatus 22B may be omitted, but by arranging two RO apparatuses in a series, it is possible to lower the conductivity of the water to be treated that is supplied to deionization chamber 43. Either first membrane degassing apparatus 23 or second RO apparatus 22B may be arranged on the upstream side of the other. That is, first membrane degassing apparatus 23 may also be provided between first RO apparatus 22A and second RO apparatus 22B. In this case, second heat exchanger 24 is positioned between second RO apparatus 22B and EDI 25. First heat exchanger 21 adjusts the temperature of the water to be treated that is supplied to first RO apparatus 22A. The viscosity of water is high when the temperature is low and is low when the temperature is high. If water to be treated having a low temperature is supplied to first RO apparatus 22A, then it may be difficult to obtain a desired flow rate because the water to be treated is less apt to pass through the membrane due to high viscosity. The temperature of the water to be treated supplied to first RO apparatus 22A is adjusted to be about 25° C. by first heat exchanger 21. When the temperature of the water to be treated is 25° C. or more at the inlet of first RO apparatus 22A, or when a sufficient pressure of filtered water pump 5 can be ensured to obtain a desired flow rate even if water to be treated having high viscosity passes through the membrane at a low water temperature, first heat exchanger 21 may be omitted. First membrane-degassing apparatus 23 is provided between second RO apparatus 22B and EDI 25 and removes dissolved gas in the water to be treated. The water to be treated is supplied to EDI 25 via second heat exchanger 24. Accordingly, the water to be treated supplied to EDI 25 has been treated by first and second RO apparatuses 22A, 22B and first membrane-degassing apparatus 23, which are provided upstream of EDI 25. When the amount of carbonic acid dissolved in the water to be treated (dissolved carbon dioxide) is limited, or when carbonic acid is removed upstream of first membrane-degassing apparatus 23 by adjusting pH by first RO apparatus 22A etc., the burden of EDI 25 decreases. In these cases, first membrane-degassing apparatus 23 may be omitted, and dissolved gas may be removed by second membrane-degassing apparatus 34 of subsystem 3. Water treatment system 2 may be provided with additional immediate tanks or pumps, as needed.
EDI 25 is connected to water-to-be-treated line L4 in which the water to be treated flows, treated water line L5 in which the treated water flows, concentrated water line L6 in which the concentrated water flows and electrode water line L7 in which the electrode water flows. Water-to-be-treated line L4 is connected to first sub-deionization chamber 43A. Treated water line L5 is connected to second sub-deionization chamber 43B. Concentrated water line L6 is connected to first concentration chamber 42 and second concentration chamber 44, and electrode water line L7 is connected to anode chamber 41 and cathode chamber 45. Note that water-to-be-treated line L4 corresponds to the portion of first line L1 that is upstream of EDI 25 and to the line that connects first sub-deionization chamber 43A to second sub-deionization chamber 43B, and treated water line L5 corresponds to the portion of first line L1 that is downstream of EDI 25.
First sub-deionization chamber 43A and second sub-deionization chamber 43B are connected to each other in a series via water-to-be-treated line L4 so that the water to be treated flows from first sub-deionization chamber 43A to second sub-deionization chamber 43B. The water to be treated flows in opposite directions (in counter flow) in first sub-deionization chamber 43A and in second sub-deionization chamber 43B. Although not illustrated, more than two deionization chambers may be provided. In this case, concentration chambers are arranged on both sides of each deionization chamber. Specifically, concentration chambers and deionization chambers are alternately arranged between anode chamber 41 and cathode chamber 45, wherein anode chamber 41 and cathode chamber 45 are adjacent to concentration chambers. First cation exchange membrane 47 that separates anode chamber 41 may be omitted so that first concentration chamber 42 also works as anode chamber 41. Similarly, first anion exchange membrane 51 that separates cathode chamber 45 may be omitted so that second concentration chamber 44 also works as cathode chamber 45. In anode chamber 41 and cathode chamber 45, the electrode water flows in the direction opposite that of the concentrated water that flows in first concentration chamber 42 and second concentration chamber 44. In the illustrated example, the electrode water is supplied to anode chamber 41 and cathode chamber 45 in parallel, but, for example, the electrode water that flows out of cathode chamber 45 may be supplied to anode chamber 41.
First sub-deionization chamber 43A is charged with anion exchange resin AER. Second sub-deionization chamber 43B is charged with cation exchange resin CER in the upstream portion thereof in the direction in which the water to be treated flows and is charged with anion exchange resin AER in the downstream portion thereof. Accordingly, the water to be treated flows through anion exchange resin AER, then through cation exchange resin CER, and then through anion exchange resin AER. Such a pattern of charging the chambers with resin is effective for efficiently removing boron contained in the water to be treated. First and second concentration chambers 42, 44 are charged with anion exchange resin in a single bed. The anion exchange resin with which first and second concentration chambers 42, 44 are charged has electrical conductivity, whereby increase in electric resistance between the anode and the cathode is limited. Accordingly, first and second concentration chambers 42, 44 may be charged with cation exchange resin, which is a material having electrical conductivity, in a single bed, or charged with anion exchange resin and cation exchange resin, which are materials having electrical conductivity, in a mixed bed. Although not illustrated, first and second concentration chambers 42, 44 may be charged with ion exchange fiber instead of ion exchange resin. Although first and second concentration chambers 42, 44 are preferably charged with some kind of ion exchange material, this charging with ion exchange material may be omitted if the increase in electric resistance is within an allowable range.
The arrangement of EDI 25 is not limited to that shown in
Next, second heat exchanger 24 (means for adjusting water temperature) will be described in more detail. Second heat exchanger 24 is provided upstream of EDI 25, specifically, between second RO apparatus 22B and EDI 25, and more specifically, between first membrane-degassing apparatus 23 and EDI 25, and adjusts the temperature of the water to be treated supplied to deionization chamber 43 of EDI 25 within a range of about 10 to 23° C., and preferably 15 to 23° C. By adjusting the temperature of the water to be treated within this range, the boron-removal efficiency of EDI 25 can be enhanced. This point will be described in more detail in the Examples. Since the temperature of the water to be treated is adjusted to about 25° C. at the inlet of first RO apparatus 22A, the water to be treated is cooled by second heat exchanger 24 in the present embodiment. As second heat exchanger 24, heat exchangers of general types such as a shell-and-tube type or a plate type may be used.
Second heat exchanger 24 is connected to cooling line 28 in which cooling water flows, and cooling line 28 is provided with valve 29 that adjusts the flow rate of the cooling water. Thermometer 26 and control means 27 are provided to adjust the temperature. Thermometer 26 is provided on first line L1 between second heat exchanger 24 and EDI 25 and measures the temperature of the water to be treated that is supplied to deionization chamber 43 of EDI 25. Control means 27 controls the degree of opening of valve 29 based on the temperature of the water to be treated that is measured by thermometer 26 so as to adjust the temperature of the water to be treated that is supplied to deionization chamber 43 of EDI 25 within a range of about 10 to 23° C., and preferably 15 to 23° C. In this manner, control means 27 controls the operation of second heat exchanger 24. Control means 27 may be realized by software incorporated into a control computer (not illustrated) of ultrapure water producing system 1. The type of heat exchange is not limited to this form, and any type of heat exchange means, such as an air-cooling type, may be used to adjust the temperature of the water to be treated within the range of 10 to 23° C., and preferably 15 to 23° C. When the temperature of the pretreated water is low or when filtered water pump 5 has sufficient pressure, the temperature of the water to be treated may be less than 25° C. at the inlet of first RO apparatus 22A. In this case, second heat exchanger 24 may also heat the water to be treated. Alternatively, thermometer 26 may be provided at one location selected from among the inlets and the outlets of water-to-be-treated line L4, treated water line L5 and concentrated water line L6, and the inlet and the outlet of electrode water line L7. Thermometer 26 measures the temperature of the water to be treated, the treated water, the concentrated water, or the electrode water, depending on the line on which it is provided. There is a correlation between the temperature of the water to be treated and the temperature of the treated water, and the temperatures of the concentrated water and the electrode water are also correlated with the temperature of the water to be treated. Accordingly, the temperature of the water to be treated for EDI 25 can be controlled regardless of the line among lines L4 to L7 on which thermometer 26 is provided. For example, in Example 4 (having the arrangement shown in
As will be described in detail with reference to the Examples, as the temperature of the water to be treated falls, the boron removal rate of EDI 25 uniformly increases. Accordingly, from the viewpoint of the boron removal rate, it is preferable that the temperature of the water to be treated be low. On the other hand, the temperature of the water to be treated in subsystem 3 needs to be adjusted by heat exchanger 31 such that the temperature at the point of use is within a predetermined range. If the temperature of the water to be treated supplied to subsystem 3 is too low, then extra energy will be consumed to heat the water to be treated in subsystem 3. Accordingly, the lower limit of the temperature of the water to be treated supplied to deionization chamber 43 of EDI 25 is preferably about 10° C. Note that, in the present embodiment, water treatment system 2 (second heat exchanger 24) requires energy to cool the water to be treated (for example, the electric energy required to produce cool water), but the temperature of the water to be treated is normally increased by the heat from pure water pump 7 and the like when the water to be treated circulates in the circulating line of subsystem 3 consisting of second line L2 and recirculating line L3. Therefore, cooling the water to be treated by second heat exchanger 24 leads to a decrease in the burden of third heat exchanger 31, and providing second heat exchanger 24 does not cause a large increase in energy for the entire ultrapure water producing system 1.
As will be described in detail in the Examples, by charging first and second concentration chambers 42, 44 with ion exchange resin, the voltage between the anode and the cathode can be kept at a substantially constant level regardless of the temperature and the conductivity of the water to be treated. Accordingly, first and second concentration chambers 42, 44 are preferably charged with ion exchange resin in order to limit the increase in energy consumed in EDI 25 that is caused by cooling the water to be treated that has low conductivity. The conductivity of the water to be treated is limited to about 5 μS/cm or less by arranging two RO apparatuses in a series in the present embodiment.
First membrane-degassing apparatus 23 is provided upstream of second heat exchanger 24. First membrane-degassing apparatus 23 mainly aims at removing dissolved carbon dioxide and dissolved oxygen, and a decrease of the temperature of the water to be treated may lead to deterioration of the de-aerating performance due to increase in the solubility of gas. For this reason, the water to be treated is supplied to first membrane-degassing apparatus 23 before being cooled by second heat exchanger 24.
EDI 25 is connected to subtank 6 that stores the primary pure water. The water treated by EDI 25 (primary pure water) is stored in subtank 6 and is then supplied to subsystem 3 by pure water pump 7. In subsystem 3, third heat exchanger 31, UV oxidization apparatus 32, cartridge polisher 33, second membrane-degassing apparatus 34, and ultrafiltration membrane apparatus 35 are arranged in a series along second line L2 in which the water to be treated flows and in the direction in which the water to be treated flows from upstream to downstream. The secondary pure water produced by subsystem 3 is supplied to point of use 8. The secondary pure water that is not used at point of use 8 is returned to subsystem 3 via recirculating line L3. Recirculating line L3 is connected to subtank 6.
As described above, the temperature of the water to be treated varies due to the heat from pure water pump 7 and the like when the water to be treated circulates in the circulating line of subsystem 3 consisting of second line L2 and recirculating line L3. For this reason, the temperature of the water to be treated is adjusted by third heat exchanger 31. Next, the water to be treated is irradiated with ultraviolet rays by UV oxidization apparatus 32. The total organic carbon (TOC) contained in the water to be treated is resolved into carbon dioxide and organic acid by OH radicals generated by the irradiation with ultraviolet rays. The water to be treated is further supplied to cartridge polisher 33 where ion components are removed. Cartridge polisher 33 is a non-regenerative ion exchange apparatus, which is a cylinder charged with ion exchange resin. The water to be treated that has passed through cartridge polisher 33 is then supplied to second membrane-degassing apparatus 34 where dissolved oxygen is removed. Further, fine particles contained in the water to be treated are removed by the ultrafiltration membrane apparatus, whereby production of the secondary pure water is completed. The secondary pure water thus produced is supplied to point of use 8.
The boron removal rate of an RO apparatus is improved when the temperature of the water to be treated is low. On the other hand, ions are concentrated on the primary side (inlet side) of an RO apparatus. Thus, when the water to be treated is supplied to an RO apparatus at a low temperature, the solubility of each ion component decreases on the primary side of the RO apparatus, and precipitation of ions may occur. In particular, this tendency is greater on the primary side of first RO apparatus 22A where the ion concentration is high. However, the possibility of precipitation of ions is small on the primary side of second RO apparatus 22B because the concentration of ion components is low. The possibility of precipitation of ions can be limited by supplying the water to be treated to first RO apparatus 22A at a relatively high temperature, while the boron removal rate can be enhanced by supplying the water to be treated to second RO apparatus 22B at a relatively low temperature.
(Modifications)
Second heat exchanger 24 is provided on water-to-be-treated line L4 downstream of the branching point where concentrated water line L6 and electrode water line L7 branch off but may be provided at other locations. As shown in
Some tests were conducted using EDI 25 (hereinafter, simply referred to as an EDI) shown in
In Example 1, the boron removal rate of the EDI was obtained for various temperatures of the water to be treated supplied to the EDI.
Next, the relationship between whether first and second concentration chambers 42, 44 (hereinafter, simply referred to as concentration chambers) were charged with ion exchange resin or not and the voltage between the anode and the cathode was investigated.
Next, the relationship among the conductivity of the water to be treated, whether the concentration chambers are charged with ion exchange resin or not, and the voltage between the anode and the cathode was investigated.
In Examples 1 to 3, single deionization chamber 43 is charged with resin in a mixed bed. Thus, Examples 4, 5 are conducted in order to confirm that similar effects can be achieved for other arrangements of deionization chamber 43 and for other resin charging patterns. The arrangement of deionization chamber 43 and the resin charging pattern in Example 4 are shown in
Although certain preferred embodiments of the present invention have been shown and described in detail, it should be understood that various changes and modifications may be made without departing from the spirit or scope of the appended claims.
Number | Date | Country | Kind |
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2019-193568 | Oct 2019 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2020/029085 | 7/29/2020 | WO |