The present application is based on and claims priority from JP2020-198484 filed on Nov. 30, 2020, the disclosure of which is hereby incorporated by reference herein in its entirety.
The present invention relates to an ultrapure water production system and a method for producing ultrapure water.
An ultrapure water production system has a subsystem that produces ultrapure water from primary pure water. The subsystem has various apparatuses such as an ultraviolet ray oxidization apparatus and an ion exchange apparatus that are arranged in a series, and primary pure water is sequentially treated by these apparatuses in order to produce ultrapure water. A membrane filter apparatus such as an ultrafiltration membrane apparatus for removing fine particles is provided immediately upstream of a point of use to which ultrapure water is supplied. Recently, the demand for the water quality of ultrapure water has been increasing, and fine particles in ultrapure water is required to be controlled on the order of 10 nanometers. JP2016-64342 discloses an ultrapure water production system that has two ultrafiltration membrane apparatuses arranged in a series at the most downstream point.
The ultrapure water production system disclosed in JP2016-64342 is significantly effective from the viewpoint of reducing fine particles. However, the configuration in which two ultrafiltration membrane apparatuses are arranged in a series not only increases cost but also entails problems such as a decrease in flow rate and an increase in power consumption of pumps due to increasing pressure loss.
The present invention aims at providing an ultrapure water production system that has a simplified configuration and that can efficiently remove fine particles that are contained in ultrapure water.
An ultrapure water production system of the present invention comprises: an ultrapure water supply line that is connected to a point of use and that supplies ultrapure water to the point of use; a return line that returns the ultrapure water that has not been used at the point of use to the ultrapure water supply line; and at least one ion exchange apparatus that is provided on the ultrapure water supply line. Space velocity of water to be treated that flows in a final-stage ion exchange apparatus is 170 (1/hr) or more, and wherein the final-stage ion exchange apparatus is an ion exchange apparatus that is closest to the point of use from among the at least one ion exchange apparatus.
The inventors found that fine particles can be efficiently removed by setting the space velocity of water to be treated that flows in the final-stage ion exchange apparatus to 170 (1/hr) or more. Since an ion exchange apparatus is typically provided in an ultrapure water production system, no additional apparatus is required. Thus, according to the present invention, it is possible to provide an ultrapure water production system that has a simplified configuration and that can efficiently remove fine particles that are contained in ultrapure water.
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 that illustrate examples of the present invention.
Embodiments of the present invention will now be described with reference to the drawings.
Subsystem 1 has primary pure water tank 2, pure water supply pump 3, ultraviolet ray oxidization apparatus 4, hydrogen peroxide removal apparatus 5, membrane deaeration apparatus 7, and final-stage ion exchange apparatus 10. These apparatuses are provided on ultrapure water supply line L1 in a series in the order stated above in the flow direction of the water to be treated. Booster pump 8 is provided between membrane deaeration apparatus 7 and final-stage ion exchange apparatus 10. Booster pump 8 is provided to ensure head, for example, when membrane deaeration apparatus 7 and final-stage ion exchange apparatus 10 are arranged at different levels. Accordingly, booster pump 8 may be omitted depending on the arrangement of subsystem 1. Pure water that is produced by the primary pure water system is stored in primary pure water tank 2, and as described above, ultrapure water that has not been used at point of use P.O.U. is returned to primary pure water tank 2.
Water to be treated that is stored in primary pure water tank 2 is pumped by pure water supply pump 3, is supplied to a heat exchanger (not illustrated) for temperature adjustment, and is then supplied to ultraviolet ray oxidization apparatus 4. Ultraviolet ray oxidization apparatus 4 irradiates the water to be treated with ultraviolet rays to dissolve organic carbon contained in the water to be treated and thus reduce the TOC (total organic carbon). Hydrogen peroxide removal apparatus 5 has a catalyst such as palladium (Pd) or platinum (Pt) and dissolves hydrogen peroxide that is generated by the radiation of ultraviolet rays. Final-stage ion exchange apparatus 10 (and upstream ion exchange apparatus 6, depending on embodiments) that is downstream of hydrogen peroxide removal apparatus 5 is therefore prevented from being damaged by oxidizing materials. Membrane deaeration apparatus 7 removes dissolved oxygen and carbon dioxide contained in the water to be treated. The ultrapure water is treated by final-stage ion exchange apparatus 10 before it is supplied to point of use P.O.U. Final-stage ion exchange apparatus 10 is charged with ion exchanger resins.
Water to be treated contains fine particles, and particularly when booster pump 8 is provided, may contain a larger number of fine particles. Fine particles can be removed by final-stage ion exchange apparatus 10 because fine particles typically have electric potentials (zeta potentials) on their surfaces. Although fine particles in ultrapure water generally have negative electric potential (zeta potential) on their surfaces, it is desirable to load ion exchanger resins in the form of a mixed bed of anion exchanger resins and cation exchanger resins in order to efficiently remove fine particles having positive electric potential (zeta potentials) as well. Loading Ion exchanger resins in the form of a mixed bed is also desirable for keeping ultrapure water in a highly pure condition. As a result, both fine particles having positive electric potential and fine particles having negative electric potential can be efficiently captured, and the removal efficiency of fine particles can be enhanced. However, the effect of removing fine particles can also be obtained by anion exchanger resins or cation exchanger resins that are loaded in a single bed. In addition, since fine particles typically have negative electric potential (zeta potential), the mass ratio of anion exchanger resins is preferably larger than the mass ratio of cation exchanger resins. Water to be treated that contains fine particles flows through the resins and therefore the resins themselves function as physical filters. Thus, the resins capture fine particles not only by an electric action but also by a physical action. For these reasons, final-stage ion exchange apparatus 10 is highly capable of removing fine particles. In the present embodiment, no membrane filter apparatus is provided between final-stage ion exchange apparatus 10 and point of use P.O.U. Therefore, ultrapure water from which fine particles have been removed by final-stage ion exchange apparatus 10 cannot be contaminated with fine particles that are generated by a membrane filter apparatus.
Ion exchanger resins are generally classified into a gel type and a macroporous type, and ion exchanger resins loaded in final-stage ion exchange apparatus 10 are preferably a granular gel type. Fine particles may also be generated from the surfaces of ion exchanger resins. However, ion exchanger resins of the gel type have a smaller surface area than ion exchanger resins of the macroporous type and therefore limit fine particles that detach and flow out. Thus, ion exchanger resins of the gel type are preferably used as ion exchanger resins loaded in final-stage ion exchange apparatus 10. As ion exchanger resins, for example, strongly acidic H-type ion exchanger resins and strongly basic OH-type ion exchanger resins are used. The average particle diameters of strongly acidic ion exchanger resins and strongly basic ion exchanger resins are preferably about 500 to 800 μm. The height of the resin bed of final-stage ion exchange apparatus 10 is preferably 10 cm or more, and more preferably 30 cm or more.
The water to be treated that is supplied to final-stage ion exchange apparatus 10 is ultrapure water and therefore has extremely high purity. For this reason, the performance of final-stage ion exchange apparatus 10 does not deteriorate easily and ultrapure water from which fine particles are sufficiently removed can be reliably obtained for a long time at the outlet of final-stage ion exchange apparatus 10. Since final-stage ion exchange apparatus 10 can be used for a long time, the frequency of required maintenance is low. Accordingly, a non-regenerative ion exchange apparatus (a cartridge polisher) is advantageously used as final-stage ion exchange apparatus 10. In other words, non-generative resins are preferably used as ion exchanger resins for final-stage ion exchange apparatus 10. However, generative resins may alternatively be used. Final-stage ion exchange apparatus 10 is replaced when the concentration of fine particles at the outlet exceeds a predetermined value, but alternatively may be replaced when the conductivity of treated water at the outlet exceeds a predetermined value. Final-stage ion exchange apparatus 10 may also be an ion exchange apparatus that is charged with monolithic ion exchangers.
In order to further limit the generation of fine particles, final-stage ion exchange apparatus 10 has its inlet for ultrapure water above the exchanger resin bed and its outlet for ultrapure water below the exchanger resin bed. Consequently, the water to be treated is supplied to final-stage ion exchange apparatus 10 in the downward direction or as a downward flow. Thus, the ion exchanger resin layer is less likely to move and the generation of fine particles that is caused by friction between ion exchanger resins can be limited. As water supply continues, ion exchanger resins are pressed and compacted, whereby the ion exchanger resins are progressively less likely to move, and the generation of fine particles can be further limited. As a result, the function of the ion exchanger resins as a physical filter is also enhanced.
When the above-mentioned ultrapure water production system is operated, washing or conditioning of resins is preferably carried out in advance. When resins of an R—Na type or an R—Cl type (R is resin) are used for producing ultrapure water without any treatment, the water quality required for ultrapure water may not be satisfied due to dissociation of Na ions and Cl ions. For this reason, it is desirable to condition strongly acidic cation exchanger resins by using an acid solution and to condition strongly basic anion exchanger resins by using an alkaline solution. Furthermore, when an R—Na type is converted into an R—H type and an R—Cl type is converted into an R—OH type, the R—Na type is desirably reduced to less than 0.1% and the R—Cl type is desirably reduced to less than 1% of the total number of resins that are loaded in final-stage ion exchange apparatus 10. In addition, before ultrapure water that is treated by final-stage ion exchange apparatus 10 is supplied to point of use P.O.U., it is desirable to supply ultrapure water to the ion exchanger resins until the TOC (total organic carbon) decreases to 0.5 μg/L (ppb) or less at the outlet of final-stage ion exchange apparatus 10. The decrease in the TOC refers to the TOC at the inlet of final-stage ion exchange apparatus 10 minus the TOC at the outlet of final-stage ion exchange apparatus 10 (ΔTOC). The supply of ultrapure water is preferably continued for a longer time in order to reduce the number of fine particles. For example, as will be described later in the examples, fine particles having particle diameters of 20 nm or more can be reduced to less than 0.1 particles/ml by continuously supplying water at SV300 (1/hr) for about 24 hours. Alternatively, it is also possible to supply ultrapure water to ion exchanger resins in advance before the resins are loaded in final-stage ion exchange apparatus 10 to thereby wash the ion exchanger resins until the TOC decreases to 0.5 μg/L (ppb) or less and/or the number of discharged fine particles having particle diameters of 20 nm or more decreases to 0.1 particles/ml or less. The ion exchanger resins can then be loaded in final-stage ion exchange apparatus 10.
An ion exchange apparatus is typically provided to remove ions (metal and anion components). However, as described above, ion exchanger resins are capable of removing fine particles. It is difficult to wash or condition a filter membrane such as an ultrafiltration membrane or a microfiltration filter membrane, particularly on the secondary side (the outlet side) of the membrane. On the other hand, in the case of granular ion exchanger resins, fine particles that exist on the surfaces of the resins or inside the apparatus (the tower) of the resins can be easily removed by washing or conditioning. The inventors found that sufficient washing or conditioning can prevent ion exchanger resins from generating fine particles. According to the present embodiment, ultrapure water having a limited number of fine particles can be easily produced by providing final-stage ion exchange apparatus 10 that is mainly directed to removing fine particles.
In the present embodiment, space velocity SV of water to be treated that flows in final-stage ion exchange apparatus 10 is set to 170 (1/hr) or more, and preferably to 300 (1/hr) or more. Conventionally, a typical value of space velocity SV of water to be treated that flows in an ion exchange apparatus is about 30 to 100 (1/hr), and space velocity SV is greatly increased in comparison. In particular, the removal efficiency of fine particles is thus greatly enhanced, as will be described later in the examples.
Space velocity SV of an ion exchange apparatus (an ion exchange tower) is calculated as flow rate/quantity of resins (amount of filtering material), where
flow rate=LV×S
quantity of resins=h×S
SV=(LV×S)/(h×S)=LV/h
where LV is the linear velocity (flow rate) of the water to be treated that flows through resins in the ion exchange tower, S is the cross section of the flow channel of the ion exchange tower, and h is the height of the resin bed that is loaded in the ion exchange tower.
Accordingly, in order to increase the SV, either increasing linear velocity LV (method 1) or decreasing height h of the resin bed (method 2) may be used. It is also possible to change both linear velocity LV and height h of the resin bed, but this method also requires at least either method 1 or method 2 to be used.
Linear velocity LV can be increased by a number of methods, as described below.
(Method 1-1) Reduce cross section S of the flow channel of the ion exchange tower. When the flow rate is constant, linear velocity LV increases in inverse proportion to cross section S of the flow channel of the ion exchange tower. When subsystem 1 is newly constructed, the footprint of final-stage ion exchange apparatus 10 can be reduced.
(Method 1-2) Increase the flow rate of booster pump 8 (or pure water supply pump 3). Linear velocity LV increases in proportion to the flow rate.
(Method 1-3) When final-stage ion exchange apparatus 10 consists of a plurality of ion exchange towers that are connected in parallel, water to be treated is supplied to only some of the ion exchange towers. This method is similar to method 1-1 but is easy to carry out for existing facilities because this method only requires halting the use of some of the ion exchange towers.
Reducing height h of the resin bed only requires reducing the amount of resin to be loaded. The reduction of resin that is used leads to a reduction of the replacement of resin. This method is also easy to carry out for existing facilities.
The pore diameter, the molecular weight cut-off, and so on of membrane filter apparatus 11 may be determined depending on the fine particles to be removed. For example, when the major purpose is to remove organic fine particles that detach from resins in final-stage ion exchange apparatus 10, membrane filter apparatus 11 having a comparatively large pore diameter (or a large molecular weight cut-off) may be sufficient. Thus, the pressure loss can be reduced, and the flow rate can be increased. On the other hand, since the number of (organic) fine particles that are generated (that detach) from membrane filter apparatus 11 does not largely vary depending on pore diameter, the number of fine particles per unit volume of ultrapure water that passes through membrane filter apparatus 11 is reduced (this is a type of dilution effect that results from the increase in flow rate). Accordingly, highly pure ultrapure water can be produced.
The provision of upstream ion exchange apparatus 6 can enhance the removal efficiency of ionic impurities. In other words, upstream ion exchange apparatus 6 has the function of removing ionic impurities, which is the original function of an ion exchange apparatus, and final-stage ion exchange apparatus has the function of removing fine particles, which is a special function that is not seen in a conventional ion exchange apparatus. Both ionic impurities and fine particles can be efficiently removed by providing both apparatuses.
As illustrated in
The performance of removing fine particles was measured using the test apparatus 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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2020-198484 | Nov 2020 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2021/029007 | 8/4/2021 | WO |