JP7715893B1 - Water treatment method and water treatment device - Google Patents
Water treatment method and water treatment deviceInfo
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Abstract
【課題】紫外線照射装置に供給される被処理水が特定の水質を有する場合に有機物を効率的に分解する。
【解決手段】水処理方法は、紫外線照射装置35の入口部35Aにおいて全有機炭素濃度10μg/L以下、溶存酸素濃度30μg/L以上である被処理水を紫外線照射装置35に供給することと、入口部35Aから紫外線照射装置35に供給された被処理水に紫外線照射装置35から紫外線を照射することと、を有する。入口部35Aにおける被処理水の過酸化水素濃度は30μg/L以下である。
【選択図】図1
An ultraviolet irradiation device efficiently decomposes organic matter when the water to be treated that is supplied to the device has a specific water quality.
[Solution] The water treatment method includes supplying water to be treated, which has a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at an inlet 35A of the ultraviolet irradiation device 35, to the ultraviolet irradiation device 35, and irradiating the water to be treated supplied from the inlet 35A to the ultraviolet irradiation device 35 with ultraviolet light from the ultraviolet irradiation device 35. The hydrogen peroxide concentration of the water to be treated at the inlet 35A is 30 μg/L or less.
[Selected Figure] Figure 1
Description
本発明は水処理方法と水処理装置に関する。 The present invention relates to a water treatment method and a water treatment device.
純水水質への高度な要求が顕在化するに伴って、近年、純水中に含まれる微量の有機物を分解し除去する様々な方法が検討されている。特許文献1には、紫外線照射装置の上流で被処理水に過酸化水素を添加する水処理方法が記載されている。 As demands for higher quality pure water become more apparent, various methods for decomposing and removing trace amounts of organic matter contained in pure water have been investigated in recent years. Patent Document 1 describes a water treatment method in which hydrogen peroxide is added to the water to be treated upstream of an ultraviolet irradiation device.
紫外線照射装置に供給される被処理水が過酸化水素を含むことは、紫外線照射装置による有機物の分解を促進する上で有利である。しかし、本願発明者は紫外線照射装置に供給される被処理水が特定の水質を有している場合、過剰な量の過酸化水素は逆に紫外線照射装置による有機物の分解を阻害することを見出した。 Containing hydrogen peroxide in the water to be treated supplied to the ultraviolet irradiation device is advantageous in promoting the decomposition of organic matter by the ultraviolet irradiation device. However, the inventors of the present application have discovered that when the water to be treated supplied to the ultraviolet irradiation device has a specific water quality, excessive amounts of hydrogen peroxide can actually inhibit the decomposition of organic matter by the ultraviolet irradiation device.
本発明は、紫外線照射装置に供給される被処理水が特定の水質を有する場合に有機物を効率的に分解することのできる水処理方法を提供することを目的とする。 The present invention aims to provide a water treatment method that can efficiently decompose organic matter when the water to be treated supplied to an ultraviolet irradiation device has a specific water quality.
本発明の水処理方法は、紫外線照射装置の入口部において全有機炭素濃度が10μg/L以下、溶存酸素濃度が30μg/L以上である被処理水を紫外線照射装置に供給することと、入口部から紫外線照射装置に供給された被処理水に紫外線照射装置から紫外線を照射することと、を有する。入口部における被処理水の過酸化水素濃度は30μg/L以下である。
一態様では、紫外線照射装置の上流に設けられた脱酸素装置によって、入口部における被処理水の溶存酸素濃度を1000μg/L未満にすることをさらに有する。
他の態様では、紫外線照射装置から紫外線が照射された処理水の一部を戻し配管によって紫外線照射装置の上流に戻すことと、入口部における被処理水の過酸化水素濃度が30μg/L以下となる範囲で、(A)紫外線照射装置から照射される紫外線の照射量を調整すること、(B)紫外線照射装置の上流に設けられた脱酸素装置によって入口部における被処理水の溶存酸素濃度を調整することの少なくともいずれかを行うことと、を有する。
さらに他の態様では、紫外線照射装置から紫外線が照射された処理水の一部を紫外線照射装置の上流に戻すことと、紫外線照射装置に供給される被処理水の過酸化水素濃度を計測することと、計測された過酸化水素濃度が30μg/L以下となるように、紫外線照射装置の上流に戻す処理水の量を調整することと、をさらに有する。
The water treatment method of the present invention includes supplying water to be treated, the water having a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at an inlet of the ultraviolet irradiation device, to the ultraviolet irradiation device, and irradiating the water to be treated supplied from the inlet to the ultraviolet irradiation device with ultraviolet light from the ultraviolet irradiation device. The hydrogen peroxide concentration of the water to be treated at the inlet is 30 μg/L or less.
In one embodiment, the method further comprises reducing the dissolved oxygen concentration of the water to be treated at the inlet to less than 1000 μg/L by a deoxygenation device provided upstream of the ultraviolet irradiation device.
In another aspect, the method includes returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device to the upstream side of the ultraviolet irradiation device via a return pipe, and performing at least one of (A) adjusting the amount of ultraviolet rays irradiated from the ultraviolet irradiation device so that the hydrogen peroxide concentration of the treated water at the inlet is 30 μg/L or less, and (B) adjusting the dissolved oxygen concentration of the treated water at the inlet using a deoxygenation device provided upstream of the ultraviolet irradiation device.
In yet another aspect, the method further includes returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device to an area upstream of the ultraviolet irradiation device, measuring the hydrogen peroxide concentration of the water to be treated that is supplied to the ultraviolet irradiation device, and adjusting the amount of treated water that is returned upstream of the ultraviolet irradiation device so that the measured hydrogen peroxide concentration is 30 μg/L or less.
本発明によれば、紫外線照射装置に供給される被処理水が特定の水質を有する場合に有機物を効率的に分解することのできる水処理方法を提供することができる。 The present invention provides a water treatment method that can efficiently decompose organic matter when the water to be treated supplied to the ultraviolet irradiation device has a specific water quality.
以下、図面を参照して本発明の水処理方法と水処理装置の実施形態について説明する。図1は本発明の第1の実施形態に係る水処理装置1の概略構成を示している。水処理装置1は上流側の前処理装置2と下流側の純水製造装置3(1次システム)とを有している。水処理装置1は下流側のサブシステム(2次システム)とともに超純水製造装置を構成する。前処理装置2に供給される原水は溶存酸素と有機物を含有している。以下の説明で、上流と下流は母管における水の流通方向に関して定義される。また、「調整」とは制御装置によって各種の運転パラメータ(装置のオンオフ、流量、圧力、弁の開閉、電力量等)を自動で制御することと、オペレータが手動でこれらの運転パラメータを調整することの両者を含む。本発明は水処理装置1だけでなくサブシステムに適用することも可能である。 Embodiments of the water treatment method and water treatment device of the present invention will now be described with reference to the drawings. Figure 1 shows the schematic configuration of a water treatment device 1 according to a first embodiment of the present invention. The water treatment device 1 has an upstream pretreatment device 2 and a downstream pure water production device 3 (primary system). Together with a downstream subsystem (secondary system), the water treatment device 1 constitutes an ultrapure water production system. The raw water supplied to the pretreatment device 2 contains dissolved oxygen and organic matter. In the following description, upstream and downstream are defined with respect to the direction of water flow in the main pipe. Furthermore, "adjustment" includes both automatic control of various operating parameters (device on/off, flow rate, pressure, valve opening/closing, power consumption, etc.) by a control device and manual adjustment of these operating parameters by an operator. The present invention can be applied not only to the water treatment device 1 but also to subsystems.
前処理装置2は、比較的粒径の大きな塵埃等を除去するためのろ過器21と、高分子有機物、酸化剤などの不純物を除去するための活性炭塔22と、を含んでいる。ろ過器21として、例えば砂ろ過器を用いることができる。純水製造装置3はイオン除去装置31と、逆浸透膜装置32と、中間タンク33と、第1の脱酸素装置34と、紫外線照射装置35と、イオン交換体充填装置36と、第2の脱酸素装置37と、を有している。これらの装置やタンクは被処理水の流通方向Dに関し上流から下流に向かって、母管L1にこの順序で直列に配置されている。図示は省略するが、中間タンク33の他に、前処理装置2や純水製造装置3の各装置、例えば活性炭塔22、イオン除去装置31、逆浸透膜装置32の処理水を貯留するタンクを設けてもよい。第2の脱酸素装置37の下流で戻り配管L2が母管L1から分岐し、中間タンク33に合流している。図示は省略するが、戻り配管L2の他に、純水製造装置3のいずれかの装置の処理水の一部を上流側のタンク等に戻す配管を設けてもよい。 The pretreatment device 2 includes a filter 21 for removing relatively large particles such as dust, and an activated carbon tower 22 for removing impurities such as high-molecular-weight organic matter and oxidizing agents. The filter 21 can be, for example, a sand filter. The pure water production system 3 includes an ion removal device 31, a reverse osmosis membrane device 32, an intermediate tank 33, a first deoxygenation device 34, an ultraviolet irradiation device 35, an ion exchanger packing device 36, and a second deoxygenation device 37. These devices and tanks are arranged in series in this order on the main pipe L1 from upstream to downstream in the flow direction D of the water to be treated. Although not shown, in addition to the intermediate tank 33, tanks for storing treated water from each device of the pretreatment device 2 and the pure water production system 3, such as the activated carbon tower 22, the ion removal device 31, and the reverse osmosis membrane device 32, may also be provided. Downstream of the second deoxygenation device 37, a return pipe L2 branches off from the main pipe L1 and merges with the intermediate tank 33. Although not shown in the figure, in addition to the return pipe L2, a pipe may be provided to return a portion of the treated water from one of the devices in the pure water production system 3 to an upstream tank or the like.
イオン除去装置31は、カチオン交換樹脂が充填されたカチオン塔(図示せず)と、脱炭酸塔(図示せず)と、アニオン交換樹脂が充填されたアニオン塔(図示せず)と、を有し、これらは上流から下流に向けてこの順で直列に配置されている。脱炭酸塔の代わりに脱炭酸膜を設けてもよい。イオン除去装置31に代えて、カルシウムやマグネシウムなどの硬度成分を除去する軟化装置を上流側に、電気式脱イオン水製造装置(EDI)を下流側に直列配置することも可能である。EDIは、紫外線照射装置35における有機物分解処理の阻害物質となるイオン成分を除去する。 The ion removal device 31 comprises a cation tower (not shown) filled with cation exchange resin, a decarbonation tower (not shown), and an anion tower (not shown) filled with anion exchange resin, which are arranged in series from upstream to downstream. A decarbonation membrane may be provided instead of the decarbonation tower. Instead of the ion removal device 31, a softener that removes hardness components such as calcium and magnesium may be arranged upstream, and an electrodeionized water production device (EDI) may be arranged downstream in series. The EDI removes ionic components that inhibit the organic matter decomposition process in the ultraviolet irradiation device 35.
逆浸透膜装置32はイオンなどの不純物を除去する。本実施形態では逆浸透膜装置32の上流にイオン除去装置31が設けられているため、逆浸透膜装置32は主に有機物などの非荷電物質を除去する。逆浸透膜装置32は多段に設けてもよい。被処理水の全有機炭素濃度が高いと、紫外線照射装置35における有機物の分解効率が低下する。逆浸透膜装置32で有機物を除去することで、下流側の紫外線照射装置35の負荷が低減される。逆浸透膜装置32の前段にpH調整機構を備えていてもよい。逆浸透膜装置32の処理水は中間タンク33に貯留される。 The reverse osmosis membrane device 32 removes impurities such as ions. In this embodiment, an ion removal device 31 is provided upstream of the reverse osmosis membrane device 32, so the reverse osmosis membrane device 32 mainly removes uncharged substances such as organic matter. The reverse osmosis membrane device 32 may be provided in multiple stages. If the total organic carbon concentration of the water to be treated is high, the efficiency of decomposing organic matter in the ultraviolet irradiation device 35 decreases. Removing organic matter with the reverse osmosis membrane device 32 reduces the load on the ultraviolet irradiation device 35 downstream. A pH adjustment mechanism may be provided upstream of the reverse osmosis membrane device 32. The treated water from the reverse osmosis membrane device 32 is stored in the intermediate tank 33.
第1の脱酸素装置34は、被処理水から酸素を除去し、被処理水中の溶存酸素濃度を低下させる。第1の脱酸素装置34は同時に揮発性有機物や炭酸などを気相中(2次側)に除去し、これらの水中の濃度を低減することもできる。第1の脱酸素装置34は紫外線照射装置35の上流側に位置しているため、紫外線照射装置35には溶存酸素濃度が低下した(調整された)被処理水が供給される。第1の脱酸素装置34の種類は溶存酸素を除去できるものであれば限定されず、例えば、真空脱気装置を用いることができる。一般的に真空脱気装置では、水の表面積を増大させるための気液接触材を脱気塔に充填し、脱気塔内の気体圧力を真空ポンプで減圧し、被処理水を真空状態におき、溶存酸素を除去する。溶存酸素濃度は、真空ポンプを用いて脱気塔内の真空度を調整することによって調整可能である。真空度は真空ポンプに接続されたインバータを用いて調整することができる。さらに、窒素を流入させることで脱気性能を向上することができる。この場合、溶存酸素濃度は、真空度と窒素流入量(窒素分圧)を調整することによって調整可能である。 The first deoxygenation device 34 removes oxygen from the water being treated, reducing the dissolved oxygen concentration in the water. The first deoxygenation device 34 can also simultaneously remove volatile organic compounds and carbon dioxide into the gas phase (secondary side) to reduce their concentrations in the water. Because the first deoxygenation device 34 is located upstream of the ultraviolet irradiation device 35, the water being treated with a reduced (adjusted) dissolved oxygen concentration is supplied to the ultraviolet irradiation device 35. The type of the first deoxygenation device 34 is not limited as long as it can remove dissolved oxygen; for example, a vacuum degassing device can be used. In general, a vacuum degassing device fills a degassing tower with a gas-liquid contact material to increase the surface area of the water, reduces the gas pressure in the degassing tower with a vacuum pump, and places the water being treated in a vacuum state to remove dissolved oxygen. The dissolved oxygen concentration can be adjusted by adjusting the degree of vacuum in the degassing tower using a vacuum pump. The degree of vacuum can be adjusted using an inverter connected to the vacuum pump. Furthermore, degassing performance can be improved by introducing nitrogen. In this case, the dissolved oxygen concentration can be adjusted by adjusting the degree of vacuum and the amount of nitrogen inflow (nitrogen partial pressure).
第1の脱酸素装置34として脱気膜装置を用いてもよい。この場合も真空脱気装置と同様に真空ポンプが用いられ、溶存酸素濃度は真空度を調整することによって調整可能である。真空度は真空ポンプに接続されたインバータを用いて調整することができる。なお、第1の脱酸素装置34における真空度や窒素流入量を自動で調整する場合は、例えば、紫外線照射装置35の被処理水中の溶存酸素濃度を測定装置(図示せず)で測定し、測定値に基づいて、制御装置(図示せず)が第1の脱酸素装置34における真空度や窒素流入量を調整することができる。他の第1の脱酸素装置34として、パラジウム(Pd)などの白金族触媒を担持した白金族触媒充填装置を用いてもよい。水素を添加した被処理水を白金族触媒と接触させることで、被処理水中の溶存酸素濃度を低減することができる。以上説明した第1の脱酸素装置34は1段構成でもよいし、複数の装置が直列に接続された多段構成でもよい。 A degassing membrane device may be used as the first deoxygenation device 34. In this case, a vacuum pump is used, as in the vacuum degassing device, and the dissolved oxygen concentration can be adjusted by adjusting the degree of vacuum. The degree of vacuum can be adjusted using an inverter connected to the vacuum pump. To automatically adjust the degree of vacuum and nitrogen inflow rate in the first deoxygenation device 34, for example, the dissolved oxygen concentration in the water being treated in the ultraviolet irradiation device 35 can be measured by a measuring device (not shown), and a control device (not shown) can adjust the degree of vacuum and nitrogen inflow rate in the first deoxygenation device 34 based on the measured value. Alternatively, a platinum catalyst-loaded device carrying a platinum catalyst such as palladium (Pd) may be used as the first deoxygenation device 34. By contacting the water being treated with hydrogen-added water with the platinum catalyst, the dissolved oxygen concentration in the water can be reduced. The first deoxygenation device 34 described above may be a single-stage configuration or a multi-stage configuration in which multiple devices are connected in series.
紫外線照射装置35は被処理水に紫外線を照射して被処理水に含まれる有機物を分解する。紫外線照射装置35から照射された紫外線は水と反応して過酸化水素を生成する。紫外線照射装置35として、例えば185nm、254nmの少なくともいずれかの波長の紫外線を発生させる紫外線照射装置(例えば、低圧紫外線照射装置)を用いることができる。紫外線の照射量は水の単位容積当たりに加えられる照射エネルギー(単位:kWh/m3)で定義されるため、照射量は紫外線照射装置35の点灯ランプの本数や調光によって調整できるほか、被処理水の流量を変えることでも調整できる。なお、紫外線照射装置35における紫外線照射量を自動で調整する場合は、例えば、紫外線照射装置35の入口部35Aにおける被処理水の全有機炭素濃度(以下、TOC濃度という)をTOC計(図示せず)で測定し、測定値に基づいて、制御装置(図示せず)が紫外線照射装置35における点灯ランプの本数や調光、被処理水の流量を調整することができる。 The ultraviolet irradiation device 35 irradiates the water to be treated with ultraviolet light to decompose organic matter contained in the water. The ultraviolet light emitted from the ultraviolet irradiation device 35 reacts with the water to produce hydrogen peroxide. The ultraviolet irradiation device 35 can be, for example, an ultraviolet irradiation device (e.g., a low-pressure ultraviolet irradiation device) that generates ultraviolet light with at least one of wavelengths of 185 nm and 254 nm. The ultraviolet irradiation dose is defined as the irradiation energy applied per unit volume of water (unit: kWh/m 3 ). Therefore, the irradiation dose can be adjusted by adjusting the number of lamps and dimming of the ultraviolet irradiation device 35, as well as by changing the flow rate of the water to be treated. To automatically adjust the ultraviolet irradiation dose in the ultraviolet irradiation device 35, for example, a TOC meter (not shown) can be used to measure the total organic carbon concentration (hereinafter referred to as TOC concentration) of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35, and a control device (not shown) can adjust the number of lamps and dimming of the ultraviolet irradiation device 35 and the flow rate of the water to be treated based on the measured value.
イオン交換体充填装置36は、紫外線の照射によって紫外線照射装置35の処理水中に発生した有機物の分解生成物を除去する。イオン交換体充填装置36にはイオン交換樹脂が充填されているが、モノリス状ないし繊維状のイオン交換体を充填してもよい。イオン交換体充填装置36はイオン交換樹脂を充填したEDIでもよい。EDIは連続再生式であるため、イオン交換樹脂の再生工程が不要となる。 The ion exchanger packing device 36 removes organic decomposition products generated in the treated water from the ultraviolet irradiation device 35 by irradiating it with ultraviolet light. The ion exchanger packing device 36 is packed with ion exchange resin, but it may also be packed with monolithic or fibrous ion exchangers. The ion exchanger packing device 36 may also be an EDI packed with ion exchange resin. Because EDI is a continuous regeneration type, there is no need for a regeneration process for the ion exchange resin.
第2の脱酸素装置37はイオン交換体充填装置36の下流に位置し、第1の脱酸素装置34と同様の構成を有することができる。第2の脱酸素装置37は、被処理水中の溶存酸素、炭酸等を除去する。 The second deoxygenation device 37 is located downstream of the ion exchanger packing device 36 and can have a configuration similar to that of the first deoxygenation device 34. The second deoxygenation device 37 removes dissolved oxygen, carbon dioxide, etc. from the water to be treated.
第2の脱酸素装置37の処理水はサブシステムに送られる。第2の脱酸素装置37の下流で分岐する戻り配管L2はサブシステムに供給する純水の流量を調整する。この目的で、戻り配管L2には流量調整用の弁V1が配置されている。戻り配管L2は純水製造装置3の最下流の位置に設けるのが好ましいため、第2の脱酸素装置37の下流で母管L1から分岐しているが、第2の脱酸素装置37の上流で母管L1から分岐する他の戻り配管を設けてもよい。 The treated water from the second deoxygenation device 37 is sent to the subsystem. The return pipe L2, which branches off downstream of the second deoxygenation device 37, adjusts the flow rate of the pure water supplied to the subsystem. For this purpose, a flow rate adjustment valve V1 is provided in the return pipe L2. Since the return pipe L2 is preferably located at the most downstream position of the pure water production system 3, it branches off from the main pipe L1 downstream of the second deoxygenation device 37, but another return pipe may be provided that branches off from the main pipe L1 upstream of the second deoxygenation device 37.
上述のように、紫外線照射装置35は水から過酸化水素を発生させるため、紫外線照射装置35の下流側を流れる水には過酸化水素が含まれる。また、過酸化水素が含まれる水は戻り配管L2によって中間タンク33に戻されるが、中間タンク33と紫外線照射装置35との間には過酸化水素の除去手段が設けられていないので、中間タンク33とサブシステムの入口との間の区間を流れる水は過酸化水素を含む。換言すれば、紫外線照射装置35に供給される被処理水は過酸化水素を含んでいる。一方、原水に含まれる過酸化水素は活性炭塔22でほぼ除去されるため、イオン除去装置31と中間タンク33との間の区間を流れる水は実質的に過酸化水素を含んでいない。従って、紫外線照射装置35に供給される被処理水の過酸化水素濃度は、イオン除去装置31と中間タンク33との間の区間を流れる水の過酸化水素濃度より高い。本実施形態では、中間タンク33とサブシステムの入口との間に過酸化水素除去手段(例えば第2の実施形態の過酸化水素除去装置38、還元剤添加装置等)が設けられていないため、紫外線照射装置35の出口とサブシステムの入口との間を流れる水及び戻り配管L2を流れる水の過酸化水素濃度も、イオン除去装置31と中間タンク33との間の区間を流れる水の過酸化水素濃度より高い。なお、イオン交換体充填装置36は微量の過酸化水素を除去するが、除去効率が極めて低い。過酸化水素除去手段はイオン交換体充填装置36より過酸化水素の除去効率の高い手段をいう。 As described above, the ultraviolet irradiation device 35 generates hydrogen peroxide from water, so the water flowing downstream of the ultraviolet irradiation device 35 contains hydrogen peroxide. Furthermore, the water containing hydrogen peroxide is returned to the intermediate tank 33 via the return pipe L2. However, because no hydrogen peroxide removal means is provided between the intermediate tank 33 and the ultraviolet irradiation device 35, the water flowing through the section between the intermediate tank 33 and the inlet of the subsystem contains hydrogen peroxide. In other words, the water to be treated supplied to the ultraviolet irradiation device 35 contains hydrogen peroxide. On the other hand, because the hydrogen peroxide contained in the raw water is almost entirely removed by the activated carbon tower 22, the water flowing through the section between the ion removal device 31 and the intermediate tank 33 contains virtually no hydrogen peroxide. Therefore, the hydrogen peroxide concentration in the water to be treated supplied to the ultraviolet irradiation device 35 is higher than the hydrogen peroxide concentration in the water flowing through the section between the ion removal device 31 and the intermediate tank 33. In this embodiment, no hydrogen peroxide removal means (such as the hydrogen peroxide removal device 38 of the second embodiment or a reducing agent addition device) is provided between the intermediate tank 33 and the inlet of the subsystem. Therefore, the hydrogen peroxide concentration in the water flowing between the outlet of the ultraviolet irradiation device 35 and the inlet of the subsystem and the water flowing through the return pipe L2 is higher than the hydrogen peroxide concentration in the water flowing in the section between the ion removal device 31 and the intermediate tank 33. Note that while the ion exchanger filling device 36 removes trace amounts of hydrogen peroxide, its removal efficiency is extremely low. The hydrogen peroxide removal means refers to a means that removes hydrogen peroxide more efficiently than the ion exchanger filling device 36.
(水処理方法)
次に、水処理装置1を用いた水処理方法について説明する。上述の通り、本実施形態では、前処理装置2と純水製造装置3を構成する各装置に被処理水が順次流れ、純水が製造される。特に本実施形態では、紫外線照射装置35の入口部35Aにおいて全有機炭素濃度10μg/L以下、溶存酸素濃度30μg/L以上という特定の水質(以下、特定水質という)をもった被処理水が紫外線照射装置35に供給される。紫外線照射装置35の入口部35Aから紫外線照射装置35に供給された被処理水には、紫外線照射装置35から紫外線が照射される。紫外線照射量が高いとエネルギーコストが高くなるため、紫外線照射量は0.1kWh/m3以下が好ましく、0.08kWh/m3以下がより好ましく、0.06kWh/m3以下がさらに好ましい。紫外線照射量が低すぎると有機物の分解効率が低下するため、紫外線照射量は0.02kWh/m3以上であることが好ましい。全有機炭素濃度が低いと後段のイオン交換体充填装置36などの負荷や紫外線照射量が小さくて済むため、全有機炭素濃度は5μg/L以下であることが好ましい。
(Water treatment method)
Next, a water treatment method using the water treatment device 1 will be described. As described above, in this embodiment, the water to be treated flows sequentially through the pretreatment device 2 and the various devices constituting the pure water production device 3, producing pure water. In particular, in this embodiment, the water to be treated having a specific water quality (hereinafter referred to as specific water quality) of a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at the inlet 35A of the ultraviolet irradiation device 35 is supplied to the ultraviolet irradiation device 35. The water to be treated supplied to the ultraviolet irradiation device 35 from the inlet 35A of the ultraviolet irradiation device 35 is irradiated with ultraviolet light from the ultraviolet irradiation device 35. Because a high ultraviolet irradiation dose increases energy costs, the ultraviolet irradiation dose is preferably 0.1 kWh/m 3 or less, more preferably 0.08 kWh/m 3 or less, and even more preferably 0.06 kWh/m 3 or less. Because a too low ultraviolet irradiation dose reduces the decomposition efficiency of organic matter, the ultraviolet irradiation dose is preferably 0.02 kWh/m 3 or more. If the total organic carbon concentration is low, the load on the downstream ion exchanger packing device 36 and the amount of ultraviolet radiation can be reduced, so the total organic carbon concentration is preferably 5 μg/L or less.
図2は、紫外線照射装置35の入口部35AにおけるTOC濃度、溶存酸素濃度(以下、DO濃度という)及び過酸化水素濃度(以下、H2O2濃度という)と、紫外線照射装置35の有機物分解性能と、の関係を模式的に示している。一般に、過酸化水素は酸化促進剤であるので、紫外線照射装置35の被処理水に過酸化水素を添加することによって有機物の分解が促進される。例えば、DO濃度が30μg/L未満の場合、TOC濃度に拘わらず有機物の分解が促進される。DO濃度が30μg/L以上であっても、TOC濃度が10μg/Lより大きければ有機物の分解が促進される。これに対し、特定水質をもった水の場合、過大な濃度の過酸化水素は紫外線による有機物の分解効率を低下させる。これは、過酸化水素が紫外線による有機物分解の阻害物質となるためであると考えられる。従って、特定水質をもった被処理水についてはH2O2濃度が低い方が有機物の分解が促進しやすい。H2O2濃度は30μg/L以下が好ましく、20μg/L以下がより好ましく、10μg/L未満がさらに好ましく、5μg/L以下がより一層好ましい。但し、後述する理由のため、H2O2濃度は1μg/Lより大きいことが好ましく、2μg/L以上がさらに好ましい。 FIG. 2 shows a schematic diagram of the relationship between the TOC concentration, dissolved oxygen concentration (hereinafter referred to as DO concentration), and hydrogen peroxide concentration (hereinafter referred to as H2O2 concentration) at the inlet 35A of the ultraviolet irradiation device 35 and the organic matter decomposition performance of the ultraviolet irradiation device 35. Generally, hydrogen peroxide is an oxidation promoter, so adding hydrogen peroxide to the water being treated by the ultraviolet irradiation device 35 promotes the decomposition of organic matter. For example, when the DO concentration is less than 30 μg/L, the decomposition of organic matter is promoted regardless of the TOC concentration. Even if the DO concentration is 30 μg/L or higher, the decomposition of organic matter is promoted as long as the TOC concentration is greater than 10 μg/L. In contrast, in water with specific water quality, excessive hydrogen peroxide concentrations reduce the efficiency of organic matter decomposition by ultraviolet light. This is thought to be because hydrogen peroxide acts as an inhibitor of organic matter decomposition by ultraviolet light. Therefore, for water to be treated with a specific water quality, a lower H2O2 concentration promotes the decomposition of organic matter. The H2O2 concentration is preferably 30 μg/L or less, more preferably 20 μg/L or less, even more preferably less than 10 μg/L, and even more preferably 5 μg/L or less. However, for reasons described below, the H2O2 concentration is preferably greater than 1 μg/L, and even more preferably greater than 2 μg/L.
特定水質をもたない被処理水については、有機物の分解のために過酸化水素を添加すること(またはH2O2濃度を低下させる処理を行わないこと)が効果的である。しかし、例えばDO濃度を30μg/L未満にするためには第1の脱酸素装置34のコストアップや真空ポンプの動力費の増加が必要となることがあり、DO濃度を30μg/L以上とする方が望ましい場合もある。TOC濃度についても、上流側のイオン除去装置31や逆浸透膜装置32のコストアップや運転コストを抑えるため、紫外線照射装置35の入口部35Aである程度大きな値となることが合理的である場合がある。このように、紫外線照射装置35の被処理水が特定水質をもつか否かは、水処理装置1の設計、サブシステムを含めた超純水製造装置全体の設計、原水の水質などにも依存し、紫外線照射装置35の有機物分解性能の観点だけでは決まらないことがある。しかし、紫外線照射装置35の入口部35Aにおける被処理水が特定水質をもつ場合は、H2O2濃度を低下させる運転が好ましい。 For water not meeting the specified water quality standard, adding hydrogen peroxide to decompose organic matter (or not performing treatment to reduce the H2O2 concentration) is effective. However, reducing the DO concentration to less than 30 μg/L may require increased costs for the first deoxidizer 34 and increased power costs for the vacuum pump. Therefore, it may be preferable to maintain the DO concentration at 30 μg/L or higher. It may also be reasonable to maintain a relatively high TOC concentration at the inlet 35A of the ultraviolet irradiation device 35 in order to reduce the costs and operating costs of the upstream ion removal device 31 and reverse osmosis membrane device 32. Thus, whether the water being treated by the ultraviolet irradiation device 35 meets the specified water quality standard depends on factors such as the design of the water treatment device 1, the design of the entire ultrapure water production system including its subsystems, and the quality of the raw water. This determination cannot be based solely on the organic matter decomposition performance of the ultraviolet irradiation device 35. However, when the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 has a specific water quality, it is preferable to operate the device to reduce the H 2 O 2 concentration.
(DO濃度)
紫外線照射装置35の入口部35Aにおける被処理水のDO濃度は30μg/L以上である限り限定されないが、1000μg/L未満であることが好ましい。後述の実施例3で述べるように、1000μg/L未満とすることで紫外線による有機物の分解性能が向上する。紫外線照射装置35の入口部35Aにおける被処理水のDO濃度は500μg/L以下がより好ましく、100μg/L以下がさらに好ましい。被処理水のDO濃度は紫外線照射装置35の上流に設けられた第1の脱酸素装置34によって調整することができる。DO濃度は例えば、第1の脱酸素装置34と紫外線照射装置35との間に設けたDO濃度計(図示せず)でオンライン測定することができる。
(DO concentration)
The DO concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 is not limited as long as it is 30 μg/L or more, but is preferably less than 1000 μg/L. As described in Example 3 below, a concentration of less than 1000 μg/L improves the decomposition performance of organic matter by ultraviolet light. The DO concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 is more preferably 500 μg/L or less, and even more preferably 100 μg/L or less. The DO concentration of the water to be treated can be adjusted by the first deoxygenation device 34 provided upstream of the ultraviolet irradiation device 35. The DO concentration can be measured online, for example, using a DO concentration meter (not shown) provided between the first deoxygenation device 34 and the ultraviolet irradiation device 35.
有機物の分解効率を上げるために、紫外線照射装置35から照射される紫外線の照射量を調整することができる(方法A)。また、溶存酸素は紫外線を吸収する性質があるため、DO濃度が低いと溶存酸素に吸収される紫外線が減り、有機物の分解効率が上がる。従って、有機物の分解効率を上げるために、第1の脱酸素装置34によって被処理水のDO濃度を調整することもできる(方法B)。方法Aと方法Bは組み合わせて実行してもよいし、いずれかだけを実行してもよいが、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度が30μg/L以下となる範囲で行うことが好ましい。中間タンク33と紫外線照射装置35との間の任意の位置(本実施形態では、第1の脱酸素装置34と紫外線照射装置35との間)に過酸化水素のサンプリング配管L3を設けてあり、サンプリング配管L3で採取した水から紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度を計測することができる。H2O2濃度は中間タンク33と紫外線照射装置35との間の任意の位置(例えば、第1の脱酸素装置34と紫外線照射装置35との間)に設けたH2O2濃度計(図示せず)でオンライン測定してもよい。方法Aで紫外線の照射量を調整する場合、通常は紫外線の照射量を増加させるが、有機物の分解効率が大きく低下しない範囲で紫外線の照射量を減少させてもよい。方法Bで被処理水のDO濃度を調整する場合、通常は被処理水のDO濃度を低下させるが、有機物の分解効率が大きく低下しない範囲で被処理水のDO濃度を増加させてもよい。 To improve the decomposition efficiency of organic matter, the amount of ultraviolet light emitted from the ultraviolet irradiation device 35 can be adjusted (Method A). Furthermore, because dissolved oxygen has the property of absorbing ultraviolet light, a low DO concentration reduces the amount of ultraviolet light absorbed by dissolved oxygen, thereby improving the decomposition efficiency of organic matter. Therefore, to improve the decomposition efficiency of organic matter, the DO concentration of the treated water can also be adjusted using the first deoxygenation device 34 (Method B). Methods A and B may be performed in combination, or either method may be performed alone. However, it is preferable to perform these methods so that the H2O2 concentration of the treated water at the inlet 35A of the ultraviolet irradiation device 35 is 30 μg/L or less. A hydrogen peroxide sampling pipe L3 is installed at any position between the intermediate tank 33 and the ultraviolet irradiation device 35 (in this embodiment, between the first deoxygenation device 34 and the ultraviolet irradiation device 35). The H2O2 concentration of the treated water at the inlet 35A of the ultraviolet irradiation device 35 can be measured from the water sampled through the sampling pipe L3 . The H2O2 concentration may be measured online using an H2O2 concentration meter (not shown) installed at any position between the intermediate tank 33 and the ultraviolet irradiation device 35 (for example, between the first deoxygenation device 34 and the ultraviolet irradiation device 35). When adjusting the ultraviolet irradiation amount using method A, the ultraviolet irradiation amount is usually increased, but it may also be decreased to the extent that the decomposition efficiency of organic matter is not significantly reduced. When adjusting the DO concentration of the water to be treated using method B, the DO concentration of the water to be treated is usually decreased, but it may also be increased to the extent that the decomposition efficiency of organic matter is not significantly reduced.
方法Aと方法Bは紫外線照射装置35の被処理水または処理水中のTOC濃度に応じて実行することができる。具体的には、紫外線照射装置35の入口側(例えば、第1の脱酸素装置34と紫外線照射装置35との間)と、紫外線照射装置35の出口側(例えば、第2の脱酸素装置37の出口)にTOC計を配置する。そして、紫外線照射装置35の被処理水のTOC濃度が所定の値を超えたとき、または紫外線照射装置35の処理水のTOC濃度が所定の値を超えたときに、方法Aと方法Bの少なくともいずれか、好ましくは両方を実行することができる。なお、紫外線照射装置35の被処理水または処理水のTOC濃度が所定の値を超えていない場合でも、方法Aと方法Bの少なくともいずれかを実行することができる。 Method A and Method B can be implemented depending on the TOC concentration in the water to be treated or the treated water from the ultraviolet irradiation device 35. Specifically, a TOC meter is placed on the inlet side of the ultraviolet irradiation device 35 (e.g., between the first deoxygenation device 34 and the ultraviolet irradiation device 35) and on the outlet side of the ultraviolet irradiation device 35 (e.g., at the outlet of the second deoxygenation device 37). Then, when the TOC concentration of the water to be treated from the ultraviolet irradiation device 35 exceeds a predetermined value, or when the TOC concentration of the treated water from the ultraviolet irradiation device 35 exceeds a predetermined value, at least one of Method A and Method B, or preferably both, can be implemented. Note that at least one of Method A and Method B can be implemented even if the TOC concentration of the water to be treated or the treated water from the ultraviolet irradiation device 35 does not exceed the predetermined value.
第1の脱酸素装置34と紫外線照射装置35は紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度を30μg/L以下に調整する手段でもある。紫外線は水から過酸化水素を発生させるため、紫外線の照射量を上げれば過酸化水素の発生量も増える。DO濃度が低いと溶存酸素に吸収される紫外線が減るため、紫外線の照射量が同じであってもより多くの過酸化水素が発生する。発生した過酸化水素の一部は戻り配管L2によって紫外線照射装置35の上流に戻される。従って、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度は、第1の脱酸素装置34と紫外線照射装置35の少なくともいずれかによって調整することができる。上述のように、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度は、サンプリング配管L3で採取した水から計測することができる。計測されたH2O2濃度が30μg/Lより低い所定の基準値(例えば、25μg/L)を超えたときは、紫外線の照射量とDO濃度の少なくともいずれかを調整することで、被処理水中のH2O2濃度を調整することができる。 The first deoxygenation device 34 and ultraviolet irradiation device 35 also serve as means for adjusting the H2O2 concentration of the water to 30 μg/L or less at the inlet 35A of the ultraviolet irradiation device 35. Because ultraviolet light generates hydrogen peroxide from water, increasing the amount of ultraviolet light irradiation also increases the amount of hydrogen peroxide generated. When the DO concentration is low, less ultraviolet light is absorbed by dissolved oxygen, resulting in the generation of more hydrogen peroxide even with the same amount of ultraviolet light irradiation. A portion of the generated hydrogen peroxide is returned upstream of the ultraviolet irradiation device 35 via the return pipe L2 . Therefore, the H2O2 concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 can be adjusted by at least one of the first deoxygenation device 34 and the ultraviolet irradiation device 35. As described above, the H2O2 concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 can be measured from water sampled via the sampling pipe L3. When the measured H2O2 concentration exceeds a predetermined standard value (e.g., 25 μg/L) lower than 30 μg/L, the H2O2 concentration in the treated water can be adjusted by adjusting at least one of the ultraviolet irradiation amount and the DO concentration.
前述の通り原水に含まれる過酸化水素は活性炭塔22でほぼ除去される。このため、紫外線照射装置35の入口部35Aに存在する過酸化水素は、紫外線照射装置35で発生し戻り配管L2によって紫外線照射装置35の上流に戻されるものにほぼ限られる。そこで、被処理水のH2O2濃度が30μg/L以下となるように戻り水の流量を変えることもできる。具体的には、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度をサンプリング配管L3で計測し、計測されたH2O2濃度が30μg/Lより低い所定の基準値(例えば、25μg/L)を超えたときに、戻り配管L2から紫外線照射装置35の上流に戻す処理水の流量を減らす。これによって、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度を30μg/L以下となるように調整することができる。例えば、有機物の分解効率を上げるために紫外線の照射量を上げると処理水中のH2O2濃度が上昇する。この場合、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度の増加を抑えるため、弁V1の開度を絞り戻り水の流量を減らすことができる。 As described above, hydrogen peroxide contained in the raw water is almost entirely removed in the activated carbon tower 22. Therefore, the hydrogen peroxide present at the inlet 35A of the ultraviolet irradiation device 35 is almost entirely limited to that generated in the ultraviolet irradiation device 35 and returned upstream of the ultraviolet irradiation device 35 via the return pipe L2. Therefore, the flow rate of the return water can be adjusted so that the H2O2 concentration of the water to be treated is 30 μg /L or less. Specifically, the H2O2 concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 is measured using the sampling pipe L3. When the measured H2O2 concentration exceeds a predetermined reference value (e.g., 25 μg/L) lower than 30 μg/L, the flow rate of the treated water returned from the return pipe L2 to the upstream of the ultraviolet irradiation device 35 is reduced. This allows the H2O2 concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 to be adjusted to 30 μg/L or less. For example, increasing the amount of ultraviolet radiation to improve the decomposition efficiency of organic matter increases the H2O2 concentration in the treated water. In this case, the opening of valve V1 can be narrowed to reduce the flow rate of return water in order to suppress the increase in the H2O2 concentration in the water to be treated at the inlet 35A of the ultraviolet radiation device 35.
ただし、戻り水の流量は本来、ユースポイントでの超純水使用量及びこれに伴うサブシステムへの純水供給流量の変動に対応するように決められる。紫外線照射装置35の入口部35AにおけるH2O2濃度を下げるために戻り水の流量を下げると、ユースポイントでの超純水使用量の変動に対応することが難しくなる場合がある。従って、サブシステムへの純水供給流量を適切に調整可能とするため、紫外線照射装置35の入口部35AにおけるH2O2濃度は1μg/Lより大きいことが好ましく、2μg/L以上がより好ましい。紫外線照射装置35の入口部35AにおけるH2O2濃度を下げるためには紫外線照射量を下げることも有効であるが、紫外線照射装置35での有機物の分解効率が低下する。このように、紫外線照射装置35の入口部35AにおけるH2O2濃度を1μg/L以下まで下げると、別の観点から不利となる可能性がある。 However, the return water flow rate is originally determined to accommodate fluctuations in the amount of ultrapure water used at the point of use and the resulting fluctuations in the amount of pure water supplied to the subsystem. Reducing the return water flow rate to lower the H2O2 concentration at the inlet 35A of the UV irradiation device 35 may make it difficult to accommodate fluctuations in the amount of ultrapure water used at the point of use. Therefore, to appropriately adjust the pure water supply flow rate to the subsystem, the H2O2 concentration at the inlet 35A of the UV irradiation device 35 is preferably greater than 1 μg/L, and more preferably 2 μg/L or greater. Reducing the UV irradiation dose is also effective in reducing the H2O2 concentration at the inlet 35A of the UV irradiation device 35, but this reduces the decomposition efficiency of organic matter in the UV irradiation device 35. Thus, reducing the H2O2 concentration at the inlet 35A of the UV irradiation device 35 to 1 μg/L or less may be disadvantageous from another perspective.
(第2の実施形態)
図3は本発明の第2の実施形態に係る水処理装置1の概略構成を示している。本実施形態の水処理装置1は、紫外線照射装置35及びイオン交換体充填装置36の下流且つ第2の脱酸素装置37の上流に位置する過酸化水素除去装置38を有している。第2の実施形態はこの点を除き第1の実施形態と同じである。過酸化水素除去装置38は、紫外線照射装置35から紫外線が照射された処理水から、過酸化水素の一部を除去する。過酸化水素の一部が除去された処理水の一部は、戻り配管L2を通って紫外線照射装置35の上流に戻される。従って、過酸化水素除去装置38と戻り配管L2は、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度を30μg/L以下に調整する手段である。本実施形態では戻り配管L2を通る戻り水が過酸化水素をほとんど含まないため、紫外線照射装置35の入口部35Aにおける被処理水のH2O2濃度の増加を抑えるために弁V1の開度を上げ、戻り水の流量を増やすことができる。
Second Embodiment
FIG. 3 shows a schematic configuration of a water treatment device 1 according to a second embodiment of the present invention. The water treatment device 1 of this embodiment includes a hydrogen peroxide removal device 38 located downstream of the ultraviolet irradiation device 35 and the ion exchanger filling device 36 and upstream of the second deoxidizer 37. The second embodiment is identical to the first embodiment except for this point. The hydrogen peroxide removal device 38 removes a portion of the hydrogen peroxide from the treated water irradiated with ultraviolet light from the ultraviolet irradiation device 35. The portion of the treated water from which the hydrogen peroxide has been removed is returned upstream of the ultraviolet irradiation device 35 through the return pipe L2. Therefore, the hydrogen peroxide removal device 38 and the return pipe L2 function as a means for adjusting the H2O2 concentration of the treated water at the inlet 35A of the ultraviolet irradiation device 35 to 30 μg/L or less. In this embodiment, since the return water passing through the return pipe L2 contains almost no hydrogen peroxide, the flow rate of the return water can be increased by increasing the aperture of the valve V1 to suppress an increase in the H2O2 concentration of the treated water at the inlet 35A of the ultraviolet irradiation device 35.
過酸化水素除去装置38は、アニオン交換体(例えば樹脂)に白金族金属からなる白金族触媒が担持された白金族触媒充填装置である。白金族金属としては、白金(Pt)、パラジウム(Pd)、ルテニウム(Ru)、ロジウム(Rh)、オスミウム(Os)、イリジウム(Ir)などがあげられ、これらの1種類を単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。これらの白金族金属の中ではPtとPdが好ましく、コストの観点からはPdが好ましい。被処理水を白金族触媒と接触させることで、被処理水中のH2O2濃度を低減することができる。なお、DO濃度を低下させるため、白金族触媒充填装置の上流側に水素添加部(図示せず)を設けてもよい。代替構成として、Pdなどの金属触媒が担持されたイオン交換体をEDIに充填してもよい。この場合、EDIの陰極で発生する水素を金属触媒に接触させる水素として利用することができる。 The hydrogen peroxide removal device 38 is a platinum group catalyst-loaded device in which a platinum group catalyst made of a platinum group metal is supported on an anion exchanger (e.g., resin). Examples of platinum group metals include platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os), and iridium (Ir). These metals may be used alone or in combination. Among these platinum group metals, Pt and Pd are preferred, with Pd being preferred from a cost perspective. Contacting the treated water with a platinum group catalyst can reduce the H2O2 concentration in the treated water. A hydrogen addition section (not shown) may be provided upstream of the platinum group catalyst-loaded device to reduce the DO concentration. Alternatively, an ion exchanger supported on a metal catalyst such as Pd may be loaded into the EDI. In this case, hydrogen generated at the cathode of the EDI can be used to contact the metal catalyst.
上述の各実施形態ではH2O2濃度を30μg/L以下に調整しているが、調整を行わなくとも紫外線照射装置35の入口部35Aにおける被処理水の過酸化水素濃度が30μg/L以下である場合、過酸化水素濃度の調整は不要である。前述の通り、第1の実施形態では活性炭塔22と中間タンク33との間を流れる水にほとんど過酸化水素が含まれないため、紫外線照射装置35の入口部35Aに存在する過酸化水素は、紫外線照射装置35で発生し戻り配管L2によって紫外線照射装置35の上流に戻されるものにほぼ限られる。過酸化水素濃度は紫外線照射装置35の紫外線照射量、戻り配管L2を通る戻り水の流量などに依存するため、過酸化水素濃度の調整が不要な場合もある。第2の実施形態では活性炭塔22と中間タンク33との間を流れる水にほとんど過酸化水素が含まれず、過酸化水素除去装置38を設けたことにより、戻り配管L2を流れる水にもほとんど過酸化水素が含まれない。このため、紫外線照射装置35の紫外線照射量、戻り配管L2を通る戻り水の流量などに拘わらず、紫外線照射装置35の入口部35Aにおける被処理水の過酸化水素濃度はほぼゼロ(30μg/L以下)である。従って、第2の実施形態では過酸化水素濃度の調整は基本的に不要である。 In the above-described embodiments, the H2O2 concentration is adjusted to 30 μg/L or less. However, if the hydrogen peroxide concentration of the water to be treated at the inlet 35A of the ultraviolet irradiation device 35 is 30 μg/L or less even without adjustment, adjustment of the hydrogen peroxide concentration is not necessary. As described above, in the first embodiment, the water flowing between the activated carbon tower 22 and the intermediate tank 33 contains almost no hydrogen peroxide. Therefore, the hydrogen peroxide present at the inlet 35A of the ultraviolet irradiation device 35 is almost exclusively hydrogen peroxide generated in the ultraviolet irradiation device 35 and returned upstream to the ultraviolet irradiation device 35 via the return pipe L2. Because the hydrogen peroxide concentration depends on the amount of ultraviolet radiation emitted by the ultraviolet irradiation device 35 and the flow rate of the return water passing through the return pipe L2, adjustment of the hydrogen peroxide concentration may not be necessary. In the second embodiment, the water flowing between the activated carbon tower 22 and the intermediate tank 33 contains almost no hydrogen peroxide. Furthermore, the provision of the hydrogen peroxide removal device 38 ensures that the water flowing through the return pipe L2 also contains almost no hydrogen peroxide. Therefore, regardless of the amount of ultraviolet radiation from the ultraviolet radiation device 35, the flow rate of the return water passing through the return pipe L2, etc., the hydrogen peroxide concentration of the water to be treated at the inlet 35A of the ultraviolet radiation device 35 is almost zero (30 μg/L or less). Therefore, in the second embodiment, adjustment of the hydrogen peroxide concentration is basically not required.
(実施例1)
図4に示す試験装置を用いてTOC濃度低減率を測定した。試験装置は被処理水の流通方向Dに沿って脱酸素装置(脱気膜装置)41と紫外線照射装置42とイオン交換樹脂カラム43を順に配置したもので、紫外線照射装置42の処理水の一部をイオン交換樹脂カラム43に供給し、残りはブローラインから排水した。脱酸素装置41と紫外線照射装置42との間の被処理水のTOC濃度(T1)と、イオン交換樹脂カラム43の処理水のTOC濃度(T2)をそれぞれTOC計で測定した。TOC濃度低減率の定義は図4に示す。
Example 1
The TOC concentration reduction rate was measured using the test equipment shown in Figure 4. The test equipment consisted of a deoxygenation device (deaeration membrane device) 41, an ultraviolet irradiation device 42, and an ion exchange resin column 43 arranged in this order along the flow direction D of the water to be treated. A portion of the water treated by the ultraviolet irradiation device 42 was supplied to the ion exchange resin column 43, and the remainder was discharged through the blow line. The TOC concentration (T1) of the water to be treated between the deoxygenation device 41 and the ultraviolet irradiation device 42 and the TOC concentration (T2) of the water treated by the ion exchange resin column 43 were each measured using a TOC meter. The definition of the TOC concentration reduction rate is shown in Figure 4.
TOC濃度=10μg/L、DO濃度=100μg/L、H2O2濃度=5μg/Lに調整した原水に脱酸素装置41の上流で過酸化水素を添加し、脱酸素装置41に供給される被処理水のH2O2濃度を5μg/L(過酸化水素添加なし)、30μg/L、100μg/L、200μg/Lに調整した。脱気膜の内部の真空度を脱酸素装置41の真空ポンプで調整することで、紫外線照射装置42に供給される被処理水のDO濃度を5μg/L、30μg/L、100μg/L(真空ポンプオフ)に調整した。紫外線照射装置42への被処理水の供給流量を調整することで、紫外線照射量を0.06kWh/m3、0.1kWh/m3に調整した。H2O2濃度は吸光度法で測定した。その他の試験条件を下記に示す。
・紫外線照射装置42:低圧紫外線照射装置JPW(日本フォトサイエンス社製)
・イオン交換樹脂カラム43:カチオン交換樹脂AMBERJET 1024H形(オルガノ株式会社製)とアニオン交換樹脂AMBERJET 4002OH形(オルガノ株式会社製)の計300mLを容積比1:2で混床充填
・イオン交換樹脂のSV:60(/h)
・TOC計…M500e(VEOLIA社製)
・溶存酸素計…Orbisphere510(Hach社製)
Hydrogen peroxide was added upstream of the deoxygenation device 41 to raw water adjusted to a TOC concentration of 10 μg/L, a DO concentration of 100 μg/L, and an H2O2 concentration of 5 μg/L. The H2O2 concentration of the water to be treated supplied to the deoxygenation device 41 was adjusted to 5 μg/L (no hydrogen peroxide added), 30 μg/L, 100 μg/L, or 200 μg/L. The DO concentration of the water to be treated supplied to the ultraviolet irradiation device 42 was adjusted to 5 μg/L, 30 μg/L, or 100 μg/L (vacuum pump off) by adjusting the degree of vacuum inside the deoxygenation membrane using the vacuum pump of the deoxygenation device 41. The ultraviolet irradiation dose was adjusted to 0.06 kWh/ m3 or 0.1 kWh/ m3 by adjusting the flow rate of the water to be treated supplied to the ultraviolet irradiation device 42. The H2O2 concentration was measured by absorbance. Other test conditions are shown below.
Ultraviolet irradiation device 42: Low-pressure ultraviolet irradiation device JPW (manufactured by Japan Photo Science Co., Ltd.)
Ion exchange resin column 43: A mixed bed of cation exchange resin AMBERJET 1024H type (manufactured by Organo Corporation) and anion exchange resin AMBERJET 4002OH type (manufactured by Organo Corporation), totaling 300 mL, packed in a volume ratio of 1:2. Ion exchange resin SV: 60 (/h)
・TOC meter...M500e (VEOLIA)
・Dissolved oxygen meter: Orbisphere 510 (manufactured by Hach)
図5に紫外線照射量0.06kWh/m3でのH2O2濃度とTOC濃度低減率との関係を示す。図6に紫外線照射量0.1kWh/m3でのH2O2濃度とTOC濃度低減率との関係を示す。図5を参照すると、DO濃度5μg/Lでは、H2O2濃度が高くなるにつれTOC濃度低減率が向上し、100μg/L程度で飽和した。DO濃度30μg/Lでは、H2O2濃度30μg/LまではTOC濃度低減率はほぼ一定であるが、30μg/Lを超えると徐々に低下した。特にH2O2濃度200μg/LでTOC濃度低減率が大きく減少した。DO濃度100μg/LではDO濃度30μg/Lの場合と同様の傾向が得られ、H2O2濃度100μg/LでTOC濃度低減率が大きく減少した。以上より、DO濃度が30μg/L以上の場合、H2O2濃度を30μg/L以下に調整することで、紫外線による有機物分解性能の低下を抑制できることが分かった。また、図6に示すように、紫外線照射量0.1kWh/m3の場合も傾向は変わらないことから、紫外線照射量によらずH2O2濃度を30μg/L以下に調整することで、有機物を効率的に分解可能であることが分かった。 Figure 5 shows the relationship between H2O2 concentration and TOC concentration reduction rate at a UV irradiation dose of 0.06 kWh / m3 . Figure 6 shows the relationship between H2O2 concentration and TOC concentration reduction rate at a UV irradiation dose of 0.1 kWh / m3 . Referring to Figure 5, at a DO concentration of 5 μg/L, the TOC concentration reduction rate improved as the H2O2 concentration increased, saturating at approximately 100 μg/L. At a DO concentration of 30 μg/L, the TOC concentration reduction rate remained almost constant up to an H2O2 concentration of 30 μg/L, but gradually decreased above 30 μg /L. In particular, the TOC concentration reduction rate decreased significantly at an H2O2 concentration of 200 μg/L. At a DO concentration of 100 μg/L, a similar trend was observed as at a DO concentration of 30 μg/L, and the TOC concentration reduction rate decreased significantly at an H2O2 concentration of 100 μg/L. From the above, it was found that when the DO concentration is 30 μg/L or higher, the decrease in organic matter decomposition performance due to ultraviolet light can be suppressed by adjusting the H2O2 concentration to 30 μg/L or lower. Furthermore, as shown in Figure 6, the trend remains the same even when the ultraviolet light irradiation dose is 0.1 kWh/ m3 , which means that organic matter can be efficiently decomposed by adjusting the H2O2 concentration to 30 μg/L or lower regardless of the ultraviolet light irradiation dose.
(実施例2)
実施例1と同じ条件(DO濃度:30μg/L、照射量:0.1kWh/m3)でTOC濃度を10μg/L、30μg/L、50μg/Lに調整した。脱酸素装置41に供給される被処理水のH2O2濃度を5μg/L(過酸化水素添加なし)、30μg/L、100μg/L、200μg/Lに調整した。図7にH2O2濃度とTOC濃度低減率との関係を示す。TOC濃度10μg/Lでは、H2O2濃度が30μg/LまではTOC濃度低減率がほぼ一定であるが、30μg/Lを超えると徐々に低下した。TOC濃度30μg/L、50μg/Lでは、H2O2濃度が高くなるにつれTOC濃度低減率が向上した。以上より、TOC濃度が10μg/L以下の場合、H2O2濃度を30μg/L以下に調整することで、紫外線による有機物分解性能の低下を抑制できることが分かった。
Example 2
Under the same conditions as in Example 1 (DO concentration: 30 μg/L, irradiation dose: 0.1 kWh/ m3 ), the TOC concentration was adjusted to 10 μg/L, 30 μg/L, and 50 μg/L. The H2O2 concentration of the water to be treated supplied to the deoxygenation device 41 was adjusted to 5 μg/L (no hydrogen peroxide added), 30 μg/L, 100 μg/L, and 200 μg/L. Figure 7 shows the relationship between H2O2 concentration and the TOC concentration reduction rate. At a TOC concentration of 10 μg/L, the TOC concentration reduction rate remained almost constant up to an H2O2 concentration of 30 μg/L, but gradually decreased once the H2O2 concentration exceeded 30 μg/L. At TOC concentrations of 30 μg/L and 50 μg/L, the TOC concentration reduction rate improved as the H2O2 concentration increased. From the above, it was found that when the TOC concentration is 10 μg/L or less, the decrease in organic matter decomposition performance due to ultraviolet light can be suppressed by adjusting the H 2 O 2 concentration to 30 μg/L or less.
(実施例3)
実施例1と同じ条件(H2O2濃度:30μg/L、紫外線照射量:0.1kWh/m3)で、DO濃度を5μg/L、30μg/L、100μg/L、1000μg/L、10000μg/Lに調整した。図8にDO濃度とTOC濃度低減率との関係を示す。DO濃度5μg/L、30μg/L、100μg/Lについては実施例1と同じである。DO濃度30μg/L以上の範囲についてみると、DO濃度30μg/LでTOC濃度低減率が最も高く、DO濃度が増えるにつれTOC濃度低減率が低下している。以上より、DO濃度は1000μg/L以下が好ましいことが分かった。
Example 3
Under the same conditions as in Example 1 ( H2O2 concentration: 30 μg/L, UV irradiation dose: 0.1 kWh/ m3 ), the DO concentration was adjusted to 5 μg/L, 30 μg/L, 100 μg/L, 1000 μg/L, and 10,000 μg/L. Figure 8 shows the relationship between DO concentration and TOC concentration reduction rate. DO concentrations of 5 μg/L, 30 μg/L, and 100 μg/L are the same as in Example 1. Looking at the range of DO concentrations of 30 μg/L or more, the TOC concentration reduction rate was highest at a DO concentration of 30 μg/L, and decreased as the DO concentration increased. From the above, it was found that a DO concentration of 1000 μg/L or less is preferable.
1 水処理装置
2 前処理装置
3 純水製造装置
31 イオン除去装置
32 逆浸透膜装置
33 中間タンク
34 第1の脱酸素装置
35 紫外線照射装置
36 イオン交換体充填装置
37 第2の脱酸素装置
38 過酸化水素除去装置
REFERENCE SIGNS LIST 1 Water treatment device 2 Pretreatment device 3 Pure water production device 31 Ion removal device 32 Reverse osmosis membrane device 33 Intermediate tank 34 First deoxidation device 35 Ultraviolet irradiation device 36 Ion exchanger filling device 37 Second deoxidation device 38 Hydrogen peroxide removal device
Claims (9)
前記入口部から前記紫外線照射装置に供給された前記被処理水に前記紫外線照射装置から紫外線を照射することと、
前記紫外線照射装置の上流に設けられた脱酸素装置によって、前記入口部における前記被処理水の前記溶存酸素濃度を1000μg/L未満にすることと、を有し、
前記入口部における前記被処理水の過酸化水素濃度が30μg/L以下である水処理方法。 supplying water to be treated, the water having a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at an inlet of the ultraviolet irradiation device, to the ultraviolet irradiation device;
irradiating the water to be treated supplied from the inlet to the ultraviolet irradiation device with ultraviolet light from the ultraviolet irradiation device;
and reducing the dissolved oxygen concentration of the water to be treated at the inlet to less than 1000 μg/L by a deoxygenation device provided upstream of the ultraviolet irradiation device ,
A water treatment method, wherein the concentration of hydrogen peroxide in the water to be treated at the inlet is 30 μg/L or less.
前記入口部から前記紫外線照射装置に供給された前記被処理水に前記紫外線照射装置から紫外線を照射することと、
前記紫外線照射装置から紫外線が照射された処理水の一部を戻し配管によって前記紫外線照射装置の上流に戻すことと、
前記入口部における前記被処理水の過酸化水素濃度が30μg/L以下となる範囲で、
(A)前記紫外線照射装置から照射される紫外線の照射量を調整すること
(B)前記紫外線照射装置の上流に設けられた脱酸素装置によって前記入口部における前記被処理水の前記溶存酸素濃度を調整すること
の少なくともいずれかを行うことと、を有する水処理方法。 supplying water to be treated, the water having a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at an inlet of the ultraviolet irradiation device, to the ultraviolet irradiation device;
irradiating the water to be treated supplied from the inlet to the ultraviolet irradiation device with ultraviolet light from the ultraviolet irradiation device;
Returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device to an upstream side of the ultraviolet irradiation device through a return pipe;
The hydrogen peroxide concentration of the water to be treated at the inlet is in the range of 30 μg / L or less,
(A) adjusting the amount of ultraviolet light emitted from the ultraviolet irradiation device; and (B) adjusting the dissolved oxygen concentration of the water to be treated at the inlet portion using a deoxygenation device provided upstream of the ultraviolet irradiation device.
前記入口部から前記紫外線照射装置に供給された前記被処理水に前記紫外線照射装置から紫外線を照射することと、
前記紫外線照射装置から紫外線が照射された処理水の一部を前記紫外線照射装置の上流に戻すことと、
前記紫外線照射装置に供給される前記被処理水の過酸化水素濃度を計測することと、
計測された前記過酸化水素濃度が30μg/L以下となるように、前記紫外線照射装置の上流に戻す前記処理水の量を調整することと、を有し、
前記入口部における前記被処理水の過酸化水素濃度が30μg/L以下である水処理方法。 supplying water to be treated, the water having a total organic carbon concentration of 10 μg/L or less and a dissolved oxygen concentration of 30 μg/L or more at an inlet of the ultraviolet irradiation device, to the ultraviolet irradiation device;
irradiating the water to be treated supplied from the inlet to the ultraviolet irradiation device with ultraviolet light from the ultraviolet irradiation device;
Returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device upstream of the ultraviolet irradiation device;
measuring a hydrogen peroxide concentration of the water to be treated supplied to the ultraviolet irradiation device;
adjusting the amount of the treated water returned upstream of the ultraviolet irradiation device so that the measured hydrogen peroxide concentration is 30 μg/L or less ;
A water treatment method , wherein the concentration of hydrogen peroxide in the water to be treated at the inlet is 30 μg/L or less .
前記過酸化水素の一部が除去された前記処理水の一部を前記紫外線照射装置の上流に戻すことと、
を有する、請求項1から5のいずれか1項に記載の水処理方法。 removing a portion of the hydrogen peroxide from the treated water irradiated with ultraviolet light from the ultraviolet irradiation device by a hydrogen peroxide removal device provided downstream of the ultraviolet irradiation device;
returning a portion of the treated water from which a portion of the hydrogen peroxide has been removed upstream of the ultraviolet irradiation device;
The water treatment method according to any one of claims 1 to 5 , comprising:
前記紫外線照射装置の入口部における被処理水の過酸化水素濃度を30μg/L以下に調整する手段と、
を有し、
前記紫外線照射装置は前記入口部から供給された前記被処理水に紫外線を照射し、
前記入口部における前記被処理水の水質は、全有機炭素濃度が10μg/L以下、溶存酸素濃度が30μg/L以上であり、
前記紫外線照射装置の上流に設けられ、前記入口部における前記被処理水の前記溶存酸素濃度を1000μg/L未満にする脱酸素装置をさらに有する、水処理装置。 an ultraviolet irradiation device;
a means for adjusting the hydrogen peroxide concentration of the water to be treated at an inlet of the ultraviolet irradiation device to 30 μg/L or less;
and
The ultraviolet irradiation device irradiates the water to be treated supplied from the inlet with ultraviolet rays,
The water quality of the water to be treated at the inlet is such that the total organic carbon concentration is 10 μg/L or less and the dissolved oxygen concentration is 30 μg/L or more ,
The water treatment device further comprises a deoxygenation device provided upstream of the ultraviolet irradiation device, the deoxygenation device adjusting the dissolved oxygen concentration of the water to be treated at the inlet portion to less than 1000 μg/L .
前記紫外線照射装置の入口部における被処理水の過酸化水素濃度を30μg/L以下に調整する手段と、を有し、and a means for adjusting the hydrogen peroxide concentration of the water to be treated at an inlet of the ultraviolet irradiation device to 30 μg/L or less;
前記紫外線照射装置は前記入口部から供給された前記被処理水に紫外線を照射し、The ultraviolet irradiation device irradiates the water to be treated supplied from the inlet with ultraviolet rays,
前記入口部における前記被処理水の水質は、全有機炭素濃度が10μg/L以下、溶存酸素濃度が30μg/L以上であり、The water quality of the water to be treated at the inlet is such that the total organic carbon concentration is 10 μg/L or less and the dissolved oxygen concentration is 30 μg/L or more,
前記紫外線照射装置から、紫外線が照射された処理水の一部を前記紫外線照射装置の上流に戻す戻り配管と、a return pipe for returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device to an upstream side of the ultraviolet irradiation device;
前記紫外線照射装置の上流に設けられた脱酸素装置と、をさらに有し、a deoxidation device provided upstream of the ultraviolet irradiation device,
前記入口部における前記被処理水の前記過酸化水素濃度が30μg/L以下となる範囲で、The hydrogen peroxide concentration of the water to be treated at the inlet is in the range of 30 μg / L or less,
(A)前記紫外線照射装置が、前記紫外線照射装置から照射される紫外線の照射量を調整すること(A) the ultraviolet irradiation device adjusts the irradiation amount of ultraviolet light emitted from the ultraviolet irradiation device;
(B)前記脱酸素装置によって前記入口部における前記被処理水の前記溶存酸素濃度を調整すること(B) adjusting the dissolved oxygen concentration of the water to be treated at the inlet portion by the deoxygenation device;
の少なくともいずれかを行う、水処理装置。The water treatment device performs at least one of the above.
前記紫外線照射装置の入口部における被処理水の過酸化水素濃度を30μg/L以下に調整する手段と、を有し、and a means for adjusting the hydrogen peroxide concentration of the water to be treated at an inlet of the ultraviolet irradiation device to 30 μg/L or less;
前記紫外線照射装置は前記入口部から供給された前記被処理水に紫外線を照射し、The ultraviolet irradiation device irradiates the water to be treated supplied from the inlet with ultraviolet rays,
前記入口部における前記被処理水の水質は、全有機炭素濃度が10μg/L以下、溶存酸素濃度が30μg/L以上であり、The water quality of the water to be treated at the inlet is such that the total organic carbon concentration is 10 μg/L or less and the dissolved oxygen concentration is 30 μg/L or more,
前記紫外線照射装置から、紫外線が照射された処理水の一部を前記紫外線照射装置の上流に戻す戻り配管と、a return pipe for returning a portion of the treated water irradiated with ultraviolet rays from the ultraviolet irradiation device to an upstream side of the ultraviolet irradiation device;
前記紫外線照射装置に供給される前記被処理水の前記過酸化水素濃度を計測するためのサンプリング配管と、a sampling pipe for measuring the hydrogen peroxide concentration of the water to be treated that is supplied to the ultraviolet irradiation device;
前記戻り配管に設けられ、計測された前記過酸化水素濃度が30μg/L以下となるように、前記紫外線照射装置の上流に戻す前記処理水の量を調整する流量調整用の弁と、をさらに有する、水処理装置。a flow rate adjusting valve provided in the return pipe for adjusting the amount of the treated water returned upstream of the ultraviolet irradiation device so that the measured hydrogen peroxide concentration is 30 μg/L or less.
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| WO2009122884A1 (en) * | 2008-03-31 | 2009-10-08 | 栗田工業株式会社 | Method for producing pure water and pure water production system |
| JP2011218249A (en) * | 2010-04-05 | 2011-11-04 | Japan Organo Co Ltd | Pure water production method and device |
| JP2022138429A (en) * | 2021-03-10 | 2022-09-26 | オルガノ株式会社 | Water treatment method and device |
| JP2022174865A (en) * | 2021-05-12 | 2022-11-25 | オルガノ株式会社 | Pure water production device and pure water production method |
| WO2024080079A1 (en) * | 2022-10-14 | 2024-04-18 | 栗田工業株式会社 | Apparatus for producing pure water |
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| WO2009122884A1 (en) * | 2008-03-31 | 2009-10-08 | 栗田工業株式会社 | Method for producing pure water and pure water production system |
| JP2011218249A (en) * | 2010-04-05 | 2011-11-04 | Japan Organo Co Ltd | Pure water production method and device |
| JP2022138429A (en) * | 2021-03-10 | 2022-09-26 | オルガノ株式会社 | Water treatment method and device |
| JP2022174865A (en) * | 2021-05-12 | 2022-11-25 | オルガノ株式会社 | Pure water production device and pure water production method |
| WO2024080079A1 (en) * | 2022-10-14 | 2024-04-18 | 栗田工業株式会社 | Apparatus for producing pure water |
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