JPH0699197A - Method and equipment for purifying pure water or ultrapure water - Google Patents
Method and equipment for purifying pure water or ultrapure waterInfo
- Publication number
- JPH0699197A JPH0699197A JP3140593A JP14059391A JPH0699197A JP H0699197 A JPH0699197 A JP H0699197A JP 3140593 A JP3140593 A JP 3140593A JP 14059391 A JP14059391 A JP 14059391A JP H0699197 A JPH0699197 A JP H0699197A
- Authority
- JP
- Japan
- Prior art keywords
- water
- ozone
- exchange resin
- ultrapure water
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000012498 ultrapure water Substances 0.000 title claims abstract description 81
- 229910021642 ultra pure water Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 35
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007789 gas Substances 0.000 claims abstract description 88
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000012528 membrane Substances 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 27
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 27
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 26
- 238000000746 purification Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 15
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 241000894006 Bacteria Species 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000012510 hollow fiber Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電子工業、医薬品工業
等に用いられる超純水の製造に係わり、特に純水又は超
純水を再度処理してきわめて高純度の超純水を製造する
方法及び装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of ultrapure water used in the electronic industry, the pharmaceutical industry, etc., and particularly to the treatment of pure water or ultrapure water again to produce extremely pure ultrapure water. A method and apparatus.
【０００２】[0002]
【従来の技術】電子工業、医薬品工業等においては、各
製造工程における洗浄にきわめて高純度の水、いわゆる
超純水を多量に必要とする。さらに、要求水質はますま
す厳しくなり、特にＴＯＣ、生菌、溶存酸素の低減が大
きな課題となっている。従来超純水の製造は、前処理装
置と、ついで該前処理水をイオン交換樹脂塔、脱炭酸
塔、逆浸透膜装置、真空脱気塔、混床式カートリッジデ
ミ塔を組み合わせた一次純水製造装置と、ついで該一次
純水を紫外線照射装置、混床式カートリッジデミ、限外
ろ過膜装置を組み合わせた二次純水製造装置（サブシス
テム）で処理して行われている。2. Description of the Related Art In the electronic industry, pharmaceutical industry, etc., a large amount of extremely high-purity water, so-called ultrapure water, is required for cleaning in each manufacturing process. Furthermore, the required water quality is becoming more and more severe, and reduction of TOC, viable bacteria, and dissolved oxygen is a major issue. Conventionally, the production of ultrapure water is a primary pure water that combines a pretreatment device and then the pretreatment water with an ion exchange resin tower, a decarbonation tower, a reverse osmosis membrane equipment, a vacuum degassing tower, and a mixed bed cartridge demi tower. It is carried out by treating the primary pure water with a secondary pure water producing apparatus (subsystem) which is a combination of an ultraviolet irradiation apparatus, a mixed bed type cartridge demi, and an ultrafiltration membrane apparatus.
【０００３】[0003]
【発明が解決しようとする課題】超純水は、停滞すると
その純度が低下することは公知であり、常時超純水を循
環処理して、純度の低下を防止することが行われてい
る。ここで、超純水製造装置は、イオン交換樹脂、限外
ろ過膜等、そのほとんどが有機物質で構成されている。
また処理工程の性質上、これらの設備は接液面積が大き
く、ユースポイント及び各機器を接続する配管類の数倍
ないし数十倍の表面積を有する。すなわち、超純水設備
はそれ自体からの有機物質溶出が避けられない。しか
し、超純水製造装置における有機物質除去は、通常、逆
浸透膜による分離除去、及び紫外線照射による分解のみ
で行われている。さらに逆浸透処理は高圧が必要なため
通常サブシステムでは用いられないことから、サブシス
テムでの有機物質除去は、通常紫外線分解のみ（イオン
交換樹脂による分解生成物質の除去を含む）になってい
る。It is well known that the purity of ultrapure water decreases when it is stagnant, and the purity of ultrapure water is constantly circulated to prevent the purity from decreasing. Here, most of the ultrapure water producing apparatus, such as an ion exchange resin and an ultrafiltration membrane, is made of an organic substance.
In addition, due to the nature of the treatment process, these equipments have a large liquid contact area, and have a surface area several times to several tens of times larger than that of the point of use and the piping for connecting each device. That is, elution of organic substances from the ultrapure water equipment is unavoidable. However, removal of organic substances in an ultrapure water production apparatus is usually performed only by separation and removal by a reverse osmosis membrane and decomposition by ultraviolet irradiation. Furthermore, since reverse osmosis treatment requires high pressure and is not normally used in subsystems, the only organic substance removal in subsystems is usually UV decomposition (including removal of decomposition products by ion exchange resins). .
【０００４】ところで、有機物質分解に効果がある紫外
線は、主に２００ｎｍ以下の短波長の遠紫外線である。
しかし、この波長の照射量はかなり小さく、例えば、一
般的な紫外線照射源である低圧水銀ランプでは、１８５
ｎｍは主波長である２６５ｎｍの数分の１程度の照射量
であり、効果を上げるためには多数のランプが必要とな
る。また、純水又は超純水中には、紫外線のみでは分解
が困難な物質も存在する。すなわち、従来のサブシステ
ムにおける有機物質の除去は必ずしも十分でなく、サブ
システム等の循環処理によって有機物質が増加、蓄積す
る可能性もあった。また生菌については、従来は通常紫
外線照射のみであり、紫外線耐性菌等が発生する恐れが
あった。オゾンによる殺菌を併用する方法も行われてい
るが、溶存酸素濃度が増加し、溶存酸素の低下も求めら
れている超純水には使用困難であった。By the way, the ultraviolet rays effective for decomposing organic substances are mainly far ultraviolet rays having a short wavelength of 200 nm or less.
However, the irradiation amount of this wavelength is quite small, and for example, in a low pressure mercury lamp which is a general ultraviolet irradiation source, 185
nm is an irradiation dose of a fraction of 265 nm, which is the main wavelength, and a large number of lamps are required to improve the effect. Further, in pure water or ultrapure water, there are substances that are difficult to decompose only by ultraviolet rays. That is, the removal of the organic substance in the conventional subsystem is not always sufficient, and there is a possibility that the organic substance is increased and accumulated by the circulation processing of the subsystem and the like. Conventionally, live bacteria were usually only irradiated with ultraviolet rays, and there was a risk that ultraviolet resistant bacteria and the like would occur. A method using sterilization with ozone is also used, but it is difficult to use for ultrapure water in which the dissolved oxygen concentration is increased and the lowered dissolved oxygen is also required.
【０００５】さらに溶存酸素については、従来脱気等に
よる真空脱気、膜を介した真空脱気、窒素ガスによる曝
気、還元剤の添加などによって除去されている。しかし
これらの方法は、溶存酸素濃度が十分に低くならない、
装置が大規模になる、還元剤及び反応生成物の残留等の
問題があり、通常サブシステムでは用いられていない。
従って通常は一次純水システムのみに除去処理設備があ
り、サブシステム以降で溶存酸素が増加した場合には、
対応できなかった。また、水素添加後、パラジウム触媒
樹脂に通水する方法もあり、この方法はサブシステムで
も用いられているが、水素の溶解効率が低く、多量の水
素が必要であった。そこで本発明は、上記のような問題
点を解決し、有機物質、生菌及び溶存酸素についても、
循環処理による高純度化、及び純度の低下を容易に防止
できる超純水の精製方法とその装置を提供することを目
的とする。Further, dissolved oxygen is conventionally removed by vacuum deaeration such as deaeration, vacuum deaeration through a film, aeration with nitrogen gas, addition of a reducing agent, and the like. However, in these methods, the dissolved oxygen concentration does not become sufficiently low,
There are problems such as large-scale equipment, residual of reducing agent and reaction product, and they are not usually used in subsystems.
Therefore, usually there is a removal treatment facility only in the primary pure water system, and when the dissolved oxygen increases after the subsystem,
I couldn't handle it. There is also a method of passing water through a palladium catalyst resin after hydrogenation, and this method is also used in subsystems, but the dissolution efficiency of hydrogen was low and a large amount of hydrogen was required. Therefore, the present invention solves the above problems, and also for organic substances, viable bacteria and dissolved oxygen,
It is an object of the present invention to provide a method for purifying ultrapure water and a device therefor capable of easily preventing purification and reduction in purity due to circulation treatment.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明では、純水又は超純水からさらに高純度の超
純水を得る精製方法であって、前記精製方法が、（イ）
原水にオゾンを溶解する工程、（ロ）（イ）の処理水に
紫外線を照射する工程、（ハ）パラジウムを担持した気
体透過膜の接液側に（ロ）の処理水を通水し、接ガス側
に水素を供給する工程、（ニ）（ハ）の処理水をＨ型強
酸性カチオン交換樹脂とＯＨ型アニオン交換樹脂とを混
合したイオン交換樹脂層に通水する工程、（ホ）（ニ）
の処理水を限外ろ過する工程、からなることを特徴とす
る純水又は超純水の精製方法としたものである。また、
本発明では、純水又は超純水からさらに高純度の超純水
を得る精製方法であって、前記精製方法が、（イ）原水
の一部にオゾンを溶解する工程、（ロ）（イ）のオゾン
溶解水と残部の原水とを混合する工程、（ハ）（ロ）の
処理水に紫外線を照射する工程、（ニ）パラジウムを担
持した気体透過膜の接液側に（ハ）の処理水を通水し、
接ガス側に水素を供給する工程、（ホ）（ニ）の処理水
をＨ型強酸性カチオン交換樹脂とＯＨ型アニオン交換樹
脂とを混合したイオン交換樹脂層に通水する工程、
（ヘ）（ホ）の処理水を限外ろ過する工程、からなるこ
とを特徴とする純水又は超純水の精製方法としたのであ
る。In order to achieve the above object, the present invention is a purification method for obtaining ultrapure water of higher purity from pure water or ultrapure water. )
A step of dissolving ozone in raw water, a step of irradiating the treated water of (b) and (a) with an ultraviolet ray, and (c) passing the treated water of (b) to the liquid contact side of the gas permeable membrane carrying palladium, A step of supplying hydrogen to the gas contact side, a step of passing the treated water of (d) and (c) through an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed, (e) (D)
The method for purifying pure water or ultrapure water is characterized in that it comprises a step of ultrafiltering the treated water. Also,
In the present invention, there is provided a purification method for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the purification method comprises: (a) dissolving ozone in a part of raw water; ) Mixing ozone-dissolved water with the rest of the raw water, (c) irradiating the treated water with ultraviolet light (b), (d) adding (d) to the liquid-contacting side of the gas permeable membrane carrying palladium. Through treated water,
A step of supplying hydrogen to the gas contact side, a step of passing the treated water of (e) and (d) through an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed,
This is a method for purifying pure water or ultrapure water, comprising the steps of (f) and (e) ultrafiltration of the treated water.
【０００７】さらに、本発明では、純水又は超純水から
さらに高純度の超純水を得る精製方法であって、前記精
製方法が、（イ）ユースポイントから戻ってくる精製さ
れた未使用の超純水の一部又は全部にオゾンを溶解する
工程、（ロ）原水と（イ）のオゾン溶解水とを混合する
工程、（ハ）（ロ）の処理水に紫外線を照射する工程、
（ニ）パラジウムを担持した気体透過膜の接液側に
（ハ）の処理水を通水し、接ガス側に水素を供給する工
程、（ホ）（ニ）の処理水をＨ型強酸性カチオン交換樹
脂とＯＨ型アニオン交換樹脂とを混合したイオン交換樹
脂層に通水する工程、（ヘ）（ホ）の処理水を限外ろ過
する工程、からなることを特徴とする純水又は超純水の
精製方法としたものである。上記の本発明の精製方法に
おいて、オゾン溶解工程から排出されるオゾン含有排ガ
スと、前記水素供給工程から排出される水素含有排ガス
とを混合し、水素燃焼触媒を有する触媒層で処理するの
がよい。Further, according to the present invention, there is provided a purification method for obtaining a higher purity ultrapure water from pure water or ultrapure water, wherein the purification method is (a) a purified virgin product returned from a point of use. A step of dissolving ozone in a part or all of the ultrapure water of (b), a step of mixing raw water (b) with an ozone-dissolved water of (b), and a step of irradiating the treated water of (c) (b) with ultraviolet rays,
(D) A step of passing the treated water of (c) to the liquid contact side of the gas permeable membrane supporting palladium and supplying hydrogen to the gas contact side, (e) the treated water of (d) is H-type strongly acidic Pure water or ultrapure water, which comprises a step of passing water through an ion exchange resin layer in which a cation exchange resin and an OH type anion exchange resin are mixed, and a step of ultrafiltering the treated water of (f) and (e) This is a method for purifying pure water. In the above-described purification method of the present invention, the ozone-containing exhaust gas discharged from the ozone dissolution step and the hydrogen-containing exhaust gas discharged from the hydrogen supply step are preferably mixed and treated with a catalyst layer having a hydrogen combustion catalyst. .
【０００８】また、上記他の目的を達成するために、本
発明では、純水又は超純水からさらに高純度の超純水を
得る精製装置であって、前記精製装置が、（イ）原水に
オゾンを溶解するオゾン溶解装置と、（ロ）紫外線照射
装置と、（ハ）接液側に（ロ）の処理水を通水し、接ガ
ス側に水素を供給する手段を有するパラジウムを担持し
た気体透過膜装置と、（ニ）Ｈ型強酸性カチオン交換樹
脂とＯＨ型アニオン交換樹脂とを混合したイオン交換樹
脂層を有するイオン交換装置と、（ホ）限外ろ過装置と
を備え、（ヘ）前記（イ）から（ホ）までの装置相互間
を順次配管で接続したことを特徴とする純水又は超純水
の精製装置としたものである。また、本発明では、純水
又は超純水からさらに高純度の超純水を得る精製装置で
あって、前記精製装置が、（イ）原水の一部にオゾンを
溶解するオゾン溶解装置と、（ロ）（イ）のオゾン溶解
水と残部の原水とを混合する装置と、（ハ）紫外線照射
装置と、（ニ）接液側に（ハ）の処理水を通水し、接ガ
ス側に水素を供給する手段を有するパラジウムを担持し
た気体透過膜装置と、（ホ）Ｈ型強酸性カチオン交換樹
脂とＯＨ型アニオン交換樹脂とを混合したイオン交換樹
脂層を有するイオン交換装置と、（ヘ）限外ろ過装置と
を備え、（ト）前記（イ）から（ヘ）までの装置相互間
を順次配管で接続したことを特徴とする純水又は超純水
の精製装置としたものである。In order to achieve the above-mentioned other object, in the present invention, there is provided a purification device for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the purification device is (a) raw water. Ozone dissolving device that dissolves ozone in (2), (b) UV irradiation device, (c) Palladium having means for passing treated water of (b) to the liquid contact side and supplying hydrogen to the gas contact side A gas permeable membrane device, (d) an ion exchange device having an ion exchange resin layer in which an H-type strongly acidic cation exchange resin and an OH-type anion exchange resin are mixed, and (e) an ultrafiltration device, F) A pure water or ultrapure water purifying device characterized in that the devices (a) to (e) are sequentially connected by piping. Further, in the present invention, a purifying apparatus for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the purifying apparatus is (a) an ozone dissolving apparatus for dissolving ozone in a part of raw water, (B) A device for mixing the ozone-dissolved water of (a) with the rest of the raw water, (c) an ultraviolet irradiation device, (d) the treated water of (c) is passed to the liquid contact side, and the gas contact side A gas permeable membrane device supporting palladium having a means for supplying hydrogen to (1), and (e) an ion exchange device having an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed, F) An apparatus for purifying pure water or ultrapure water, characterized by comprising an ultrafiltration device, and (g) sequentially connecting the devices from (a) to (f) with piping. is there.
【０００９】さらに、本発明では純水又は超純水からさ
らに高純度の超純水を得る精製装置であって、前記精製
装置が、（イ）ユースポイントから戻ってくる精製され
た未使用の超純水の一部又は全部にオゾンを溶解するオ
ゾン溶解装置と、（ロ）原水と（イ）のオゾン溶解水と
を混合する装置と、（ハ）紫外線照射装置と、（ニ）接
液側に（ハ）の処理水を通水し、接ガス側に水素を供給
する手段を有するパラジウムを担持した気体透過膜装置
と、（ホ）Ｈ型強酸性カチオン交換樹脂とＯＨ型アニオ
ン交換樹脂とを混合したイオン交換樹脂層を有するイオ
ン交換装置と、（ヘ）限外ろ過装置とを備え、（ト）前
記（イ）から（ヘ）までの装置相互間を順次配管で接続
したことを特徴とする純水又は超純水の精製装置とした
ものである。前記本発明の精製装置に、電解方式のオゾ
ン発生装置を設け、発生するオゾンと水素とをそれぞれ
オゾン溶解装置と気体透過膜とに供給するための手段を
設けてもよい。Further, according to the present invention, there is provided a refining apparatus for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the refining apparatus is (a) a refined, unused and returned from the point of use. An ozone dissolving device that dissolves ozone in part or all of ultrapure water, a device that mixes (b) raw water and (a) ozone dissolved water, (c) ultraviolet irradiation device, and (d) wetted A gas permeable membrane device supporting palladium having a means for supplying treated water of (c) to the gas side and supplying hydrogen to the gas contact side, and (e) H-type strongly acidic cation exchange resin and OH-type anion exchange resin An ion exchange device having an ion exchange resin layer mixed with and (f) an ultrafiltration device is provided, and (g) the devices (a) to (f) are sequentially connected by piping. The apparatus is used as a characteristic pure water or ultrapure water purification apparatus. The refining device of the present invention may be provided with an electrolysis type ozone generator, and means for supplying the generated ozone and hydrogen to the ozone dissolving device and the gas permeable membrane, respectively.
【００１０】以下に本発明を詳細に説明する。図１は、
本発明の実施態様の一例を示すフローの説明図である。
図１を用いて、本発明の精製装置をさらに詳しく説明す
る。純水供給ライン１から供給される純水又は超純水の
一部を、三方弁２で分流してオゾン溶解器３へ供給す
る。オゾン溶解器３からのオゾン溶解水は、混合器５で
原水の純水又は超純水に合流して混合させる。ここでオ
ゾン溶解器３には、オゾン発生器からの発生オゾンをオ
ゾン供給ライン７を介して供給し、オゾン水封管１０か
らの排ガスは排ガス処理装置２０へ導入して処理する。
なお原水は全量オゾン溶解器３へ導いてもよい。該オゾ
ン溶解水を含む純水を、紫外線照射塔１１へ導入する。
ついで該紫外線処理水をパラジウムを担持した気体透過
膜１３を有する気体透過膜モジュール１２の接液側に導
入する。このとき該装置の接ガス側にはオゾン発生器８
から発生する水素ガスを供給し、水素水封管１４からの
排ガスは、水素燃焼触媒を有する排ガス処理装置２０へ
導入して処理する。ついで該処理水をポンプ１７を介し
てイオン交換樹脂塔１８へ導入し、ついで限外ろ過装置
１９へ導入する。The present invention will be described in detail below. Figure 1
It is explanatory drawing of the flow which shows an example of the embodiment of this invention.
The refining apparatus of the present invention will be described in more detail with reference to FIG. A part of pure water or ultrapure water supplied from the pure water supply line 1 is branched by the three-way valve 2 and supplied to the ozone dissolver 3. The ozone-dissolved water from the ozone dissolver 3 is mixed with the pure water or ultrapure water of the raw water by the mixer 5. Here, ozone generated from the ozone generator is supplied to the ozone dissolver 3 through the ozone supply line 7, and the exhaust gas from the ozone water sealing tube 10 is introduced into the exhaust gas processing device 20 to be processed.
The raw water may be entirely introduced into the ozone dissolver 3. Pure water containing the ozone-dissolved water is introduced into the ultraviolet irradiation tower 11.
Then, the ultraviolet-treated water is introduced to the liquid contact side of the gas permeable membrane module 12 having the gas permeable membrane 13 carrying palladium. At this time, the ozone generator 8 is provided on the gas contact side of the device.
The exhaust gas from the hydrogen water sealing tube 14 is supplied to the exhaust gas treatment device 20 having a hydrogen combustion catalyst and treated. Then, the treated water is introduced into the ion exchange resin tower 18 through the pump 17, and then into the ultrafiltration device 19.
【００１１】図２は、本発明の実施態様の他の一例を示
すフローの説明図である。本装置では、ユースポイント
２３から戻ってくる未使用の超純水の一部又は全部をオ
ゾン溶解器３へ供給する。オゾン溶解器３からのオゾン
溶解水や残部の未使用の超純水は、通常タンク２１へ供
給し、ユースポイントで使用された超純水量又はそれ以
上の量の原水を純水供給ライン１より供給混合する。こ
こでオゾン溶解器３には、オゾン発生器８からの発生オ
ゾンをオゾン供給ライン７を介して供給し、オゾン水封
間１０からの排ガスは排ガス処理装置２０へ導入して処
理する。また、未使用の超純水でオゾン溶解器３へ供給
しない残部は、サブシステムに供給して別途使用しても
よい。該オゾン溶解水を含む純水を、紫外線照射塔１１
へ導入する。ついで該紫外線処理水をパラジウムを担持
した気体透過膜１３を有する気体透過膜モジュール１２
の接液側に導入する。このとき該装置の接ガス側にはオ
ゾン発生器８から発生する水素ガスを供給し、水素水封
管１４からの排ガスは、水素燃焼触媒を有する排ガス処
理装置２０へ導入して処理する。ついで該処理水をポン
プ１７を介してイオン交換樹脂塔１８へ導入し、ついで
限外ろ過装置１９へ導入する。次いで該処理水をユース
ポイント２３へ供給し、ユースポイントで使用されなか
った超純水は熱交換器２５を経て、リターンラインを通
ってタンク２へ循環される。また未使用の超純水を、オ
ゾン溶解器への供給水を除いて二次純水装置のリターン
ラインに戻すこともできる。この場合熱交換器２５は必
要ではない。FIG. 2 is an explanatory diagram of a flow showing another example of the embodiment of the present invention. In this device, a part or all of the unused ultrapure water returned from the use point 23 is supplied to the ozone dissolver 3. The ozone-dissolved water from the ozone dissolver 3 and the remaining unused ultrapure water are normally supplied to the tank 21, and the amount of ultrapure water used at the point of use or more raw water is supplied from the pure water supply line 1. Supply and mix. Here, the ozone generated from the ozone generator 8 is supplied to the ozone dissolver 3 through the ozone supply line 7, and the exhaust gas from the ozone water sealing space 10 is introduced into the exhaust gas processing device 20 to be processed. The remaining part of the ultrapure water that is not supplied to the ozone dissolver 3 may be supplied to the subsystem and used separately. The pure water containing the ozone-dissolved water is supplied to the ultraviolet irradiation tower 11
Introduce to. Next, a gas permeable membrane module 12 having a gas permeable membrane 13 carrying the ultraviolet-treated water with palladium.
Introduce into the wetted side of. At this time, hydrogen gas generated from the ozone generator 8 is supplied to the gas contact side of the apparatus, and the exhaust gas from the hydrogen water sealing tube 14 is introduced into the exhaust gas processing apparatus 20 having a hydrogen combustion catalyst for processing. Then, the treated water is introduced into the ion exchange resin tower 18 through the pump 17, and then into the ultrafiltration device 19. Next, the treated water is supplied to the use point 23, and the ultrapure water not used at the use point is circulated to the tank 2 through the heat exchanger 25 and the return line. In addition, unused ultrapure water can be returned to the return line of the secondary pure water device except for the water supplied to the ozone dissolver. In this case, the heat exchanger 25 is not necessary.
【００１２】ここで、紫外線照射光源は、波長４００ｎ
ｍ以下の紫外線を照射するものであれば良く、オゾンの
ラジカル化波長とされる２００〜３００ｎｍ、及び有機
物質の分解波長とされる２００ｎｍ以下の波長を照射で
きるものが特に望ましい。ランプ及び保護管に人工石英
を用いた低圧水銀ランプを好ましく用いることが出来
る。気体透過膜モジュールは、パラジウムを担持した気
体透過膜を有したものである。該気体透過膜は、水素は
透過させ、液体は透過しない膜にパラジウムを担持させ
たものであれば良く、接ガス側には水素を供給する。気
体透過膜へのパラジウムの担持は、本発明者らが既に提
案しているが、プラスチックへのメッキ方法またはイオ
ン交換樹脂等への担持方法に準じて行うことができる。
接ガス側への水素供給は、該溶存オゾン酸素除去装置へ
の流入水中に溶解している酸素及びオゾンの等量から等
量の３倍を供給する。The ultraviolet irradiation light source has a wavelength of 400n.
It is only necessary to irradiate ultraviolet rays of m or less, and it is particularly desirable to irradiate a wavelength of 200 to 300 nm which is a radicalization wavelength of ozone and a wavelength of 200 nm or less which is a decomposition wavelength of an organic substance. A low pressure mercury lamp using artificial quartz for the lamp and the protective tube can be preferably used. The gas permeable membrane module has a gas permeable membrane supporting palladium. The gas permeable film may be any film in which palladium is supported on a film that allows hydrogen to permeate and does not allow liquid to permeate, and hydrogen is supplied to the gas contact side. The support of palladium on the gas permeable membrane can be performed according to the method of plating on plastic or the method of supporting on ion exchange resin or the like, which has been already proposed by the present inventors.
The supply of hydrogen to the gas contacting side is 3 times as much as the equivalent amount of oxygen and ozone dissolved in the inflow water to the dissolved ozone oxygen removing device.
【００１３】混床式イオン交換樹脂塔は、Ｈ型強酸性カ
チオン交換樹脂とＯＨ型強塩基性アニオン交換樹脂との
混合樹脂であり、混合前に高度に再生し、十分に水洗し
ておくことが望ましい。ここで水洗は、４０℃程度に加
温した超純水または純水を用いて行うことが望ましい。
限外ろ過装置としては、外圧型中空糸限外ろ過膜を用い
ることが望ましい。オゾン溶解器は、気体透過膜を介し
てオゾンを溶解させる装置であり、膜の一方に水を通
し、他方を気体で加圧することによって気体を溶解させ
ることができる。気体透過膜としてはポリ四弗化エチレ
ン系の膜を好ましく用いることができる。また散気管、
散気ノズル等によるオゾン溶解器を用いることもでき
る。The mixed bed type ion-exchange resin tower is a mixed resin of H-type strongly acidic cation-exchange resin and OH-type strongly basic anion-exchange resin, and it should be highly regenerated and thoroughly washed with water before mixing. Is desirable. It is desirable that the washing with water is performed using ultrapure water or pure water heated to about 40 ° C.
As the ultrafiltration device, it is desirable to use an external pressure type hollow fiber ultrafiltration membrane. The ozone dissolver is a device that dissolves ozone through a gas permeable membrane, and can dissolve the gas by passing water through one side of the membrane and pressurizing the other side with the gas. As the gas permeable film, a polytetrafluoroethylene-based film can be preferably used. Also an air diffuser,
It is also possible to use an ozone dissolver with a diffuser nozzle or the like.
【００１４】[0014]
【作用】本発明の作用を各処理工程に従って説明する。
オゾン溶解器では、被処理水の一部にオゾンを溶解す
る。一部のみに溶解させることによって、オゾン溶解に
伴う気体透過膜の接液面積を少なくでき、圧損等を少な
くすることもできる。オゾン発生器は、水電解型を用い
ることによって、副生する水素を溶存オゾン酸素除去装
置に供給できる利点がある。また、高濃度のオゾンを供
給できることから随伴する酸素の供給量を少なくするこ
とができる。オゾンが溶解している被処理水に２１０〜
３００ｎｍの紫外線を照射すると、紫外線によって分解
されるオゾンのラジカルによって被処理水中の有機物質
が分解される。またバクテリア等の殺菌も行われる。こ
こで殺菌及び有機物質分解効果は、紫外線またはオゾン
単独に比較して効果が大きいことが公知である。また、
有機物質分解に照射量の大きい低圧水銀ランプの波長２
５４ｎｍの紫外線を有効に活性できるため、遠紫外線の
波長１８５ｎｍのみを用いるのに比較して効果が大き
い。従って、この処理工程では、有機物質はイオン性の
分解生成物に、また、バクテリアは微粒子（死菌）とな
る。しかしこの処理工程、及びこの前段のオゾン溶解工
程では、オゾン及び酸素の濃度が増加する。The operation of the present invention will be described according to each processing step.
The ozone dissolver dissolves ozone in a part of the water to be treated. By dissolving only in a part, the liquid contact area of the gas permeable film due to ozone dissolution can be reduced, and pressure loss and the like can also be reduced. The ozone generator has an advantage that hydrogen produced as a by-product can be supplied to the dissolved ozone / oxygen removing device by using the water electrolysis type. Further, since a high concentration of ozone can be supplied, the amount of accompanying oxygen can be reduced. 210 to water to be treated in which ozone is dissolved
When irradiated with 300 nm ultraviolet rays, the organic substances in the water to be treated are decomposed by the radicals of ozone decomposed by the ultraviolet rays. In addition, bacteria etc. are sterilized. Here, it is known that the effects of sterilization and decomposition of organic substances are greater than those of ultraviolet rays or ozone alone. Also,
Wavelength of low-pressure mercury lamp with high irradiation dose for decomposition of organic substances 2
Since the ultraviolet ray of 54 nm can be effectively activated, the effect is large as compared with the case of using only the wavelength of 185 nm of far ultraviolet ray. Therefore, in this processing step, the organic substances become ionic decomposition products, and the bacteria become fine particles (dead bacteria). However, the concentration of ozone and oxygen increases in this treatment step and the ozone dissolution step in the preceding stage.
【００１５】次に、接ガス側に水素を供給した、パラジ
ウムを担持した気体透過膜を有する溶存オゾン酸素除去
装置では、パラジウムの存在下で、 Ｏ3 ＋ ３Ｈ2 → ３Ｈ2 Ｏ Ｏ2 ＋ ２Ｈ2 → ２Ｈ2 Ｏ と模式的に表される反応が行われる。このとき水素は気
体透過膜を介しているため、水との接触効率が高く、さ
らに気体透過膜表面上のパラジウムと溶解した形で酸素
またはオゾンに接触する。従って、例えば水素を溶解し
た水をパラジウム触媒樹脂等に通水する方法に比較して
反応効率が高い。またこの反応は生成物が水であるた
め、不純物の増加がない。なお、この処理工程によって
残留する水素はわずかであるが、必要であれば膜脱気装
置等によって除去することも可能である。さらにイオン
交換樹脂塔では、被処理水中に含まれる無機イオン、シ
リカ等の他、紫外線分解によるイオン性の分解生成物、
及びパラジウムを担持した気体透過膜から極微量溶出す
るパラジウムを除去する。最後に限外ろ過装置によって
微粒子を除去する。この微粒子は被処理水中に含まれる
ものの他、バクテリアの死菌、ポンプの発塵、イオン交
換樹脂及び気体透過膜等からの漏出物を含む。排ガス処
理装置は、オゾンを含有する排ガスと水素を含有する排
ガスとを混合して、触媒燃焼させることによって、無害
化するものである。タンクは、ユースポイントでの超純
水使用量と装置へ供給される純水供給量とのバランスを
取り、ユースポイントへ供給する超純水の流量及び圧力
を定常化する。又オゾンとの接触時間を長くすることに
よって殺菌及び有機物質分解効果を高める。Next, in the dissolved ozone oxygen removing apparatus having a gas permeable membrane supporting palladium, in which hydrogen is supplied to the gas contact side, in the presence of palladium, O 3 + 3H 2 → 3H 2 O 2 + 2H The reaction represented schematically as 2 → 2H 2 O is performed. At this time, since hydrogen passes through the gas permeable membrane, it has a high contact efficiency with water, and further comes into contact with oxygen or ozone in a dissolved form with palladium on the surface of the gas permeable membrane. Therefore, for example, the reaction efficiency is high as compared with the method in which water in which hydrogen is dissolved is passed through a palladium catalyst resin or the like. In addition, since the product of this reaction is water, there is no increase in impurities. Although a small amount of hydrogen remains in this treatment step, it can be removed by a membrane degassing device or the like if necessary. Furthermore, in the ion exchange resin tower, in addition to inorganic ions contained in the water to be treated, silica, etc., ionic decomposition products due to ultraviolet decomposition,
And a very small amount of palladium which is eluted from the gas permeable membrane supporting palladium is removed. Finally, fine particles are removed by an ultrafiltration device. The fine particles include not only those contained in the water to be treated but also bacteria killed by bacteria, dust generated by the pump, leaked substances from the ion exchange resin, the gas permeable membrane and the like. The exhaust gas treatment device is a device that detoxifies the exhaust gas containing ozone and the exhaust gas containing hydrogen by mixing them and catalytically burning them. The tank balances the amount of ultrapure water used at the point of use with the amount of pure water supplied to the device, and stabilizes the flow rate and pressure of the ultrapure water supplied to the point of use. In addition, the effect of sterilization and decomposition of organic substances is enhanced by prolonging the contact time with ozone.
【００１６】[0016]
【実施例】以下に本発明を実施例及び比較例を上げて説
明するが、本発明はこれらの実施例に限定されるもので
はない。 実施例１ 水道水を原水とし、逆浸透膜装置、真空脱気装置、イオ
ン交換装置、メンブレンフィルタ等で構成された１次純
水装置で処理して得られた１次純水を、図１に示す精製
装置に３ｍ3 ／ｈで供給した。三方弁２で被処理水を分
流し、オゾン溶解器３へ１０リットル／ｈで供給した。
オゾン溶解器３は、ポリ四弗化エチレン系の中空糸気体
透過膜４を有する、膜面積０．４ｍ2 のモジュールを用
いた。このガス透過膜の内側に被処理水を１０リットル
／ｈで供給し、外側にオゾン化ガスを供給した。このオ
ゾン化ガスは、オゾン発生能力０．３ｇ／ｈの固体高分
子電解質水電解方式のオゾン発生器８より供給した。紫
外線照射装置１１の有効容積は約３２リットルであり、
人工石英管を介して消費電力１００Ｗの低圧水銀ランプ
７本を点灯させた。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 Primary pure water obtained by treating tap water as a raw water with a primary pure water device composed of a reverse osmosis membrane device, a vacuum degassing device, an ion exchange device, a membrane filter, etc. It was supplied at 3 m 3 / h to the purifying apparatus shown in FIG. The water to be treated was divided by the three-way valve 2 and supplied to the ozone dissolver 3 at 10 l / h.
As the ozone dissolver 3, a module having a membrane area of 0.4 m 2 having a polytetrafluoroethylene-based hollow fiber gas permeable membrane 4 was used. Water to be treated was supplied to the inside of this gas permeable membrane at a rate of 10 liters / hour, and ozonized gas was supplied to the outside. This ozonized gas was supplied from a solid polymer electrolyte water electrolysis type ozone generator 8 having an ozone generation capacity of 0.3 g / h. The effective volume of the ultraviolet irradiation device 11 is about 32 liters,
Seven low-pressure mercury lamps with power consumption of 100 W were lit through the artificial quartz tube.
【００１７】次にパラジウム担持気体透過膜モジュール
１２は、内側に無電解メッキ法に準じてパラジウムによ
る触媒化、活性化までを行ってパラジウムを担持したポ
リオレフィン−ポリウレタン系の中空糸複合膜を有する
モジュールである。膜面積６ｍ2 のモジュールを４本用
いた。このガス透過膜の内側に被処理水を通水し、外側
にオゾン発生器８からの水素ガスを０．１ｋｇｆ／ｃｍ
2 、２５ｍｌ／ｍｉｎで供給した。水素水封管１４から
の排ガス及びオゾン発生器８からの過剰水素ガスは、パ
ラジウム系の水素燃焼触媒を有する排ガス処理装置２０
へ導入して処理した。次に、カートリッジ型イオン交換
樹脂塔１８には、十分洗浄したＨ型強酸性カチオン交換
樹脂（ダウエックスモノスフィア６５０Ｃ）１０リット
ルと、ＯＨ型強塩基性アニオン交換樹脂（ダウエックス
モノスフィア５５０Ａ）２０リットルとを混合してＦＲ
Ｐ製容器に充填したもの２本を用いた。次に、限外ろ過
装置１９は、外圧型中空糸膜モジュール（旭化成ＯＬＴ
−３０２６）を用いた。この限外ろ過装置出口圧力が
２．５ｋｇｆ／ｃｍ2 となるように調整した。本精製装
置で得られた処理水の水質を表１に示した。Next, the palladium-supporting gas permeable membrane module 12 has a polyolefin-polyurethane-based hollow fiber composite membrane on which palladium is supported by catalyzing and activating with palladium according to an electroless plating method. Is. Four modules having a membrane area of 6 m 2 were used. Water to be treated is passed inside the gas permeable membrane, and hydrogen gas from the ozone generator 8 is passed through the outside at 0.1 kgf / cm 2.
2 , supplied at 25 ml / min. The exhaust gas from the hydrogen water sealing pipe 14 and the excess hydrogen gas from the ozone generator 8 are exhaust gas treating apparatus 20 having a palladium-based hydrogen combustion catalyst.
Was introduced and processed. Next, in the cartridge type ion exchange resin tower 18, 10 liters of the H-type strongly acidic cation exchange resin (Dowex Monosphere 650C) and the OH type strongly basic anion exchange resin (Dowex Monosphere 550A) 20 which have been thoroughly washed are placed. FR mixed with liter
Two pieces filled in a P container were used. Next, the ultrafiltration device 19 is an external pressure type hollow fiber membrane module (Asahi Kasei OLT
-3026) was used. The outlet pressure of this ultrafiltration device was adjusted to be 2.5 kgf / cm 2 . Table 1 shows the water quality of the treated water obtained by the present purifier.
【００１８】比較例１ 実施例１と同様の一次純水を、図３に示す従来のサブシ
ステムに３ｍ3 ／ｈで供給して処理した。図３中の紫外
線照射装置１１、カートリッジ型イオン交換型樹脂塔１
８、及び限外ろ過装置１９は実施例１に使用したものと
同様の仕様のものを用いた。処理水の水質を表１に合わ
せた示した。処理水中の有機物質（ＴＯＣ）及び生菌の
除去効果が低いことが認められる。Comparative Example 1 The same primary pure water as in Example 1 was supplied to the conventional subsystem shown in FIG. 3 at 3 m 3 / h for treatment. The ultraviolet irradiation device 11 and the cartridge type ion exchange type resin tower 1 in FIG.
8 and an ultrafiltration device 19 having the same specifications as those used in Example 1 were used. The water quality of the treated water is shown in Table 1. It is recognized that the effect of removing organic substances (TOC) and viable bacteria in the treated water is low.
【表１】 [Table 1]
【００１９】実施例２ 供給する純水として、一次純水を更に紫外線殺菌装置、
イオン交換カートリッジ、及び限外ろ過装置で構成され
た２次純水製造装置（サブシステム）で処理して得られ
たいわゆる超純水を用いた他は、実施例１と同様の装置
を用いて処理した。処理水の水質を表２に示した。Example 2 As pure water to be supplied, primary pure water was further added to an ultraviolet sterilizer,
An apparatus similar to that of Example 1 was used except that so-called ultrapure water obtained by treatment with a secondary pure water producing apparatus (subsystem) composed of an ion exchange cartridge and an ultrafiltration apparatus was used. Processed. The water quality of the treated water is shown in Table 2.
【００２０】比較例２ 実施例２と同様のいわゆる超純水を、更に図３に示す従
来のサブシステムに３ｍ3 ／ｈで供給して処理した。図
３中の紫外線照射装置１１、カートリッジ型イオン交換
型樹脂塔１８、及び限外ろ過装置１９は実施例１に使用
したものと同様の仕様のものを用いた。処理水の水質を
表２に合わせた示した。従来型のサブシステムで、２回
処理しても処理水中の有機物質（ＴＯＣ）及び生菌の除
去効果はほとんど大きくならないことが認められる。Comparative Example 2 The same so-called ultrapure water as in Example 2 was further supplied to the conventional subsystem shown in FIG. 3 at 3 m 3 / h for treatment. The ultraviolet irradiation device 11, the cartridge type ion exchange type resin tower 18 and the ultrafiltration device 19 shown in FIG. 3 have the same specifications as those used in Example 1. The water quality of the treated water is shown in Table 2. It is recognized that the effect of removing organic substances (TOC) and viable bacteria in the treated water by the conventional sub-system hardly increases even if the treatment is performed twice.
【００２１】比較例３ 実施例２と同様のいわゆる超純水を、図４に示すオゾン
殺菌装置付きサブシステムに３ｍ3 ／ｈで供給して処理
した。図４中の紫外線照射装置１１、カートリッジ型イ
オン交換型樹脂塔１８、及び限外ろ過装置１９、及びオ
ゾン添加用の設備すなわちオゾン溶解器３、オゾン発生
器８等は実施例１に使用したものと同様の仕様のものを
用いた。処理水の水質を表２に合わせた示した。処理水
中の溶存酸素濃度が増加していることが認められる。Comparative Example 3 The same so-called ultrapure water as in Example 2 was supplied to the subsystem with an ozone sterilizer shown in FIG. 4 at 3 m 3 / h for treatment. The ultraviolet irradiation device 11, the cartridge type ion exchange type resin tower 18, the ultrafiltration device 19 and the equipment for ozone addition, that is, the ozone dissolver 3 and the ozone generator 8 in FIG. The same specifications as above were used. The water quality of the treated water is shown in Table 2. It can be seen that the dissolved oxygen concentration in the treated water is increasing.
【表２】 [Table 2]
【００２２】実施例３ 実施例２と同様のいわゆる超純水を図２に示す精製装置
に供給して処理した。容量１００リットルのタンク２１
には、上記超純水、ユースポイントからの未使用の超純
水、及びオゾン溶解水を供給した。本装置は、ポンプ１
７によって３ｍ3 ／ｈで循環処理を行った。また、この
タンクには窒素シールをつけ、水位の変動に対処した。
その他、オゾン発生器及び溶解装置、パラジウム担持気
体透過膜、イオン交換樹脂塔、紫外線照射塔、限外ろ過
装置、排ガス処理装置等は、実施例１と同様の仕様のも
のを用いた。処理水の水質を表３に示した。Example 3 The same so-called ultrapure water as in Example 2 was supplied to the purification apparatus shown in FIG. 2 for treatment. 100-liter tank 21
Was supplied with the above ultrapure water, unused ultrapure water from the point of use, and ozone-dissolved water. This device is a pump 1
According to No. 7, circulation treatment was carried out at 3 m 3 / h. In addition, a nitrogen seal was attached to this tank to cope with fluctuations in water level.
In addition, the ozone generator and the dissolving device, the palladium-supporting gas permeable membrane, the ion exchange resin tower, the ultraviolet irradiation tower, the ultrafiltration device, the exhaust gas treatment device, and the like had the same specifications as in Example 1. The water quality of the treated water is shown in Table 3.
【００２３】比較例４ 実施例１と同様のいわゆる超純水を、図５に示すオゾン
殺菌装置付きサブシステムに３ｍ3 ／ｈで供給して処理
した。紫外線照射装置、イオン交換樹脂塔、限外ろ過装
置、及びオゾン添加用の装置等は実施例３と同様の仕様
のものを用いた。処理水の水質を表３に合わせて示し
た。処理水中の溶存酸素濃度が増加していることが認め
られる。Comparative Example 4 The same so-called ultrapure water as in Example 1 was supplied to the subsystem with an ozone sterilizer shown in FIG. 5 at 3 m 3 / h for treatment. The ultraviolet irradiation device, the ion-exchange resin tower, the ultrafiltration device, the ozone addition device, and the like had the same specifications as in Example 3. The water quality of the treated water is also shown in Table 3. It can be seen that the dissolved oxygen concentration in the treated water is increasing.
【表３】 [Table 3]
【００２４】[0024]
【発明の効果】以上のように、純水あるいは超純水を精
製するに際し、本発明の装置は １）超純水製造設備等から溶出した有機物質を、オゾン
と紫外線照射とを併用して分解すると同時に殺菌をも行
い、 ２）被処理水に溶存していた溶存酸素（ＤＯ）、及びオ
ゾンの添加で増加したオゾン及び酸素を、パラジウムを
添加した気体透過膜モジュールの接ガス側に水素を、接
液側に水を供給することによって除去し、 ３）イオン交換処理及び限外ろ過処理を行うことによ
り、純水あるいは超純水の純度を更に高くすることがで
きた。As described above, in purifying pure water or ultrapure water, the apparatus of the present invention is: 1) The organic substance eluted from the ultrapure water production facility or the like is used in combination with ozone and ultraviolet irradiation. 2) Dissolved oxygen (DO) dissolved in the water to be treated and ozone and oxygen increased by the addition of ozone are added to the gas contacting side of the gas permeable membrane module containing palladium, and hydrogen is decomposed. Was removed by supplying water to the liquid contact side, and 3) by performing ion exchange treatment and ultrafiltration treatment, the purity of pure water or ultrapure water could be further increased.
【図１】本発明の実施態様の一例を示す模式図である。FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention.
【図２】本発明の実施態様の他の一例を示す模式図であ
る。FIG. 2 is a schematic view showing another example of the embodiment of the present invention.
【図３】従来のサブシステムの模式図である。FIG. 3 is a schematic diagram of a conventional subsystem.
【図４】従来のオゾン殺菌併用サブシステムの模式図で
ある。FIG. 4 is a schematic diagram of a conventional ozone sterilization combined use subsystem.
【図５】従来のオゾン殺菌併用サブシステムの他の一例
を示す模式図である。FIG. 5 is a schematic view showing another example of a conventional ozone sterilization combined use subsystem.
１：純水供給ライン、２：三方弁、３：オゾン溶解器、
４：気体透過膜、５：混合器、６：オゾン水ライン、
７：オゾンガス供給ライン、８：オゾン発生器、９：オ
ゾン排ガスライン、１０：オゾン水封管、１１：紫外線
照射塔、１２：パラジウム担持気体透過膜モジュール、
１３：パラジウム担持気体透過膜、１４：水素水封管、
１５：水素排ガスライン、１６：水素ガス供給ライン、
１７：ポンプ、１８：カートリッジ型イオン交換樹脂
塔、１９：限外ろ過装置、２０：排ガス処理装置、２
１：タンク、２２：超純水供給ライン、２３：ユースポ
イント、２４：リターンライン、２５：熱交換器、２
６：窒素シール1: Pure water supply line, 2: Three-way valve, 3: Ozone dissolver,
4: Gas permeable membrane, 5: Mixer, 6: Ozone water line,
7: Ozone gas supply line, 8: Ozone generator, 9: Ozone exhaust gas line, 10: Ozone water sealing tube, 11: Ultraviolet irradiation tower, 12: Palladium-supported gas permeable membrane module,
13: Palladium-supported gas permeable membrane, 14: Hydrogen water sealed tube,
15: Hydrogen exhaust gas line, 16: Hydrogen gas supply line,
17: Pump, 18: Cartridge type ion exchange resin tower, 19: Ultrafiltration device, 20: Exhaust gas treatment device, 2
1: Tank, 22: Ultrapure water supply line, 23: Use point, 24: Return line, 25: Heat exchanger, 2
6: Nitrogen seal
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年９月２５日[Submission date] September 25, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【図３】 [Figure 3]
【図２】 [Fig. 2]
【図４】 [Figure 4]
【図５】 [Figure 5]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０２Ｆ 1/70 Ｚ 9045−4Ｄ 1/78 9045−4Ｄ (72)発明者 斉藤 孝行 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 (72)発明者 中島 健 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 (72)発明者 嶋 弘之 東京都大田区羽田旭町11番１号 株式会社 荏原製作所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication location C02F 1/70 Z 9045-4D 1/78 9045-4D (72) Inventor Takayuki Saito Fujisawa City, Kanagawa Prefecture Hon Fujisawa 4-2-1 Ebara Research Institute Ltd. (72) Inventor Ken Nakajima Fujisawa, Kanagawa Prefecture 4-2-1 Hon Fujisawa Research Institute Ebara Research Institute (72) Inventor Hiroyuki Shima Shima 11-1 Haneda-Asahi-cho, Ota-ku Ebara Corporation
Claims (8)
水を得る精製方法であって、前記精製方法が、（イ）原
水にオゾンを溶解する工程、（ロ）（イ）の処理水に紫
外線を照射する工程、（ハ）パラジウムを担持した気体
透過膜の接液側に（ロ）の処理水を通水し、接ガス側に
水素を供給する工程、（ニ）（ハ）の処理水をＨ型強酸
性カチオン交換樹脂とＯＨ型アニオン交換樹脂とを混合
したイオン交換樹脂層に通水する工程、（ホ）（ニ）の
処理水を限外ろ過する工程、からなることを特徴とする
純水又は超純水の精製方法。1. A purification method for obtaining even higher-purity ultrapure water from pure water or ultrapure water, the purification method comprising: (a) dissolving ozone in raw water; and (b) (a) A step of irradiating the treated water with ultraviolet rays, (c) a step of passing the treated water of (b) to the liquid contact side of the gas permeable membrane supporting palladium and supplying hydrogen to the gas contact side, (d) (iii) ), The step of passing the treated water through the ion exchange resin layer in which the H-type strongly acidic cation exchange resin and the OH type anion exchange resin are mixed, and the step (e) (d) of ultrafiltering the treated water. A method for purifying pure water or ultrapure water.
水を得る精製方法であって、前記精製方法が、（イ）原
水の一部にオゾンを溶解する工程、（ロ）（イ）のオゾ
ン溶解水と残部の原水とを混合する工程、（ハ）（ロ）
の処理水に紫外線を照射する工程、（ニ）パラジウムを
担持した気体透過膜の接液側に（ハ）の処理水を通水
し、接ガス側に水素を供給する工程、（ホ）（ニ）の処
理水をＨ型強酸性カチオン交換樹脂とＯＨ型アニオン交
換樹脂とを混合したイオン交換樹脂層に通水する工程、
（ヘ）（ホ）の処理水を限外ろ過する工程、からなるこ
とを特徴とする純水又は超純水の精製方法。2. A purification method for obtaining even higher-purity ultrapure water from pure water or ultrapure water, the purification method comprising: (a) dissolving ozone in a part of raw water; (A) A step of mixing the ozone-dissolved water with the rest of the raw water, (c) (b)
Irradiating the treated water with ultraviolet light, (d) passing the treated water of (c) to the liquid contact side of the gas permeable membrane supporting palladium and supplying hydrogen to the gas contact side, (e) ( D) passing the treated water through an ion exchange resin layer in which an H-type strongly acidic cation exchange resin and an OH-type anion exchange resin are mixed,
(F) a step of ultrafiltering the treated water of (e), and a method for purifying pure water or ultrapure water.
水を得る精製方法であって、前記精製方法が、（イ）ユ
ースポイントから戻ってくる精製された未使用の超純水
の一部又は全部にオゾンを溶解する工程、（ロ）原水と
（イ）のオゾン溶解水とを混合する工程、（ハ）（ロ）
の処理水に紫外線を照射する工程、（ニ）パラジウムを
担持した気体透過膜の接液側に（ハ）の処理水を通水
し、接ガス側に水素を供給する工程、（ホ）（ニ）の処
理水をＨ型強酸性カチオン交換樹脂とＯＨ型アニオン交
換樹脂とを混合したイオン交換樹脂層に通水する工程、
（ヘ）（ホ）の処理水を限外ろ過する工程、からなるこ
とを特徴とする純水又は超純水の精製方法。3. A purification method for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the purification method is (a) purified unused ultrapure water returned from a point of use. Of (b) raw water and (a) ozone-dissolved water, (c) (b)
Irradiating the treated water with ultraviolet light, (d) passing the treated water of (c) to the liquid contact side of the gas permeable membrane supporting palladium and supplying hydrogen to the gas contact side, (e) ( D) passing the treated water through an ion exchange resin layer in which an H-type strongly acidic cation exchange resin and an OH-type anion exchange resin are mixed,
(F) a step of ultrafiltering the treated water of (e), and a method for purifying pure water or ultrapure water.
ン含有排ガスと、前記水素供給工程から排出される水素
含有排ガスとを混合し、水素燃焼触媒を有する触媒層で
処理することを特徴とする請求項１、２又は３記載の純
水又は超純水の精製方法。4. The ozone-containing exhaust gas discharged from the ozone dissolution step and the hydrogen-containing exhaust gas discharged from the hydrogen supply step are mixed and treated with a catalyst layer having a hydrogen combustion catalyst. Item 4. A method for purifying pure water or ultrapure water according to item 1, 2 or 3.
水を得る精製装置であって、前記精製装置が、（イ）原
水にオゾンを溶解するオゾン溶解装置と、（ロ）紫外線
照射装置と、（ハ）接液側に（ロ）の処理水を通水し、
接ガス側に水素を供給する手段を有するパラジウムを担
持した気体透過膜装置と、（ニ）Ｈ型強酸性カチオン交
換樹脂とＯＨ型アニオン交換樹脂とを混合したイオン交
換樹脂層を有するイオン交換装置と、（ホ）限外ろ過装
置とを備え、（ヘ）前記（イ）から（ホ）までの装置相
互間を順次配管で接続したことを特徴とする純水又は超
純水の精製装置。5. A refining apparatus for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the refining apparatus comprises (a) an ozone dissolving device for dissolving ozone in raw water, and (b) ultraviolet rays. Pass the treated water of (b) to the irradiation device and (c) liquid contact side,
A gas permeable membrane device supporting palladium having a means for supplying hydrogen to the gas contact side, and (d) an ion exchange device having an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed. And (e) an ultrafiltration device, and (f) a device for purifying pure water or ultrapure water, characterized in that the devices (a) to (e) are connected to each other in sequence by pipes.
水を得る精製装置であって、前記精製装置が、（イ）原
水の一部にオゾンを溶解するオゾン溶解装置と、（ロ）
（イ）のオゾン溶解水と残部の原水とを混合する装置
と、（ハ）紫外線照射装置と、（ニ）接液側に（ハ）の
処理水を通水し、接ガス側に水素を供給する手段を有す
るパラジウムを担持した気体透過膜装置と、（ホ）Ｈ型
強酸性カチオン交換樹脂とＯＨ型アニオン交換樹脂とを
混合したイオン交換樹脂層を有するイオン交換装置と、
（ヘ）限外ろ過装置とを備え、（ト）前記（イ）から
（ヘ）までの装置相互間を順次配管で接続したことを特
徴とする純水又は超純水の精製装置。6. A refining device for obtaining even higher purity ultrapure water from pure water or ultrapure water, wherein the refining device comprises: (a) an ozone dissolving device for dissolving ozone in a part of raw water; B)
(A) A device for mixing the ozone-dissolved water with the rest of the raw water, (c) an ultraviolet irradiation device, (d) passing the treated water of (c) to the liquid contact side, and hydrogen to the gas contact side. A gas permeable membrane device supporting palladium having a supplying means, and (e) an ion exchange device having an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed,
(F) An ultrafiltration device, and (g) a device for purifying pure water or ultrapure water, characterized in that the devices (a) to (f) are sequentially connected by piping.
水を得る精製装置であって、前記精製装置が、（イ）ユ
ースポイントから戻ってくる精製された未使用の超純水
の一部又は全部にオゾンを溶解するオゾン溶解装置と、
（ロ）原水と（イ）のオゾン溶解水とを混合する装置
と、（ハ）紫外線照射装置と、（ニ）接液側に（ハ）の
処理水を通水し、接ガス側に水素を供給する手段を有す
るパラジウムを担持した気体透過膜装置と、（ホ）Ｈ型
強酸性カチオン交換樹脂とＯＨ型アニオン交換樹脂とを
混合したイオン交換樹脂層を有するイオン交換装置と、
（ヘ）限外ろ過装置とを備え、（ト）前記（イ）から
（ヘ）までの装置相互間を順次配管で接続したことを特
徴とする純水又は超純水の精製装置。7. A purification apparatus for obtaining ultrapure water of higher purity from pure water or ultrapure water, wherein the purification apparatus returns (a) purified, unused ultrapure water. An ozone dissolving device that dissolves ozone in part or all of
(B) A device that mixes raw water and (a) ozone-dissolved water, (c) an ultraviolet irradiation device, (d) water that passes through (c) the treated water to the wetted side, and hydrogen to the gas contacted side. A gas permeable membrane device supporting palladium having a means for supplying hydrogen, and (e) an ion exchange device having an ion exchange resin layer in which an H type strongly acidic cation exchange resin and an OH type anion exchange resin are mixed,
(F) An ultrafiltration device, and (g) a device for purifying pure water or ultrapure water, characterized in that the devices (a) to (f) are sequentially connected by piping.
装置を設け、発生するオゾンと水素とをそれぞれオゾン
溶解装置と気体透過膜とに供給するための手段を設けた
ことを特徴とする請求項５、６又は７記載の純水又は超
純水の精製装置。8. The refining apparatus is provided with an electrolysis type ozone generator, and means for supplying the generated ozone and hydrogen to the ozone dissolving device and the gas permeable membrane, respectively. Item 5. A device for purifying pure water or ultrapure water according to item 6 above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3140593A JPH0818040B2 (en) | 1991-05-17 | 1991-05-17 | Purification method and device for pure water or ultrapure water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3140593A JPH0818040B2 (en) | 1991-05-17 | 1991-05-17 | Purification method and device for pure water or ultrapure water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0699197A true JPH0699197A (en) | 1994-04-12 |
| JPH0818040B2 JPH0818040B2 (en) | 1996-02-28 |
Family
ID=15272304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3140593A Expired - Fee Related JPH0818040B2 (en) | 1991-05-17 | 1991-05-17 | Purification method and device for pure water or ultrapure water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0818040B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001038364A (en) * | 1999-08-02 | 2001-02-13 | Kurita Water Ind Ltd | Sterilization method and device for ultrapure water production and feed device |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| JP2002057136A (en) * | 2000-08-09 | 2002-02-22 | Sekisui Chem Co Ltd | Wafer washing device |
| EP1188473A1 (en) * | 1999-04-27 | 2002-03-20 | Kurita Water Industries Ltd. | Apparatus for producing water containing dissolved ozone |
| JP2004169746A (en) * | 2002-11-18 | 2004-06-17 | Japan Organo Co Ltd | Fluid transfer piping, fluid transfer device, and assembling method |
| WO2005095280A1 (en) * | 2004-03-31 | 2005-10-13 | Kurita Water Industries Ltd. | Apparatus for producing ultrapure water |
| KR100796561B1 (en) * | 2006-08-16 | 2008-01-23 | 지은상 | Deionized water system with membrabe separation technology for power plant |
| KR100823460B1 (en) * | 2007-06-04 | 2008-05-08 | 주식회사 현진기업 | An apparatus of virus and bacteria remove using sterilizer and oxygen supply |
| JP2009140632A (en) * | 2007-12-04 | 2009-06-25 | Toshiba Fuel Cell Power Systems Corp | Fuel cell system |
| JP4552327B2 (en) * | 2001-01-18 | 2010-09-29 | 栗田工業株式会社 | Ultrapure water production equipment |
| JP2010240642A (en) * | 2009-03-18 | 2010-10-28 | Japan Organo Co Ltd | Method of manufacturing dissolved oxygen-removed water, apparatus for manufacturing dissolved oxygen-removed water, dissolved oxygen treatment tank, method of manufacturing ultrapure water, method of manufacturing hydrogen dissolved water, apparatus for manufacturing hydrogen dissolved water, and method of cleaning electronic components |
| KR20110053946A (en) * | 2008-07-28 | 2011-05-24 | 쿠리타 고교 가부시키가이샤 | Process and equipment for the treatment of water containing organic matter |
| JP2012525247A (en) * | 2009-04-30 | 2012-10-22 | ロワラ | Purification method and apparatus for removing xenobiotics in water |
| CN105858967A (en) * | 2016-05-27 | 2016-08-17 | 河南师范大学 | Method for deeply treating municipal sewage and reusing treated sewage in circulating cooling water system |
-
1991
- 1991-05-17 JP JP3140593A patent/JPH0818040B2/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1188473A1 (en) * | 1999-04-27 | 2002-03-20 | Kurita Water Industries Ltd. | Apparatus for producing water containing dissolved ozone |
| EP1188473A4 (en) * | 1999-04-27 | 2005-10-12 | Kurita Water Ind Ltd | Apparatus for producing water containing dissolved ozone |
| JP2001038364A (en) * | 1999-08-02 | 2001-02-13 | Kurita Water Ind Ltd | Sterilization method and device for ultrapure water production and feed device |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| JP2002057136A (en) * | 2000-08-09 | 2002-02-22 | Sekisui Chem Co Ltd | Wafer washing device |
| JP4636659B2 (en) * | 2000-08-09 | 2011-02-23 | 積水化学工業株式会社 | Substrate cleaning device |
| JP4552327B2 (en) * | 2001-01-18 | 2010-09-29 | 栗田工業株式会社 | Ultrapure water production equipment |
| JP2004169746A (en) * | 2002-11-18 | 2004-06-17 | Japan Organo Co Ltd | Fluid transfer piping, fluid transfer device, and assembling method |
| JPWO2005095280A1 (en) * | 2004-03-31 | 2008-02-21 | 栗田工業株式会社 | Ultrapure water production equipment |
| WO2005095280A1 (en) * | 2004-03-31 | 2005-10-13 | Kurita Water Industries Ltd. | Apparatus for producing ultrapure water |
| JP5045099B2 (en) * | 2004-03-31 | 2012-10-10 | 栗田工業株式会社 | Ultrapure water production apparatus and operation method of ultrapure water production apparatus |
| KR100796561B1 (en) * | 2006-08-16 | 2008-01-23 | 지은상 | Deionized water system with membrabe separation technology for power plant |
| KR100823460B1 (en) * | 2007-06-04 | 2008-05-08 | 주식회사 현진기업 | An apparatus of virus and bacteria remove using sterilizer and oxygen supply |
| JP2009140632A (en) * | 2007-12-04 | 2009-06-25 | Toshiba Fuel Cell Power Systems Corp | Fuel cell system |
| KR20110053946A (en) * | 2008-07-28 | 2011-05-24 | 쿠리타 고교 가부시키가이샤 | Process and equipment for the treatment of water containing organic matter |
| JP2010240642A (en) * | 2009-03-18 | 2010-10-28 | Japan Organo Co Ltd | Method of manufacturing dissolved oxygen-removed water, apparatus for manufacturing dissolved oxygen-removed water, dissolved oxygen treatment tank, method of manufacturing ultrapure water, method of manufacturing hydrogen dissolved water, apparatus for manufacturing hydrogen dissolved water, and method of cleaning electronic components |
| JP2012525247A (en) * | 2009-04-30 | 2012-10-22 | ロワラ | Purification method and apparatus for removing xenobiotics in water |
| CN105858967A (en) * | 2016-05-27 | 2016-08-17 | 河南师范大学 | Method for deeply treating municipal sewage and reusing treated sewage in circulating cooling water system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0818040B2 (en) | 1996-02-28 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |