JPH11258219A - Method for monitoring break-through of ion adsorption film for manufacturing extra-pure water - Google Patents
Method for monitoring break-through of ion adsorption film for manufacturing extra-pure waterInfo
- Publication number
- JPH11258219A JPH11258219A JP10057174A JP5717498A JPH11258219A JP H11258219 A JPH11258219 A JP H11258219A JP 10057174 A JP10057174 A JP 10057174A JP 5717498 A JP5717498 A JP 5717498A JP H11258219 A JPH11258219 A JP H11258219A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- membrane
- adsorbing
- film
- impurities
- 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
- 238000000034 method Methods 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000012544 monitoring process Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 title abstract description 81
- 239000012535 impurity Substances 0.000 claims abstract description 69
- 239000012528 membrane Substances 0.000 claims description 92
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 45
- 239000012498 ultrapure water Substances 0.000 claims description 45
- 238000005342 ion exchange Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 239000008213 purified water Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 description 37
- 150000001768 cations Chemical class 0.000 description 13
- 150000001450 anions Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000013522 chelant Substances 0.000 description 8
- 238000005349 anion exchange Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 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 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- -1 ion ion Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超純水の製造方法
に関する。更に詳しくは、本発明は、超純水製造装置の
ユースポイント直前に設けられていたイオン吸着膜の破
過をより正確に予測する方法、及びこの方法を利用した
超純水の製造方法に関する。[0001] The present invention relates to a method for producing ultrapure water. More specifically, the present invention relates to a method for more accurately predicting breakthrough of an ion adsorption film provided immediately before a use point of an ultrapure water production apparatus, and a method for producing ultrapure water using this method.
【０００２】[0002]
【従来の技術】半導体製造産業において、不純物を高度
に除去した超純水は必須のアイテムである。超純水は、
一般に、１次系純水製造装置及び２次系純水製造装置
（サブシステム）を経て製造され、不純物の定量も困難
である程の純度を有する。上記サブシステムには、１種
または２種以上のイオン交換樹脂が用いられている。2. Description of the Related Art In the semiconductor manufacturing industry, ultrapure water from which impurities are highly removed is an essential item. Ultrapure water is
Generally, it is produced through a primary pure water production device and a secondary pure water production device (subsystem), and has such a purity that it is difficult to quantify impurities. One or two or more ion exchange resins are used in the subsystem.
【０００３】さらに、超純水が含む超微量成分が半導体
デバイスに与える影響は、デバイスの集積度が高くなる
と、無視できなくなり、従来の超純水より高い純度を有
する超純水の必要性も検討さている。例えば、サブシス
テムで製造された超純水は配管を経てユースポイントに
供給されるが、サブシステムとユースポイント間の配管
は、長いときには数百メートルに及ぶ場合がある。その
ため、この配管から微粒子（パーティクル）や金属イオ
ン成分等の不純物が超純水に僅かではあるが混入し、デ
バイスの特性に悪影響を及ぼす場合がある。Further, the influence of ultra-trace components contained in ultra-pure water on a semiconductor device cannot be ignored as the degree of integration of the device increases, and the necessity of ultra-pure water having higher purity than conventional ultra-pure water is also required. Is under consideration. For example, the ultrapure water produced in the subsystem is supplied to the point of use via a pipe, but the pipe between the subsystem and the point of use can be hundreds of meters long. For this reason, impurities such as fine particles (particles) and metal ion components may be slightly mixed into the ultrapure water from the pipe, which may adversely affect the characteristics of the device.
【０００４】このような状況に対処する手段として、ユ
ースポイント直前で、超純水をさらに処理するユースポ
イントモジュールシステムが提案さている（特開平８−
８９９５４号公報）。このユースポイントモジュールシ
ステムは、膜内部にイオン交換基を有する高分子鎖が保
持されている中空糸状多孔膜であって、膜１ｇ当たり
０．２〜１０ミリ当量のイオン交換基を有し、平均孔径
０．０１〜１μｍの中空糸状多孔膜を充填したモジュー
ルをユースポイント直前に配置したものである。即ち、
イオン交換樹脂を多孔膜化したものである。As means for coping with such a situation, a point-of-use module system for further processing ultrapure water immediately before a point of use has been proposed (Japanese Unexamined Patent Publication No. Hei 8 (1996) -1994).
89954). This use point module system is a hollow fiber-like porous membrane in which a polymer chain having an ion exchange group is retained inside the membrane, and has 0.2 to 10 milliequivalents of ion exchange groups per gram of the membrane. A module filled with a hollow fiber porous membrane having a pore size of 0.01 to 1 μm is arranged immediately before a use point. That is,
It is a porous membrane of an ion exchange resin.
【０００５】[0005]
【発明が解決すべき課題】上記イオン吸着膜モジュール
は、超純水製造装置のユースポイント直前に設けられ、
破過前に、新品に交換される。超純水の品質に対する要
求は極めて厳しく、破過経過後のイオン吸着膜が使用さ
れることは、デバイスの物性に多大の悪影響を及ぼすか
らである。The above-mentioned ion adsorption membrane module is provided immediately before the point of use of the ultrapure water production apparatus.
Before the breakthrough, it is replaced with a new one. The requirement for the quality of ultrapure water is extremely severe, and the use of an ion-adsorbed film after the passage of breakthrough has a great adverse effect on the physical properties of the device.
【０００６】ところが、上記イオン吸着膜の実際の破過
時間は、流量が一定の場合、超純水製造用のサブシステ
ム（２次系純水製造装置）から得られる水質により変化
する。このような状況下で、イオン吸着膜の交換を破過
の直前に行うことは難しく、超純水の品質低下によるデ
バイス物性の悪化を回避するため、実際の破過よりかな
り前にイオン吸着膜を交換する必要がある。また、超純
水の純度（水質）は、現存の分析機器の精度では検出で
きない程度にまで高められている。そのため、超純水自
体の分析から、イオン吸着膜の破過を予測することは事
実上困難であり、ユースポイント直前に設けらるイオン
吸着膜の寿命を監視することはできなかった。また、実
用上、実際の破過に限りなく近い時期にイオン吸着膜を
交換できれば、生産効率は高まる。However, when the flow rate is constant, the actual breakthrough time of the ion-adsorbing film varies depending on the water quality obtained from the ultrapure water production subsystem (secondary pure water production apparatus). Under such circumstances, it is difficult to replace the ion-adsorbing membrane immediately before the breakthrough, and to avoid deteriorating the device properties due to the deterioration of the ultrapure water quality, the ion-adsorbing membrane is long before the actual breakthrough. Need to be replaced. In addition, the purity (water quality) of ultrapure water has been increased to such an extent that it cannot be detected with the accuracy of existing analytical instruments. Therefore, it is practically difficult to predict the breakthrough of the ion-adsorbing film from the analysis of the ultrapure water itself, and it has not been possible to monitor the life of the ion-adsorbing film provided immediately before the use point. Further, if the ion-adsorbing membrane can be replaced at a time near the actual breakthrough in practical use, the production efficiency will increase.
【０００７】そこで本発明の目的は、超純水製造に使用
されるイオン吸着膜の破過を予測できる新たな方法及び
その方法を利用してイオン吸着膜を有効利用できる超純
水の製造方法を提供することにある。Accordingly, an object of the present invention is to provide a new method capable of predicting breakthrough of an ion-adsorbing film used for producing ultrapure water and a method of producing ultrapure water capable of effectively utilizing the ion-adsorbing film by using the method. Is to provide.
【０００８】[0008]
【課題を解決するための手段】そこで本発明は、超純水
製造装置のユースポイント直前において用いられるイオ
ン吸着膜の破過をモニタリングする方法であって、モニ
タリングすべきイオン吸着膜（Ａ）と同じ性能を有する
イオン吸着膜（Ｂ）をイオン吸着膜（Ａ）と並列に設
け、このイオン吸着膜（Ｂ）に被精製水を接触させ、捕
獲された不純物量からイオン吸着膜（Ａ）の破過到達時
期を予測することを特徴とする方法に関する。さらに本
発明は、超純水製造装置のユースポイント直前において
イオン吸着膜を用いる超純水の製造方法であって、上記
の方法を利用して予測される破過前に上記イオン吸着膜
を交換することを特徴とする方法に関する。SUMMARY OF THE INVENTION Accordingly, the present invention is a method for monitoring breakthrough of an ion-adsorbing membrane used immediately before a point of use of an ultrapure water production apparatus, comprising: an ion-adsorbing membrane (A) to be monitored; An ion-adsorbing film (B) having the same performance is provided in parallel with the ion-adsorbing film (A), and the purified water is brought into contact with the ion-adsorbing film (B). The present invention relates to a method characterized by predicting a breakthrough arrival time. Further, the present invention is a method for producing ultrapure water using an ion-adsorbing membrane immediately before the point of use of the ultrapure water producing apparatus, wherein the ion-adsorbing membrane is replaced before the breakthrough predicted using the above method. To a method characterized by:
【０００９】[0009]
【発明の実施の形態】本発明は、超純水製造装置のユー
スポイント直前において用いられるイオン吸着膜の破過
をモニタリングする方法である。超純水製造装置のユー
スポイント直前において用いられるイオン吸着膜には特
に制限はない。例えば、膜内部にイオン交換機能を有す
る高分子鎖が保持されている多孔膜であって、膜１ｇ当
たり０．２〜１０ミリ当量のイオン交換基を有し、平均
孔径０．０１〜１μｍの多孔膜を充填したモジュールで
あるイオン吸着膜モジュールを挙げることができる。こ
のようなイオン吸着膜モジュールとしては、例えば、特
開平８−８９９５４号公報に開示されているものを挙げ
ることができる。より具体的には、イオン吸着膜とし
て、例えば、アニオン交換機能を有するアニオン吸着
膜、カチオン交換機能を有するカチオン吸着膜、キレー
ト形成基を有するキレート膜等を挙げることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is a method for monitoring breakthrough of an ion adsorption film used immediately before a point of use of an ultrapure water production apparatus. There is no particular limitation on the ion adsorption film used immediately before the use point of the ultrapure water production apparatus. For example, a porous membrane in which a polymer chain having an ion exchange function is retained inside the membrane, having 0.2 to 10 milliequivalents of ion exchange groups per gram of the membrane and having an average pore diameter of 0.01 to 1 μm An ion adsorption membrane module which is a module filled with a porous membrane can be given. Examples of such an ion-adsorbing membrane module include those disclosed in Japanese Patent Application Laid-Open No. 8-89954. More specifically, examples of the ion adsorption membrane include an anion adsorption membrane having an anion exchange function, a cation adsorption membrane having a cation exchange function, and a chelate membrane having a chelate-forming group.
【００１０】アニオン吸着膜は、アニオン交換基として
４級アミンを有するものであり、例えば、クロロメチル
スチレンを４級化したアニオン交換基を有する膜が好適
に用いられる。但し、ピリジン系やイミダゾール系など
の複素環の窒素原子を４級化したアニオン交換基もアニ
オン吸着膜として使用可能である。カチオン吸着膜とし
ては、カチオン交換基として、例えば、スルホン酸基、
リン酸基、またはカルボキシル基等を有する膜を挙げる
ことができる。キレート膜としては、キレート形成基と
して、水中の金属イオンとキレートを形成する機能を持
った官能基である、例えば、イミノジ酢酸基、メルカプ
ト基、エチレンジアミンなどを有する膜を挙げることが
できる。The anion-adsorbing membrane has a quaternary amine as an anion exchange group. For example, a membrane having an anion exchange group obtained by quaternizing chloromethylstyrene is preferably used. However, an anion exchange group obtained by quaternizing a nitrogen atom of a heterocyclic ring such as a pyridine type or an imidazole type can also be used as the anion adsorption film. As the cation adsorption membrane, as a cation exchange group, for example, a sulfonic acid group,
A film having a phosphate group, a carboxyl group, or the like can be given. Examples of the chelate film include a film having, as a chelate-forming group, a functional group having a function of forming a chelate with metal ions in water, such as an iminodiacetic acid group, a mercapto group, and ethylenediamine.
【００１１】上記イオン吸着膜は、膜1gあたり0.2〜10
ミリ当量のイオン交換基（キレート膜の場合にはキレ−
ト形成基）を有し、好ましくは0.5〜5ミリ等量のイオン
交換基あるいはキレ−ト形成基を有する。これは、イオ
ン交換基またはキレ−ト形成基の量が膜1gあたり0.2ミ
リ当量未満では、イオン等に対する吸着容量が減少し、
交換頻度が増大するため好ましくないからである。ま
た、イオン交換基あるいはキレ−ト形成基の量が膜1gあ
たり10ミリ当量を超えると、膜の寸法変化が大きくな
り、強度が低下するため、長時間使用に耐えられなくな
る傾向がある。また、イオン吸着膜は、平均孔径が０．
０１〜１μｍの多孔膜であることが適当であり、好まし
くは平均孔径が０．０５〜０．５μｍの範囲である。平
均孔径が０．０１μｍ未満では、膜透過抵抗が大きくな
り、１μｍを超えると微粒子の除去性能が不十分になる
とうい不都合がある。なお平均孔径は、ＡＳＴＭ、Ｆ３
１６−７０に記載されているエアフロー法と呼ばれる方
法で得られた値である。また、膜１ｇあたりとは、比較
的巨視的に膜全体を見た値であり、ある一部分の膜につ
いて言っているものではない。その測定方法は、アニオ
ン交換基を保持した膜の場合、得られた膜について、１
Ｎ水酸化ナトリウム溶液を十分量通水し、アニオン交換
基をＯＨ型にした後、乾燥重量を測定し、再び、水に濡
らした後、１ＮのＮａＣｌ水溶液を通水して、Ｃｌイオ
ンを吸着させた後、１Ｎ硝酸カリウム溶液を十分量通水
し、透過液について、沈殿適定し、Ｃｌイオン吸着量を
求め、該Ｃｌ吸着量を膜乾燥重量で割った値としてアニ
オン交換基保持量を求める。[0011] The ion-adsorbing membrane is 0.2 to 10 per gram of the membrane.
Milli-equivalent ion exchange groups (in the case of chelate membranes,
And preferably 0.5 to 5 milliequivalents of an ion exchange group or a chelate forming group. This is because if the amount of ion-exchange groups or chelate-forming groups is less than 0.2 meq / g of membrane, the adsorption capacity for ions and the like decreases,
This is because the frequency of replacement increases, which is not preferable. On the other hand, if the amount of the ion-exchange groups or chelate-forming groups exceeds 10 milliequivalents per gram of the membrane, the dimensional change of the membrane becomes large and the strength is reduced, so that it tends not to be able to withstand long-term use. The ion-adsorbing membrane has an average pore size of 0.1.
It is suitable that the porous membrane has a diameter of from 01 to 1 μm, and preferably has an average pore diameter in the range of from 0.05 to 0.5 μm. When the average pore diameter is less than 0.01 μm, the membrane permeation resistance increases, and when it exceeds 1 μm, there is a disadvantage that the performance of removing fine particles becomes insufficient. The average pore size was determined by ASTM, F3
It is a value obtained by a method called an air flow method described in 16-70. Further, "per gram of film" is a value obtained by relatively macroscopically viewing the entire film, and does not refer to a part of the film. The measurement method is as follows. In the case of a membrane holding an anion exchange group, 1
After passing a sufficient amount of N sodium hydroxide solution to make the anion exchange group OH type, measure the dry weight, wet again with water, pass 1N NaCl aqueous solution to adsorb Cl ion. After that, a sufficient amount of a 1N potassium nitrate solution was passed through, the precipitate was determined for the permeated solution, the amount of Cl ion adsorbed was obtained, and the Cl adsorbed amount divided by the dry weight of the membrane was used to obtain the anion exchange group holding amount. .
【００１２】カチオン交換基を保持した膜の場合は、１
Ｎ塩酸で、Ｈ型にした後、やはり、０．１ＮのＮａＣｌ
水溶液を通水して、Ｎａイオンを吸着させ、通水後の液
について、中和適定を行い、Ｎａイオン吸着量を求め、
イオン交換基量を求めた。キレート形成基を保持した膜
の場合は、１Ｎ塩酸で、Ｈ型にした後、100ppmの硫酸銅
溶液を通水して、Ｃｕイオンを吸着させ、１Ｎ塩酸で脱
着し、脱着液について、原子吸光法で銅イオン濃度を求
め、キレート形成基量を求めた。In the case of a membrane holding a cation exchange group, 1
After being made into H-form with N hydrochloric acid, 0.1N NaCl
The aqueous solution is passed through to allow Na ions to be adsorbed, and the neutralized solution is subjected to neutralization to determine the amount of Na ions adsorbed.
The amount of ion exchange groups was determined. In the case of a film holding a chelate-forming group, after making it H-type with 1N hydrochloric acid, 100 ppm of copper sulfate solution is passed through to adsorb Cu ions and desorbed with 1N hydrochloric acid. The copper ion concentration was determined by the method, and the amount of the chelating group was determined.
【００１３】上記イオン吸着膜は、その種類により、除
去できる物質の種類や濃度が異なる。例えば、アニオン
吸着膜の場合、微粒子及びアニオン類、イオン状シリ
カ、コロイド成分、及び一部の遷移金属類を極低濃度ま
で除去することができる。カチオン吸着膜の場合、微粒
子及びアルカリ及びアルカリ土類金属、遷移金属類、及
びカチオン成分を極低濃度まで除去することができる。
キレ−ト膜の場合、微粒子及び遷移金属類を極低濃度ま
で除去することが可能であり、除去機構上、一度捕らえ
た金属を離しにくいという特徴を持つ。アルカリ金属の
除去が必要ない場合はキレ−ト膜の使用が望ましい。The type and concentration of the substance that can be removed from the ion-adsorbing film vary depending on the type. For example, in the case of an anion adsorption film, fine particles and anions, ionic silica, colloid components, and some transition metals can be removed to an extremely low concentration. In the case of a cation adsorption film, fine particles and alkali and alkaline earth metals, transition metals, and cation components can be removed to extremely low concentrations.
In the case of the chelate film, it is possible to remove fine particles and transition metals to an extremely low concentration, and it is characterized in that it is difficult to release the once captured metal due to the removal mechanism. When removal of alkali metal is not necessary, use of a chelate film is desirable.
【００１４】さらに、超純水に要求される純度等を考慮
して、上記イオン吸着膜を２種以上組み合わせて使用す
ることもある。例えば、カチオン吸着膜とアニオン吸着
膜とを組み合わせると微粒子、アルカリ金属及びアルカ
リ土類金属、遷移金属類、カチオン成分、アニオン成
分、並びにコロイド成分を極低濃度まで除去することが
できる。Further, in consideration of the purity required for ultrapure water and the like, two or more of the above-mentioned ion adsorption films may be used in combination. For example, when a cation adsorption film and an anion adsorption film are combined, fine particles, alkali metals and alkaline earth metals, transition metals, cation components, anion components, and colloid components can be removed to extremely low concentrations.
【００１５】本発明の方法では、モニタリングすべきイ
オン吸着膜（Ａ）と同じ性能を有するイオン吸着膜
（Ｂ）を用いる。ここでイオン吸着膜の性能とは、膜１
ｇ当たりのイオン交換基の量及び多孔膜の場合、平均孔
径を意味する。イオン交換基の量、及び多孔膜の場合、
さらに平均孔径が同等であれば、そのほかの点は異なっ
てもよい。例えば、後述するように、モニタリングすべ
きイオン吸着膜（Ａ）とイオン吸着膜（Ｂ）の膜面積は
異なっても良い。このようなイオン吸着膜（Ｂ）をモニ
タリングすべきイオン吸着膜（Ａ）と並列に設ける。こ
の状態をイオン吸着膜がカチオン吸着膜である場合を例
に図１に示す。イオン吸着膜（Ｂ）はイオン吸着膜
（Ａ）のバイパスとなり、イオン吸着膜（Ａ）と同質の
被精製水である超純水が接触させられる。これにより、
イオン吸着膜（Ａ）において捕獲されるであろう不純物
がイオン吸着膜（Ｂ）においても捕獲される。In the method of the present invention, an ion adsorption membrane (B) having the same performance as the ion adsorption membrane (A) to be monitored is used. Here, the performance of the ion-adsorbing membrane is defined as membrane 1
In the case of the amount of ion exchange groups per g and the porous membrane, it means the average pore size. The amount of ion exchange groups, and for porous membranes,
Further, other points may be different as long as the average pore diameter is the same. For example, as described later, the film areas of the ion adsorption film (A) and the ion adsorption film (B) to be monitored may be different. Such an ion adsorption film (B) is provided in parallel with the ion adsorption film (A) to be monitored. This state is shown in FIG. 1 by taking as an example the case where the ion adsorption film is a cation adsorption film. The ion-adsorbing film (B) serves as a bypass of the ion-adsorbing film (A), and is brought into contact with the ion-adsorbing film (A) by ultrapure water, which is water to be purified. This allows
Impurities that would be captured in the ion adsorption film (A) are also captured in the ion adsorption film (B).
【００１６】イオン吸着膜（Ｂ）に捕獲された不純物量
は、破壊または非破壊検査により測定される。イオン吸
着膜（Ｂ）に捕獲された不純物量は、例えば、イオン吸
着膜（Ｂ）に捕獲された不純物を物理化学的に脱離し、
脱離した不純物を常法により定量することにより求める
ことができる。例えば、カチオン吸着膜の場合、膜に吸
着した不純物を少量の硝酸や硫酸等の酸で溶離すること
ができる。アニオン吸着膜の場合、アニオンやコロイド
を溶離させる場合はアンモニア等のアルカリあるいは高
濃度の塩で溶離することができ、金属を溶離する場合は
硝酸や硫酸等の酸を溶離液として用いることができる。
キレ−ト膜の場合、硝酸や硫酸等の酸で溶離することが
できる。それぞれ、溶離した液体の分析をすることで不
純物量を定量することができる。不純物の溶離は膜を装
置から取り外して行っても、取り付けたまま行ってもよ
い。The amount of impurities captured by the ion-adsorbing film (B) is measured by a destructive or non-destructive inspection. The amount of the impurities captured by the ion-adsorbing film (B) is, for example, physicochemically desorbing the impurities captured by the ion-adsorbing film (B).
It can be determined by quantifying the eliminated impurities by a conventional method. For example, in the case of a cation adsorption membrane, impurities adsorbed on the membrane can be eluted with a small amount of an acid such as nitric acid or sulfuric acid. In the case of an anion adsorption membrane, when eluting anions or colloids, it can be eluted with an alkali such as ammonia or a high concentration salt, and when eluting metals, an acid such as nitric acid or sulfuric acid can be used as an eluent. .
In the case of a chelate film, it can be eluted with an acid such as nitric acid or sulfuric acid. The amount of impurities can be quantified by analyzing the eluted liquid. Elution of impurities may be performed with the membrane removed from the apparatus or with the membrane attached.
【００１７】不純物の分析方法としては、不純物が金属
の場合、例えば、原子吸光光度法やICP質量分析装置やI
CP発光等の分析装置を用いることができる。不純物がシ
リカの場合、例えば、原子吸光光度法やICP質量分析装
置、ICP発光、イオンクロマトグラフィーを用いること
ができる。不純物がハロゲンやフッ素の場合、例えば、
イオンクロマトグラフィーやICP−発光、ICP-MSを用い
ることができる。これらの分析の結果からイオン吸着膜
（Ｂ）に捕獲された不純物の定量を行ない、その吸着量
から吸着サイト（イオン交換基）の何％が不純物の吸着
により使用されているかが推定できる。さらにこの結果
により、イオン吸着膜（Ａ）に捕獲されているであろう
不純物量が推定でき、同時に不純物の吸着によるイオン
吸着膜（Ａ）の吸着サイトの使用率が推定できる。な
お、吸着サイトの使用率と破過との関係（吸着サイトの
何％が使用された時点で破過が起こるかの関係）を別途
調べておくことで、上記イオン吸着膜（Ａ）の吸着サイ
ト使用率の推定結果から、イオン吸着膜（Ａ）の破過が
起こる時期を予測することができる。吸着サイトの使用
率と破過との関係は、例えば、別途用意した液（実際に
イオン吸着膜（Ａ）に通水する水そのものか、あるいは
それに近い不純物濃度のモデル水）をイオン吸着膜に通
水し、破過が生じた時点で通水をやめ、該イオン吸着膜
に吸着させた不純物の量を前述の方法にて定量して破過
時点での吸着サイト使用率を決定することで実施でき
る。破過が起こったかどうかの判定は、例えばイオン吸
着膜の濾過水を清浄なシリコン基板の表面に連続して接
触させ、随時該シリコン基板上の不純物の付着量を測定
していくことで実施することができる。As a method of analyzing impurities, when the impurities are metals, for example, atomic absorption spectroscopy, ICP mass spectrometry,
An analyzer such as CP emission can be used. When the impurity is silica, for example, atomic absorption spectrometry, ICP mass spectrometry, ICP emission, ion chromatography can be used. When the impurity is halogen or fluorine, for example,
Ion chromatography, ICP-luminescence, and ICP-MS can be used. From the results of these analyses, impurities trapped in the ion-adsorbing film (B) are quantified, and it can be estimated from the amount of adsorption that what percentage of the adsorption sites (ion exchange groups) are used by the adsorption of the impurities. Further, from this result, the amount of impurities that may be captured by the ion-adsorbing film (A) can be estimated, and at the same time, the usage rate of the adsorption sites of the ion-adsorbing film (A) due to the adsorption of the impurities can be estimated. By separately examining the relationship between the usage rate of the adsorption site and the breakthrough (the relationship of what percentage of the adsorption site is used when breakthrough occurs), the adsorption of the ion-adsorbing film (A) can be determined. From the estimation result of the site usage rate, it is possible to predict when breakthrough of the ion-adsorbing film (A) occurs. The relationship between the usage rate of the adsorption site and the breakthrough can be determined, for example, by using a separately prepared liquid (water itself that actually passes through the ion adsorption membrane (A) or model water having an impurity concentration close thereto) to the ion adsorption membrane. By passing water, when the breakthrough occurs, stop the flow of water, and determine the amount of impurities adsorbed on the ion-adsorbing membrane by the above-described method to determine the use rate of the adsorption site at the time of the breakthrough. Can be implemented. The determination as to whether breakthrough has occurred is performed, for example, by continuously contacting the filtered water of the ion-adsorbing membrane with the surface of a clean silicon substrate and measuring the amount of impurities deposited on the silicon substrate as needed. be able to.
【００１８】また、イオン吸着膜（Ｂ）に捕獲された不
純物量は、イオン吸着膜（Ｂ）に捕獲された不純物を脱
離することなく定量することにより求めることもでき
る。例えば、膜に不純物が付着した状態のままで分析す
る方法としては、例えば、蛍光Ｘ線や、オ−ジェ電子分
光分析器（AES）、２次イオン質量分析装置（SIMS）、
Ｘ線光電子分光光度装置（XPS,ESCA）等を挙げることが
できる。分析結果から、不純物の吸着量を求め、上記と
同様にイオン吸着膜の寿命を推定できる。即ちイオン吸
着膜（Ｂ）に捕獲された不純物量からイオン吸着膜
（Ａ）に捕獲されているであろう不純物量を推測し、そ
の破過到達時期を予測することができる。Further, the amount of impurities trapped in the ion-adsorbing film (B) can be determined by quantifying the impurities trapped in the ion-adsorbing film (B) without desorbing. For example, as a method of analyzing a film with impurities attached thereto, for example, X-ray fluorescence, Auger electron spectroscopy (AES), secondary ion mass spectrometer (SIMS),
An X-ray photoelectron spectrophotometer (XPS, ESCA) can be used. From the analysis results, the amount of impurities adsorbed is obtained, and the life of the ion adsorption film can be estimated in the same manner as described above. That is, the amount of impurities that will be captured by the ion adsorption film (A) can be estimated from the amount of impurities captured by the ion adsorption film (B), and the breakthrough time can be predicted.
【００１９】尚、モニタリングする対象の不純物として
は、例えば、金属類、シリカ、ハロゲン（特に、フッ
素）等を挙げることができ、モニタリングすべき不純物
の種類に応じて上記分析方法を選択することができる。The impurities to be monitored include, for example, metals, silica, halogens (especially fluorine), and the like. The above analysis method can be selected according to the type of impurities to be monitored. it can.
【００２０】本発明のモニタリング方法において、イオ
ン吸着膜（Ｂ）への単位膜当たりの被精製水の接触量
を、イオン吸着膜（Ａ）への単位膜当たりの被精製水の
接触量より多くすることができる。これにより、単位膜
当たりのイオン吸着膜（Ｂ）への不純物負荷量を増や
し、不純物の定量を容易にすることができる。また、本
発明のモニタリング方法において、イオン吸着膜（Ｂ）
の膜面積をイオン吸着膜（Ａ）の膜面積より小さくする
こともできる。この場合も上記と同様に、単位膜当たり
のイオン吸着膜（Ｂ）への不純物負荷量を増やし、不純
物の定量を容易にすることができる。イオン吸着膜
（Ｂ）への被精製水の接触量と膜面積の小型化を組み合
わせることもできる。In the monitoring method of the present invention, the contact amount of the purified water per unit membrane to the ion adsorption membrane (B) is larger than the contact amount of the purified water per unit membrane to the ion adsorption membrane (A). can do. This makes it possible to increase the impurity load on the ion-adsorbing film (B) per unit film and to facilitate the quantitative determination of impurities. In the monitoring method of the present invention, the ion-adsorbing film (B)
Can be made smaller than the film area of the ion-adsorbing film (A). Also in this case, similarly to the above, it is possible to increase the impurity load on the ion-adsorbing film (B) per unit film and to facilitate the quantification of impurities. It is also possible to combine the contact amount of the purified water with the ion-adsorbing membrane (B) and the reduction of the membrane area.
【００２１】上記本発明は、超純水製造装置のユースポ
イント直前においてイオン吸着膜を用いる超純水の製造
方法も包含する。イオン吸着膜は、上記で説明したとお
りである。また、超純水製造装置のユースポイントと
は、１次系純水製造装置及び２次系純水製造装置（サブ
システム）を経て供給された超純水でウエハ洗浄を行う
ところである。本発明の方法では、上記本発明のモニタ
リング方法を利用して予測される破過前に上記イオン吸
着膜を交換する。The present invention also includes a method for producing ultrapure water using an ion-adsorbing membrane immediately before the point of use of the apparatus for producing ultrapure water. The ion adsorption membrane is as described above. The point of use of the ultrapure water production apparatus is where wafer cleaning is performed with ultrapure water supplied via the primary pure water production apparatus and the secondary pure water production apparatus (subsystem). In the method of the present invention, the ion-adsorbing membrane is replaced before the breakthrough predicted using the monitoring method of the present invention.
【００２２】[0022]
【実施例】以下本発明を実施例によりさらに詳細に説明
する。なお、本実施例で用いたイオン吸着膜は、T. Hor
i et al., J. Membr. Sci., 132(1997) 203-211記載の
方法に従って作製した。 実施例１ 図１に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインにNaの吸着
サイトが0.12mol/モジュールのカチオン吸着膜（イオン
交換容量１．６mmol/ｇ、孔径０．１μｍ）を2系列設置
した。そのうち1系列をイオン吸着膜の交換時期を決定
するための不純物測定用として3ヶ月通水を行った。不
純物測定用の膜に付着した不純物を酸で脱離した後、脱
離された不純物の内、NaについてICP-MSを用いて分析し
た。その結果、Na量は３．２mmol/モジュールであり、
吸着サイト使用は２．７％であった。吸着サイトの３０
％が使用されるであろう時期を交換時期と仮定すれば、
交換時期は使用開始後約３３ヶ月であった。結果を表１
にまとめて示す。The present invention will be described in more detail with reference to the following examples. Note that the ion-adsorbing film used in this example was T. Hor.
i et al., J. Membr. Sci., 132 (1997) 203-211. Example 1 As shown in FIG. 1, a cation adsorption membrane (0.12 mol / module) having 0.12 mol / module of Na adsorption site in a washing line branched from a main loop of a use point pipe of an ultrapure water system. 6 mmol / g, pore size 0.1 μm) were installed in two lines. One of them was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane. After the impurities attached to the film for impurity measurement were desorbed with an acid, Na among the desorbed impurities was analyzed using ICP-MS. As a result, the amount of Na is 3.2 mmol / module,
The use of the adsorption site was 2.7%. 30 of adsorption sites
Assuming the exchange time is when the% will be used,
The replacement period was about 33 months after the start of use. Table 1 shows the results
Are shown together.
【００２３】[0023]
【表１】 →推定交換時期：使用開始33ヶ月以内[Table 1] → Estimated replacement time: Within 33 months of use
【００２４】実施例２ 図１に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインに、Feの吸
着サイトが0.28mol/モジュールのカチオン吸着膜（イオ
ン交換容量１．６mmol/ｇ、孔径０．１μｍ）を2系列設
置した。そのうち1系列をイオン吸着膜の交換時期を決
定するための不純物測定用として３ヶ月通水を行った。
不純物測定用の膜に付着した不純物を酸で脱離した後、
脱離された不純物のうち遷移金属であるをICP-MSによっ
て分析した。その結果及び実施例１と同様にして推定さ
れた交換時期を表２に示す。EXAMPLE 2 As shown in FIG. 1, a washing line branched from a main loop of a use point pipe of an ultrapure water system is provided with a cation adsorption membrane (ion) having an Fe adsorption site of 0.28 mol / module. An exchange capacity of 1.6 mmol / g and a pore size of 0.1 μm) were installed in two lines. One of the series was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane.
After removing the impurities attached to the impurity measurement film with acid,
The transition metal among the desorbed impurities was analyzed by ICP-MS. Table 2 shows the results and the replacement time estimated in the same manner as in Example 1.
【００２５】[0025]
【表２】 →推定交換時期：使用開始34ヶ月後[Table 2] → Estimated replacement time: 34 months after starting use
【００２６】実施例３ 図２に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインに、シリカ
の吸着サイトが0.05mol/モジュールのアニオン吸着膜
（イオン交換容量２．６mmol/ｇ、孔径０．１μｍ）を2
系列設置した。そのうち1系列をイオン吸着膜の交換時
期を決定するための不純物測定用として３ヶ月通水を行
った。不純物測定用の膜に付着した不純物をアルカリで
脱離した後、脱離された不純物のうちシリカをICP-MSに
よって分析した。その結果及び実施例１と同様にして推
定された交換時期を表３に示す。Example 3 As shown in FIG. 2, an anion adsorption membrane (ion ion) having 0.05 mol / module of silica adsorption site was added to a washing line branched from a main loop of a use point pipe of an ultrapure water system. Exchange capacity 2.6 mmol / g, pore size 0.1 μm)
A series was established. One of the series was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane. After impurities adhering to the film for impurity measurement were desorbed with alkali, silica among the desorbed impurities was analyzed by ICP-MS. Table 3 shows the results and the replacement time estimated in the same manner as in Example 1.
【００２７】[0027]
【表３】 →推定交換時期：使用開始25ヶ月後[Table 3] → Estimated replacement time: 25 months after use
【００２８】実施例4 図２に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインに、Clの吸
着サイトが0.16mol/モジュールのアニオン吸着膜（イオ
ン交換容量２．６mmol/ｇ、孔径０．１μｍ）を2系列設
置した。そのうち1系列をイオン吸着膜の交換時期を決
定するための不純物測定用として３ヶ月通水を行った。
不純物測定用の膜に付着した不純物をアルカリで脱離し
た後、脱離された不純物のうちハロゲン（Cl）をイオン
クロマトによって分析した。その結果及び実施例１と同
様にして推定された交換時期を表４に示す。EXAMPLE 4 As shown in FIG. 2, an anion adsorption membrane (ion) having 0.16 mol / module of Cl adsorption site was added to a cleaning line branched from a main loop of a use point pipe of an ultrapure water system. An exchange capacity of 2.6 mmol / g and a pore size of 0.1 μm) were installed in two lines. One of the series was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane.
After the impurities attached to the impurity measurement film were desorbed with alkali, halogen (Cl) among the desorbed impurities was analyzed by ion chromatography. Table 4 shows the results and the replacement time estimated in the same manner as in Example 1.
【００２９】[0029]
【表４】 →推定交換時期：使用開始46ヶ月後[Table 4] → Estimated replacement time: 46 months after use
【００３０】実施例５ 図２に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインにフッ素の
吸着サイトが0.14mol/モジュールのアニオン吸着膜（イ
オン交換容量２．６mmol/ｇ、孔径０．１μｍ）を2系列
設置した。そのうち1系列をイオン吸着膜の交換時期を
決定するための不純物測定用として３ヶ月通水を行っ
た。不純物測定用の膜に付着した不純物をアルカリで脱
離した後、脱離された不純物のうちフッ素をイオンクロ
マトによって分析した。その結果及び実施例１と同様に
して推定された交換時期を表５に示す。EXAMPLE 5 As shown in FIG. 2, an anion adsorption membrane (ion exchange membrane) having a fluorine adsorption site of 0.14 mol / module in a cleaning line branched from a main loop of a use point pipe of an ultrapure water system. A capacity of 2.6 mmol / g and a pore size of 0.1 μm) were installed in two lines. One of the series was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane. After the impurities attached to the impurity measurement film were desorbed with alkali, fluorine among the desorbed impurities was analyzed by ion chromatography. Table 5 shows the results and the replacement time estimated in the same manner as in Example 1.
【００３１】[0031]
【表５】 →推定交換時期：使用開始35ヶ月後[Table 5] → Estimated replacement time: 35 months after use
【００３２】実施例６ 図２に示すうように超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインにFeの吸着
サイトが0.3mol/モジュールのカチオン吸着膜（イオン
交換容量１．６mmol/ｇ、孔径０．１μｍ）を2系列設置
した。そのうち1系列をイオン吸着膜の交換時期を決定
するための不純物測定用として３ヶ月通水を行った。不
純物測定用の膜に付着したFeの量を蛍光Ｘ線によって分
析した。その結果及び実施例１と同様にして推定された
交換時期を表６に示す。EXAMPLE 6 As shown in FIG. 2, a cation adsorption membrane (ion exchange) having an Fe adsorption site of 0.3 mol / module in a cleaning line branched from a main loop of a use point pipe of an ultrapure water system. A capacity of 1.6 mmol / g and a pore size of 0.1 μm) were installed in two lines. One of the series was passed for 3 months to measure impurities for determining the replacement time of the ion adsorption membrane. The amount of Fe adhering to the film for impurity measurement was analyzed by X-ray fluorescence. Table 6 shows the results and the replacement time estimated in the same manner as in Example 1.
【００３３】[0033]
【表６】 →推定交換時期：使用開始29ヶ月後[Table 6] → Estimated replacement time: 29 months after use
【００３４】実施例７ 図2に示すように、超純水システムのユ−スポイント配
管のメインル−プから分岐された洗浄ラインにFeの吸着
サイトが0.3mol/モジュールのカチオン吸着膜（イオン
交換容量１．６mmol/ｇ、孔径０．１μｍ）を2系列設置
した。そのうち1系列をイオン吸着膜の交換時期を決定
するための不純物測定用に使用するために洗浄用のイオ
ン吸着膜の1.2倍の通水速度で3ヶ月通水を行った。不純
物測定用の膜に付着した不純物を酸で脱離した後、脱離
された不純物のうちFeをICP-MSによって分析した。その
結果及び実施例１と同様にして推定された交換時期を表
７に示す。Embodiment 7 As shown in FIG. 2, a cation adsorption membrane (ion exchange) having a Fe adsorption site of 0.3 mol / module in a washing line branched from a main loop of a use point pipe of an ultrapure water system. A capacity of 1.6 mmol / g and a pore size of 0.1 μm) were installed in two lines. In order to use one of the series for measuring impurities to determine the replacement time of the ion-adsorbing membrane, water was passed for three months at a water-passing rate 1.2 times that of the ion-adsorbing membrane for cleaning. After impurities adhering to the film for impurity measurement were desorbed with an acid, Fe among the desorbed impurities was analyzed by ICP-MS. Table 7 shows the results and the replacement time estimated in the same manner as in Example 1.
【００３５】[0035]
【表７】 →推定交換時期：使用開始37ヶ月後[Table 7] → Estimated replacement time: 37 months after use
【００３６】[0036]
【発明の効果】本発明によれば、超純水製造に使用され
るイオン吸着膜の破過を予測できる新たな方法を提供す
ることができ、さらにこの方法を利用してイオン吸着膜
を有効利用した超純水の製造方法を提供することができ
る。これにより、ブレ−ク前に膜の交換が可能となり、
デバイス特性を悪化させる要因となる不純物が確実に除
去された清浄な超純水の安定供給ができる。According to the present invention, it is possible to provide a new method capable of predicting breakthrough of an ion-adsorbing film used for producing ultrapure water, and to use this method to effectively use the ion-adsorbing film. It is possible to provide a method for producing ultrapure water using the method. This allows the membrane to be replaced before the break,
It is possible to stably supply clean ultrapure water from which impurities that cause deterioration of device characteristics are surely removed.
【図１】 超純水システムのユ−スポイント配管のメイ
ンル−プから分岐された洗浄ラインにカチオン吸着膜を
（Ａ）（Ｂ）2系列設置した場合の概略説明図。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic explanatory view of a case where two cation adsorption membranes (A) and (B) are installed in a cleaning line branched from a main loop of a use point pipe of an ultrapure water system.
【図２】 超純水システムのユ−スポイント配管のメイ
ンル−プから分岐された洗浄ラインにアニオン吸着膜を
（Ａ）（Ｂ）2系列設置した場合の概略説明図。FIG. 2 is a schematic explanatory view showing a case where two anion adsorption membranes (A) and (B) are installed in a washing line branched from a main loop of a use point pipe of an ultrapure water system.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久保田 昇 静岡県富士市鮫島２番地の１ 旭化成工業 株式会社内 (72)発明者 橋野 昌年 静岡県富士市鮫島２番地の１ 旭化成工業 株式会社内 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Noboru Kubota 1 at Asame Kasei Kogyo Co., Ltd., Fuji City, Shizuoka Prefecture (72) Inventor Masanori Hashino 2 at Samejima Kagoshima Kogyo Co., Ltd., Fuji City, Shizuoka Prefecture Asahi Kasei Kogyo Co., Ltd.
Claims (7)
おいて用いられるイオン吸着膜の破過をモニタリングす
る方法であって、モニタリングすべきイオン吸着膜（以
下、イオン吸着膜（Ａ）という）と同じ性能を有するイ
オン吸着膜（以下、イオン吸着膜（Ｂ）という）をイオ
ン吸着膜（Ａ）と並列に設け、このイオン吸着膜（Ｂ）
に被精製水を接触させ、捕獲された不純物量からイオン
吸着膜（Ａ）の破過到達時期を予測することを特徴とす
る方法。1. A method for monitoring breakthrough of an ion-adsorbing film used immediately before a use point of an ultrapure water production apparatus, the same method as an ion-adsorbing film to be monitored (hereinafter referred to as an ion-adsorbing film (A)). An ion-adsorbing film having performance (hereinafter referred to as an ion-adsorbing film (B)) is provided in parallel with the ion-adsorbing film (A).
A water to be purified, and predicting the breakthrough arrival time of the ion-adsorbing membrane (A) from the amount of captured impurities.
能を有する高分子鎖が保持されている多孔膜であって、
膜１ｇ当たり０．２〜１０ミリ当量のイオン交換基を有
し、平均孔径０．０１〜１μｍの多孔膜を充填したモジ
ュールである請求項１に記載の方法。2. The ion-adsorbing membrane is a porous membrane in which a polymer chain having an ion exchange function is held inside the membrane.
The method according to claim 1, wherein the module is a module packed with a porous membrane having an ion exchange group of 0.2 to 10 milliequivalents per gram of the membrane and having an average pore size of 0.01 to 1 µm.
被精製水の接触量を、イオン吸着膜（Ａ）への単位膜当
たりの被精製水の接触量より多くする請求項１または２
に記載の方法。3. The method according to claim 1, wherein the contact amount of the purified water per unit membrane to the ion-adsorbing membrane (B) is larger than the contact amount of the purified water per unit membrane to the ion-adsorbing membrane (A). 2
The method described in.
着膜（Ａ）の膜面積より小さくする請求項１〜３のいず
れか１項に記載の方法。4. The method according to claim 1, wherein the film area of the ion-adsorbing film (B) is smaller than the film area of the ion-adsorbing film (A).
量を、イオン吸着膜（Ｂ）に捕獲された不純物を脱離
し、脱離した不純物を定量することにより求める請求項
１〜４のいずれか１項に記載の方法。5. The method according to claim 1, wherein the amount of impurities captured by the ion-adsorbing film is determined by desorbing the impurities captured by the ion-adsorbing film and quantifying the desorbed impurities. A method according to any one of the preceding claims.
量を、イオン吸着膜（Ｂ）に捕獲された不純物を脱離す
ることなく定量することにより求める請求項１〜４のい
ずれか１項に記載の方法。6. The method according to claim 1, wherein the amount of impurities trapped in the ion-adsorbing film (B) is determined by quantifying the impurities trapped in the ion-adsorbing film (B) without desorbing the impurities. The method described in the section.
おいてイオン吸着膜を用いる超純水の製造方法であっ
て、請求項１〜６のいずれか１項に記載の方法を利用し
て予測される破過前に上記イオン吸着膜を交換すること
を特徴とする方法。7. A method for producing ultrapure water using an ion-adsorbing membrane immediately before a point of use of an ultrapure water production apparatus, the method being predicted using the method according to claim 1. Replacing the ion-adsorbing membrane before breakthrough.
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|---|---|---|---|
| JP05717498A JP3584308B2 (en) | 1998-03-09 | 1998-03-09 | Method for monitoring breakthrough of ion adsorption membrane for ultrapure water production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05717498A JP3584308B2 (en) | 1998-03-09 | 1998-03-09 | Method for monitoring breakthrough of ion adsorption membrane for ultrapure water production |
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| Publication Number | Publication Date |
|---|---|
| JPH11258219A true JPH11258219A (en) | 1999-09-24 |
| JP3584308B2 JP3584308B2 (en) | 2004-11-04 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005177651A (en) * | 2003-12-22 | 2005-07-07 | Hitachi Ltd | Emission control device, its program, its recording medium, its system and wastewater treatment system |
| JP2006051477A (en) * | 2004-08-16 | 2006-02-23 | Kurita Water Ind Ltd | Water supply system and water supply method |
| WO2018131209A1 (en) * | 2017-01-10 | 2018-07-19 | 栗田工業株式会社 | Method for operating water treatment apparatus |
-
1998
- 1998-03-09 JP JP05717498A patent/JP3584308B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005177651A (en) * | 2003-12-22 | 2005-07-07 | Hitachi Ltd | Emission control device, its program, its recording medium, its system and wastewater treatment system |
| JP2006051477A (en) * | 2004-08-16 | 2006-02-23 | Kurita Water Ind Ltd | Water supply system and water supply method |
| WO2018131209A1 (en) * | 2017-01-10 | 2018-07-19 | 栗田工業株式会社 | Method for operating water treatment apparatus |
| JP2018111058A (en) * | 2017-01-10 | 2018-07-19 | 栗田工業株式会社 | Operation method of water treatment equipment |
| CN110139835A (en) * | 2017-01-10 | 2019-08-16 | 栗田工业株式会社 | Method for operating water treatment apparatus |
| KR20190100161A (en) * | 2017-01-10 | 2019-08-28 | 쿠리타 고교 가부시키가이샤 | Operation method of water treatment device |
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| Publication number | Publication date |
|---|---|
| JP3584308B2 (en) | 2004-11-04 |
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