JP6983582B2 - Cartridge for water purifier and water purifier for softening - Google Patents
Cartridge for water purifier and water purifier for softening Download PDFInfo
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- JP6983582B2 JP6983582B2 JP2017165929A JP2017165929A JP6983582B2 JP 6983582 B2 JP6983582 B2 JP 6983582B2 JP 2017165929 A JP2017165929 A JP 2017165929A JP 2017165929 A JP2017165929 A JP 2017165929A JP 6983582 B2 JP6983582 B2 JP 6983582B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- 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 description 58
- 239000003729 cation exchange resin Substances 0.000 claims description 58
- 239000003957 anion exchange resin Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 42
- 229920000768 polyamine Polymers 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 36
- 239000008399 tap water Substances 0.000 claims description 25
- 235000020679 tap water Nutrition 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005349 anion exchange Methods 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000004581 coalescence Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 84
- 238000010828 elution Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 101100127285 Drosophila melanogaster unc-104 gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Description
本発明は、水道水を浄化する共に軟化する軟化用浄水器及びそれに用いられる浄水器用カートリッジに関する。 The present invention relates to a water purifier for softening that purifies and softens tap water and a cartridge for a water purifier used therein.
軟水の効能として、（ａ）お茶やコーヒーの味をまろやかにする、（ｂ）調理器具等のスケール発生を防止する、（ｃ）石鹸の泡立ちが良くなる、（ｄ）グラス等容器へのウォーターマーク発生を抑制する等がある。このため、従来から、軟化機能を有する浄水器が広く利用されている。 The effects of soft water include (a) mellowing the taste of tea and coffee, (b) preventing scale generation in cooking utensils, (c) improving the foaming of soap, and (d) water in containers such as glasses. There are measures such as suppressing the generation of marks. Therefore, conventionally, a water purifier having a softening function has been widely used.
水の軟化方法としては、（１）カチオン交換樹脂を用いる方法、（２）ＮＦ（Ｎａｎｏｆｉｌｔｒａｔｉｏｎ；ナノろ過）又はＲＯ（Ｒｅｖｅｒｓｅ Ｏｓｍｏｓｉｓ；逆浸透）膜を用いる方法、（３）アルカリ剤を添加することにより沈澱したものを除去する方法などがある。これらの中で、エネルギー効率や装置の維持管理面から、上記（１）のカチオン交換樹脂を用いる方法が優れている。 As a method for softening water, (1) a method using a cation exchange resin, (2) a method using an NF (Nanofiltration; nanofiltration) or RO (Reverse Osmosis; reverse osmosis) membrane, and (3) adding an alkaline agent. There is a method of removing the sedimented material. Among these, the method using the cation exchange resin described in (1) above is excellent from the viewpoints of energy efficiency and maintenance of the apparatus.
軟化用浄水器として、カチオン交換樹脂を用いる方法を選択した場合、硬度除去性能が重要視されることはもちろんのこと、カチオン交換樹脂自体からの不純物の溶出により、処理水品質を損なわないことも重要である。 When a method using a cation exchange resin is selected as the water purifier for softening, not only the hardness removal performance is emphasized, but also the elution of impurities from the cation exchange resin itself does not impair the quality of the treated water. is important.
カチオン交換樹脂自体からの溶出物対策としては、例えば、特開平７−２０４６３１号公報（特許文献１）に、カチオン交換樹脂と活性炭を混合した浄水器が開示されている。 As a measure against elution from the cation exchange resin itself, for example, Japanese Patent Application Laid-Open No. 7-204631 (Patent Document 1) discloses a water purifier in which a cation exchange resin and activated carbon are mixed.
また、特開２０１６−２２４４３号公報（特許文献２）には、強酸性カチオン交換樹脂からのホルムアルデヒドの溶出を抑制するために、架橋度が１６〜２４％の強酸性カチオン交換樹脂が充填された浄水器用カートリッジが開示されている。 Further, Japanese Patent Application Laid-Open No. 2016-22443 (Patent Document 2) is filled with a strong acid cation exchange resin having a degree of cross-linking of 16 to 24% in order to suppress the elution of formaldehyde from the strong acid cation exchange resin. Cartridges for water purifiers are disclosed.
しかし、カチオン交換樹脂からの溶出物のうち、ホルムアルデヒドは、活性炭に吸着され難いため、引用文献１の浄水器では、カチオン交換樹脂からのホルムアルデヒドの除去は不十分であった。 However, among the eluates from the cation exchange resin, formaldehyde is difficult to be adsorbed on the activated carbon, so that the water purifier of Cited Document 1 did not sufficiently remove formaldehyde from the cation exchange resin.
また、引用文献２の浄水器用カートリッであってもなお、強酸性カチオン交換樹脂から溶出するホルムアルデヒドの除去が不十分であるとの問題、特に一定時間静置後、通水再開初期の軟化水へのホルムアルデヒドの溶出量が多いとの問題があった。 Further, even in the case of the water purifier cartridge of Cited Document 2, there is a problem that formaldehyde eluted from the strong acid cation exchange resin is insufficiently removed. There was a problem that the amount of formaldehyde elution was large.
従って、本発明の目的は、強酸性カチオン交換樹脂から溶出するホルムアルデヒドを低減することができる浄水器用カートリッジ及びそれが用いられている軟化用浄水器を提供することにある。 Therefore, an object of the present invention is to provide a water purifier cartridge capable of reducing formaldehyde eluted from a strongly acidic cation exchange resin and a water purifier for softening in which the cartridge is used.
このような上記課題は、以下の本発明によって解決される。
すなわち、本発明（１）は、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材とを有し、
該軟化処理材は、上流側に積層されている第一層と、下流側に積層されている第二層と、で形成されており、該第一層は、基体がスチレン−ジビニルベンゼン共重合体であり且つＮａ形又はＫ形の強酸性カチオン交換樹脂からなり、該第二層は、ポリアミン型のアニオン交換樹脂からなること、
を特徴とする浄水器用カートリッジを提供するものである。
Such a problem is solved by the following invention.
That is, the present invention (1) includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
It has a softening material that is filled in the filling area of the softening material in the cartridge container.
The softened material is formed of a first layer laminated on the upstream side and a second layer laminated on the downstream side, and the substrate of the first layer has a styrene-divinylbenzene copolymer weight. It is a coalescence and is made of a Na-type or K-type strong acid cation exchange resin, and the second layer is made of a polyamine-type anion exchange resin.
It is intended to provide a cartridge for a water purifier, which is characterized by the above.
また、本発明（２）は、前記塩形の強酸性カチオン交換樹脂のカチオン交換容量（ｅｑ／Ｌ−Ｒ）に対する前記ポリアミン型のアニオン交換樹脂のアニオン交換容量（ｅｑ／Ｌ−Ｒ）の比（アニオン交換容量／カチオン交換容量）が、０．０１〜０．２であることを特徴とする（１）の浄水器用カートリッジを提供するものである。 Further, in the present invention (2), the ratio of the anion exchange capacity (eq / L-R) of the polyamine type anion exchange resin to the cation exchange capacity (eq / L-R) of the salt-type strongly acidic cation exchange resin. Provided is the cartridge for a water purifier according to (1), wherein (anion exchange capacity / cation exchange capacity) is 0.01 to 0.2.
また、本発明（３）は、前記ポリアミン型のアニオン交換樹脂の一部が、塩酸形であることを特徴とする（１）又は（２）いずれかの浄水器用カートリッジを提供するものである。 Further, the present invention (3) provides a cartridge for a water purifier according to either (1) or (2), wherein a part of the polyamine type anion exchange resin is in the hydrochloric acid type.
また、本発明（４）は、前記第二層が、更に、粒状活性炭を含有することを特徴とする（１）〜（３）いずれかの浄水器用カートリッジを提供するものである。 Further, the present invention (4) provides a cartridge for a water purifier according to any one of (1) to (3), wherein the second layer further contains granular activated carbon.
また、本発明（５）は、前記ポリアミン型のアニオン交換樹脂に対する前記粒状活性炭の混合割合（粒状活性炭／ポリアミン型のアニオン交換樹脂）が、体積基準で、０．５〜２．０であることを特徴とする（１）〜（４）いずれかの浄水器用カートリッジを提供するものである。 Further, in the present invention (5), the mixing ratio of the granular activated carbon to the polyamine type anion exchange resin (granular activated carbon / polyamine type anion exchange resin) is 0.5 to 2.0 on a volume basis. (1) to (4) for providing a cartridge for a water purifier.
本発明（６）は、（１）〜（５）いずれかの浄水器用カートリッジと、
該浄水器用カートリッジを収納する筐体と、
を有することを特徴とする軟化用浄水器を提供するものである。
The present invention (6) includes a cartridge for a water purifier according to any one of (1) to (5).
A housing for storing the water purifier cartridge and
It is intended to provide a water purifier for softening, which is characterized by having.
本発明によれば、強酸性カチオン交換樹脂から溶出するホルムアルデヒドを低減することができる浄水器用カートリッジ及びそれが用いられている軟化用浄水器を提供することができる。 According to the present invention, it is possible to provide a water purifier cartridge capable of reducing formaldehyde eluted from a strongly acidic cation exchange resin and a water purifier for softening in which the cartridge is used.
本発明の浄水器用カートリッジは、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材と、
を有し、
該軟化処理材は、上流側に積層されている第一層と、下流側に積層されている第二層と、で形成されており、該第一層は、塩形の強酸性カチオン交換樹脂からなり、該第二層は、ポリアミン型のアニオン交換樹脂からなること、
を特徴とする浄水器用カートリッジである。なお、本発明において、上流側とは、軟化処理材の充填領域の水道水の供給側を指し、また、下流側とは、軟化処理材の充填領域の軟化水の排出側を指す。
The cartridge for a water purifier of the present invention includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
The softening material filled in the filling area of the softening material in the cartridge container,
Have,
The softening material is formed of a first layer laminated on the upstream side and a second layer laminated on the downstream side, and the first layer is a salt-type strong acid cation exchange resin. The second layer is made of a polyamine type anion exchange resin.
It is a cartridge for a water purifier characterized by. In the present invention, the upstream side refers to the supply side of tap water in the filled region of the softened material, and the downstream side refers to the discharge side of the softened water in the filled region of the softened material.
本発明の浄水器用カートリッジは、水道水の供給口及び軟化水の排出口が形成されているカートリッジ容器と、カートリッジ容器内の軟化処理材の充填領域に充填されて軟化処理材と、を有する。そして、本発明の浄水器用カートリッジは、水道水の供給口と、軟化用浄水器の筐体内に形成されている水道水の供給経路とが繋がり、且つ、軟化水の排出口と、軟化用浄水器の筐体内に形成されている軟化水の排出経路とが繋がるように、軟化用浄水器の筐体内に設置される。 The cartridge for a water purifier of the present invention has a cartridge container in which a tap water supply port and a softening water discharge port are formed, and a softening treatment material filled in a filling region of the softening treatment material in the cartridge container. In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier are connected, and the softened water discharge port and the softening water purification water are connected. It is installed in the housing of the water purifier for softening so as to be connected to the discharge path of the softened water formed in the housing of the vessel.
本発明の浄水器用カートリッジに係る軟化処理材は、上流側に積層されている第一層と、下流側に積層されている第二層と、の２つの充填層が積層されて形成されている。第一層は、塩形の強酸性カチオン交換樹脂からなる。第二層は、ポリアミン型のアニオン交換樹脂からなるか、又はポリアミン型のアニオン交換樹脂と粒状活性炭の混合物からなる。軟化処理材は、本発明の浄水器用カートリッジのカートリッジ容器内の軟化処理材の充填領域に充填されて、軟化処理材層を形成している。 The softened material according to the cartridge for a water purifier of the present invention is formed by laminating two packed layers, a first layer laminated on the upstream side and a second layer laminated on the downstream side. .. The first layer is made of a salt-type strong acid cation exchange resin. The second layer consists of a polyamine-type anion exchange resin or a mixture of a polyamine-type anion exchange resin and granular activated carbon. The softening treatment material is filled in the filling region of the softening treatment material in the cartridge container of the cartridge for a water purifier of the present invention to form a softening treatment material layer.
塩形の強酸性カチオン交換樹脂の基体は、スチレン−ジビニルベンゼン共重合体である。塩形の強酸性カチオン交換樹脂の基体を形成する樹脂材は、水道水と接触すると、ホルムアルデヒドを発生させ、被処理水へホルムアルデヒドを放出する。 The substrate of the salt-type strong acid cation exchange resin is a styrene-divinylbenzene copolymer. When the resin material forming the substrate of the salt-type strong acid cation exchange resin comes into contact with tap water, it generates formaldehyde and releases formaldehyde into the water to be treated.
塩形の強酸性カチオン交換樹脂は、ゲル型構造、マクロポーラス型構造、ポーラス型構造のいずれの構造でもよい。そして、塩形の強酸性カチオン交換樹脂の構造は、ゲル型構造が、交換容量が高いので硬度吸着量が多くなる点で、好ましい。 The salt-type strong acid cation exchange resin may have any of a gel-type structure, a macroporous type structure, and a porous type structure. The structure of the salt-type strong acid cation exchange resin is preferable because the gel-type structure has a high exchange capacity and therefore a large amount of hardness adsorption.
塩形の強酸性カチオン交換樹脂のカチオン交換基は、スルホン酸基である。また、塩形の強酸性カチオン樹脂の塩形は、Ｎａ形又はＫ形である。 The cation exchange group of the salt-type strong acid cation exchange resin is a sulfonic acid group. The salt form of the salt form of the strongly acidic cationic resin is Na form or K form.
塩形の強酸性カチオン交換樹脂としては、例えば、ダウケミカル製のアンバージェット１２２０Ｎａ、住化ケムテックス製のイマックＨＰ１２２０Ｎａが挙げられる。また、塩形の強酸性カチオン交換樹脂としては、強酸性カチオン交換樹脂であるダウエックス製のアンバージェット１０２０Ｈ等を、Ｎａ形又はＫ形に変換したものでもよい。 Examples of the salt-type strong acid cation exchange resin include Amberjet 1220Na manufactured by Dow Chemical and Imac HP1220Na manufactured by Sumika Chemtex. Further, as the salt-type strong acid cation exchange resin, a strong acid cation exchange resin such as Amber Jet 1020H manufactured by Dowex may be converted into a Na type or a K type.
塩形の強酸性カチオン交換樹脂の湿潤状態のイオン交換容量は、好ましくは１．５〜３．０（ｅｑ／Ｌ−Ｒ）、特に好ましくは１．７〜２．７（ｅｑ／Ｌ−Ｒ）である。 The wet ion exchange capacity of the salt-type strong acid cation exchange resin is preferably 1.5 to 3.0 (eq / L-R), particularly preferably 1.7 to 2.7 (eq / L-R). ).
塩形の強酸性カチオン交換樹脂の調和平均径は、好ましくは４００〜９００μｍ、特に好ましくは５００〜８００μｍである。 The harmonic mean diameter of the salt-type strong acid cation exchange resin is preferably 400 to 900 μm, particularly preferably 500 to 800 μm.
ポリアミン型のアニオン交換樹脂の基体は、特に制限されず、例えば、スチレン−ジビニルベンゼン共重合体、アクリル酸−ジビニルベンゼン共重合体等が挙げられる。ポリアミン型のアニオン交換樹脂の架橋度は、樹脂材の種類により、適宜選択される。 The substrate of the polyamine type anion exchange resin is not particularly limited, and examples thereof include a styrene-divinylbenzene copolymer and an acrylic acid-divinylbenzene copolymer. The degree of cross-linking of the polyamine type anion exchange resin is appropriately selected depending on the type of resin material.
ポリアミン型のアニオン交換樹脂は、ゲル型構造、マクロポーラス型構造、ポーラス型構造のいずれの構造でもよい。そして、ポリアミン型のアニオン交換樹脂の構造は、マクロポーラス型が好ましい。 The polyamine type anion exchange resin may have any of a gel type structure, a macroporous type structure, and a porous type structure. The structure of the polyamine type anion exchange resin is preferably a macroporous type.
ポリアミン型のアニオン交換樹脂のアニオン交換基は、第一級アミン基、第二級アミン基、第三級アミン基及び第四級アンモニウム基のうちのいずれか１種、又はこれらのうちの２種以上の組み合わせである。第一級アミン基、第二級アミン基、第三級アミン基及び第四級アンモニウム基としては、通常、ポリアミン型のアニオン交換樹脂に用いられている基であれば、特に制限されない。ポリアミン型のアニオン交換樹脂中のアミン基は、塩酸形に変換されていてもよい。 The anion exchange group of the polyamine type anion exchange resin is one of a primary amine group, a secondary amine group, a tertiary amine group and a quaternary ammonium group, or two of them. The above combination. The primary amine group, secondary amine group, tertiary amine group and quaternary ammonium group are not particularly limited as long as they are groups usually used for polyamine type anion exchange resins. The amine group in the polyamine type anion exchange resin may be converted to the hydrochloric acid form.
ポリアミン型のアニオン交換樹脂は、一部が塩酸形であることが、処理水である軟化水のｐＨを７近くに調節し易くなる点で、好ましい。ポリアミン型のアニオン交換樹脂中のアミン基が塩酸形に変換されている割合は、アミン基の種類や導入量等により、適宜選択される。 It is preferable that a part of the polyamine type anion exchange resin is in the form of hydrochloric acid in that the pH of the softened water, which is the treated water, can be easily adjusted to around 7. The ratio of the amine group converted to the hydrochloric acid form in the polyamine type anion exchange resin is appropriately selected depending on the type of amine group, the amount introduced, and the like.
ポリアミン型のアニオン交換樹脂としては、例えば、ピュロライト社製のピュロライトＡ８３０Ｗ、三菱化学社製のダイアイオンＷＡ２０等が挙げられる。 Examples of the polyamine type anion exchange resin include Purolite A830W manufactured by Purolite Co., Ltd., Diaion WA20 manufactured by Mitsubishi Chemical Corporation, and the like.
ポリアミン型のアニオン交換樹脂の湿潤状態のイオン交換容量は、好ましくは２〜４（ｅｑ／Ｌ−Ｒ）、特に好ましくは２．５〜３．５（ｅｑ／Ｌ−Ｒ）である。ポリアミン型のアニオン交換樹脂のイオン交換容量が、上記範囲であることにより、ホルムアルデヒドの吸着性能が高くなる。 The wet ion exchange capacity of the polyamine type anion exchange resin is preferably 2 to 4 (eq / L-R), particularly preferably 2.5 to 3.5 (eq / L-R). When the ion exchange capacity of the polyamine type anion exchange resin is within the above range, the formaldehyde adsorption performance is enhanced.
ポリアミン型のアニオン交換樹脂の調和平均径は、好ましくは３００〜１２００μｍ、特に好ましくは５００〜１０００μｍである。 The harmonic mean diameter of the polyamine type anion exchange resin is preferably 300 to 1200 μm, particularly preferably 500 to 1000 μm.
本発明の浄水器用カートリッジに係る軟化処理材は、上流側に積層されており且つ塩形の強酸性カチオン交換樹脂からなる第一層と、下流側に積層されており且つポリアミン型のアニオン交換樹脂からなる第二層と、の２つの充填層が積層されて形成されている。そして、本発明の浄水器用カートリッジでは、軟化処理材の上流側に塩形の強酸性カチオン交換樹脂が配置され、且つ、下流側にポリアミン型のアニオン交換樹脂が配置されていることにより、ホルムアルデヒドの発生源である強酸性カチオン交換樹脂の層（第一層）の直後に、ホルムアルデヒドの吸着能が高いポリアミン型のアニオン交換樹脂の層（第二層）が存在しているので、ホルムアルデヒドが、強酸性カチオン交換樹脂から溶出しても、速やかに、ポリアミン型のアニオン交換樹脂に吸着される。そのため、本発明の浄水器用カートリッジに係る軟化処理材は、強酸性カチオン交換樹脂から溶出するホルムアルデヒドの除去性能に優れる。 The softened material according to the cartridge for a water purifier of the present invention is a first layer made of a salt-type strong acid cation exchange resin laminated on the upstream side and a polyamine type anion exchange resin laminated on the downstream side. It is formed by laminating two packed layers, that is, a second layer made of. In the water purifier cartridge of the present invention, the salt-type strong acid cation exchange resin is arranged on the upstream side of the softening treatment material, and the polyamine-type anion exchange resin is arranged on the downstream side. Immediately after the layer of the strongly acidic cation exchange resin (first layer), which is the source, there is a layer of the polyamine type anion exchange resin (second layer), which has a high ability to adsorb formaldehyde. Even if it elutes from the sex cation exchange resin, it is rapidly adsorbed on the polyamine type anion exchange resin. Therefore, the softening material according to the cartridge for a water purifier of the present invention is excellent in the ability to remove formaldehyde eluted from the strongly acidic cation exchange resin.
軟化処理材として、塩形の強酸性カチオン交換樹脂のみ、又は塩形の強酸性カチオン交換樹脂と粒状活性炭の混合物で、水道水を処理する場合、連続して軟化処理材に水道水が流通されているときは、被処理水と強酸性カチオン交換樹脂との接触時間が非常に短いので、ホルムアルデヒドが強酸性カチオン交換樹脂から溶出してきたとしも、処理水である軟化水中のホルムアルデヒド濃度は非常に低く、ホルムアルデヒドの溶出が問題になることはない。また、軟化処理材への水道水の流通が停止されている時間が短いときは、軟化水へのホルムアルデヒドの溶出量が少ないため、ホルムアルデヒドの溶出が問題になることは少ない。それに対して、一定時間軟化処理材への水道水の流通がされないまま静置されている状態が続くと、浄水器用カートリッジの軟化処理材の充填領域で、被処理水と強酸性カチオン交換樹脂とが接触している時間が長くなるので、軟化処理材の充填領域内の軟化水へ溶出して蓄積されるホルムアルデヒド量が多くなる。そのため、一定時間静置後、通水再開初期の軟化水中のホルムアルデヒドの濃度が高くなってしまい、軟化水へのホルムアルデヒドの溶出の問題が生じる。 When tap water is treated with only a salt-type strong acid cation exchange resin or a mixture of a salt-type strong acid cation exchange resin and granular activated charcoal as the softening treatment material, tap water is continuously distributed to the softening treatment material. In this case, the contact time between the water to be treated and the strong acid cation exchange resin is very short, so even if formaldehyde elutes from the strong acid cation exchange resin, the formaldehyde concentration in the softened water, which is the treated water, is very high. It is low and elution of formaldehyde is not a problem. Further, when the flow of tap water to the softened material is stopped for a short time, the amount of formaldehyde eluted into the softened water is small, so that the elution of formaldehyde is less likely to be a problem. On the other hand, if the tap water is left to stand for a certain period of time without being circulated to the softened material, the water to be treated and the strongly acidic cation exchange resin are formed in the filled area of the softened material of the water purifier cartridge. Since the contact time is long, the amount of formaldehyde that elutes and accumulates in the softened water in the filling region of the softening material increases. Therefore, after standing for a certain period of time, the concentration of formaldehyde in the softened water at the initial stage of resuming water flow becomes high, which causes a problem of elution of formaldehyde into the softened water.
塩形の強酸性カチオン交換樹脂とポリアミン型のアニオン交換樹脂の混合物が充填領域に充填されていると、被処理水と強酸性カチオン交換樹脂とが長時間接触しても、強酸性カチオン交換樹脂から溶出するホルムアルデヒドが、近傍に存在しているポリアミン型のアニオン交換樹脂にすぐに吸着されるので、溶出したホルムアルデヒドの除去性は高くなる。しかし、この場合、負の電荷を有する強酸性カチオン交換樹脂と正の電荷を有するポリアミン型のアニオン交換樹脂が、電気的に凝集してクランピングを起こし、体積が膨張してしまう。そのため、カートリッジ容器の容積を大きくする必要が生じる。 When the packed region is filled with a mixture of a salt-type strong acid cation exchange resin and a polyamine type anion exchange resin, the strong acid cation exchange resin is used even if the water to be treated and the strong acid cation exchange resin come into contact with each other for a long time. Since the formaldehyde eluted from is immediately adsorbed on the polyamine type anion exchange resin present in the vicinity, the removability of the eluted formaldehyde is improved. However, in this case, the strongly acidic cation exchange resin having a negative charge and the polyamine type anion exchange resin having a positive charge electrically aggregate and cause clamping, and the volume expands. Therefore, it becomes necessary to increase the volume of the cartridge container.
それに対して、本発明の浄水器用カートリッジでは、軟化処理材の充填領域の上流側に塩形の強酸性カチオン交換樹脂が、下流側にポリアミン型のアニオン交換樹脂が、それぞれ別の層として積層されて充填されているので、強酸性カチオン交換樹脂とポリアミン型のアニオン交換樹脂との電気的な凝集によるクランピングが起こらない。そのため、本発明の浄水器用カートリッジは、カートリッジの容積が大きくなり過ぎず、且つ、一定時間静置後、通水再開初期の軟化水中のホルムアルデヒドの溶出の問題を防ぐことができる。 On the other hand, in the water purifier cartridge of the present invention, a salt-type strong acid cation exchange resin is laminated on the upstream side of the filling region of the softening treatment material, and a polyamine-type anion exchange resin is laminated on the downstream side as separate layers. Since it is filled with a strong acid cation exchange resin, clamping due to electrical aggregation between the strongly acidic cation exchange resin and the polyamine type anion exchange resin does not occur. Therefore, the cartridge for a water purifier of the present invention does not have an excessively large volume of the cartridge, and can prevent the problem of formaldehyde elution in the softened water at the initial stage of resumption of water flow after being allowed to stand for a certain period of time.
軟化処理材中の塩形の強酸性カチオン交換樹脂の湿潤状態のカチオン交換容量（ｅｑ／Ｌ−Ｒ）に対するポリアミン型のアニオン交換樹脂の湿潤状態のアニオン交換容量（ｅｑ／Ｌ−Ｒ）の比（アニオン交換容量／カチオン交換容量）は、好ましくは０．０１〜０．２、特に好ましくは０．０１〜０．１である。軟化処理材中の塩形の強酸性カチオン交換樹脂のカチオン交換容量に対するポリアミン型のアニオン交換樹脂のアニオン交換容量の比が、上記範囲にあることにより、強酸性カチオン交換樹脂から溶出するホルムアルデヒドの除去性能が高くなり、かつポリアミン樹脂からの溶出物が処理水質に悪影響を与えない。 The ratio of the wet anion exchange capacity (eq / L-R) of the polyamine type anion exchange resin to the wet cation exchange capacity (eq / L-R) of the salt-type strongly acidic cation exchange resin in the softened material. (Anion exchange capacity / cation exchange capacity) is preferably 0.01 to 0.2, and particularly preferably 0.01 to 0.1. When the ratio of the anion exchange capacity of the polyamine type anion exchange resin to the cation exchange capacity of the salt-type strong acid cation exchange resin in the softening material is within the above range, the formaldehyde eluted from the strong acid cation exchange resin is removed. The performance is high, and the eluate from the polyamine resin does not adversely affect the treated water quality.
軟化処理材を形成する第二層は、ポリアミン型のアニオン交換樹脂に加え、更に、粒状活性炭を含有するもの、すなわち、ポリアミン型のアニオン交換樹脂と、粒状活性炭と、からなる混合物であってもよい。粒状活性炭は、水道水中の残留塩素除去、強酸性カチオン樹脂からの溶出有機物除去、ポリアミン樹脂からの溶出有機物除去の機能を果たす。 The second layer forming the softening material may be a mixture of a polyamine type anion exchange resin and a granular activated carbon, that is, a polyamine type anion exchange resin and a granular activated carbon. good. Granular activated carbon fulfills the functions of removing residual chlorine in tap water, removing eluted organic substances from strongly acidic cationic resins, and removing eluted organic substances from polyamine resins.
粒状活性炭は、球形又は不定形の粒状の活性炭である。粒状活性炭としては、木粉系、ヤシガラ系、フェノール樹脂系、石油コークス系、石炭コークス系、ピッチ系等の原料が賦活された材料が挙げられる。粒状活性炭としては、例えば、フタムラ社製の太閤活性炭ＣＷ４８０ＰＧＲ、ＣＮ４８０Ｇや、クラレ製のクラレコールＧＷ−Ｂ等が挙げられる。 Granular activated carbon is spherical or amorphous granular activated carbon. Examples of the granular activated carbon include materials in which raw materials such as wood powder, coconut husk, phenol resin, petroleum coke, coal coke, and pitch are activated. Examples of the granular activated carbon include Taiko activated carbon CW480PGR and CN480G manufactured by Futamura, and Kuraraycol GW-B manufactured by Kuraray.
粒状活性炭の比表面積は、好ましくは６００〜１８００ｍ２／ｇ、特に好ましくは８００〜１８００ｍ２／ｇである。また、粒状活性炭の全細孔容積は、好ましくは０．４〜１．４ｍＬ／ｇ、特に好ましくは０．６〜１．４ｍＬ／ｇである。 The specific surface area of the granular activated carbon is preferably 600 to 1800 m 2 / g, and particularly preferably 800 to 1800 m 2 / g. The total pore volume of the granular activated carbon is preferably 0.4 to 1.4 mL / g, particularly preferably 0.6 to 1.4 mL / g.
粒状活性炭は、体積基準の粒度分布において、０．１８０〜２．３６ｍｍの範囲に９０％以上存在しているものが好ましく、０．１８０〜２．３６ｍｍの範囲に９５％以上存在しているものが特に好ましい。 The granular activated carbon preferably has 90% or more in the range of 0.180 to 2.36 mm, and 95% or more in the range of 0.180 to 2.36 mm in the volume-based particle size distribution. Is particularly preferable.
粒状活性炭の真密度は、好ましくは１．５〜２．５ｇ／ｍＬ、特に好ましくは１．９〜２．３ｇ／ｍＬである。 The true density of the granular activated carbon is preferably 1.5 to 2.5 g / mL, particularly preferably 1.9 to 2.3 g / mL.
軟化処理材中、ポリアミン型のアニオン交換樹脂の量に対する粒状活性炭の量の比（粒状活性炭／ポリアミン型のアニオン交換樹脂）は、体積基準で、０．５〜２．０であることが好ましく、０．５〜１．０であることが特に好ましい。 The ratio of the amount of granular activated carbon (granular activated carbon / polyamine type anion exchange resin) to the amount of polyamine type anion exchange resin in the softened material is preferably 0.5 to 2.0 on a volume basis. It is particularly preferably 0.5 to 1.0.
本発明の浄水器用カートリッジは、水道水の供給口と、本発明の軟化用浄水器の筐体内に形成されている水道水の供給経路とが繋がり、且つ、軟化水の排出口と、本発明の軟化用浄水器の筐体内に形成されている軟化水の排出経路とが繋がるように、本発明の軟化用浄水器の筐体内に設置される。 In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier of the present invention are connected, and the softened water discharge port and the present invention are used. It is installed in the housing of the water purifier for softening of the present invention so as to be connected to the discharge path of the softened water formed in the housing of the water purifier for softening.
そして、水道水が、本発明の軟化浄水器内に供給され、本発明の軟化用浄水器の筐体内の水道水の供給経路を経て、軟化処理材の充填領域内に供給されて、軟化処理材層に通液される。水道水が、軟化処理材層を通過するときに、軟化処理材により、水道水中の硬度成分であるＣａイオン及びＭｇイオンが、軟化処理材の塩形の強酸性カチオン交換樹脂のＮａイオン又はＫイオンに交換されて、水道水が軟化される。軟化された処理水は、本発明の軟化浄水器の筐体内の軟化水の排出経路を経て、本発明の軟化用浄水器の外に排出され、軟化水として使用される。 Then, tap water is supplied into the softening water purifier of the present invention, is supplied into the filling region of the softening treatment material via the tap water supply path in the housing of the softening water purifier of the present invention, and is softened. The liquid is passed through the material layer. When tap water passes through the softening treatment material layer, the softening treatment material causes Ca ions and Mg ions, which are hardness components in the tap water, to be Na ions or K, which are salt-type strongly acidic cation exchange resins of the softening treatment material. It is exchanged for ions and the tap water is softened. The softened treated water is discharged to the outside of the softening water purifier of the present invention through the softened water discharge path inside the housing of the softened water purifier of the present invention, and is used as softened water.
本発明の軟化用浄水器は、本発明の浄水器用カートリッジと、本発明の浄水器用カートリッジを収納する筐体と、を有することを特徴とする軟化用浄水器である。 The water purifier for softening of the present invention is a water purifier for softening, which comprises a cartridge for the water purifier of the present invention and a housing for accommodating the cartridge for the water purifier of the present invention.
本発明の軟化用浄水器により処理される被処理水は、水道水である。 The water to be treated by the water purifier for softening of the present invention is tap water.
以下、本発明を実施例に基づき詳細に説明する。ただし、本発明は、以下の実施例に制限されるものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.
（実施例１）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、イオン交換容量２．２（ｅｑ／Ｌ−Ｒ、湿潤状態）、調和平均径６１０μｍのＮａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）９００ｍＬを上流側に、イオン交換容量３．０（ｅｑ／Ｌ−Ｒ、湿潤状態）、調和平均径８５０μｍのポリアミン型のアニオン交換樹脂、ピュロライトＡ８３０Ｗ、ピュロライト社製）１８ｍＬを下流側に積層する形で充填し、カートリッジを作製した。
次いで、そのカートリッジ内に、水温２３℃の水道水をＳＶ６０ＢＶ／ｈｒで１５分間通水を行った。その後、カーリッジ内に水道水が溜まった状態で、２３℃の調節した室内にて、２４時間放置した。
２４時間放置後、再び、水温２３℃の水道水をＳＶ６０ＢＶ／ｈｒで１分間通水し、その間の処理水を採取した。次いで、処理水のホルムアルデヒド濃度を分析した。その結果を表１に示す。
(Example 1)
Na-type strongly acidic cation exchange resin (Amberjet 1220Na, Dow Chemical) with an ion exchange capacity of 2.2 (eq / L-R, wet state) and a harmonized average diameter of 610 μm in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. 900 mL on the upstream side, ion exchange capacity 3.0 (eq / L-R, wet state), polyamine type anion exchange resin with harmonious average diameter of 850 μm, Purolite A830W, Purolite) 18 mL on the downstream side The cartridge was prepared by filling in a laminated form.
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the car ridge, it was left in a room adjusted at 23 ° C. for 24 hours.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the formaldehyde concentration of the treated water was analyzed. The results are shown in Table 1.
＜イオン交換樹脂の調和平均径の測定方法＞
ベックマンコールター社製のレーザー回折散乱法粒度分布測定装置（商品名：ＬＳ １３ ３２０（湿式システム））を用いて測定した。
<Measurement method of harmonic mean diameter of ion exchange resin>
The measurement was performed using a laser diffraction / scattering method particle size distribution measuring device (trade name: LS 13 320 (wet system)) manufactured by Beckman Coulter.
（比較例１）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、Ｎａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）９００ｍＬと、ポリアミン型のアニオン交換樹脂（ピュロライトＡ８３０Ｗ、ピュロライト社製）１８ｍＬの混合物を充填したこと以外は、実施例１と同様に行った。その結果を表１に示す。
(Comparative Example 1)
In an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm, 900 mL of Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) and 18 mL of polyamine-type anion exchange resin (Purolite A830W, manufactured by Dow Chemical Co., Ltd.) The procedure was the same as in Example 1 except that the mixture was filled. The results are shown in Table 1.
（比較例２）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、Ｎａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）を９００ｍＬと、比表面積１４００ｍ２／ｇ、粒径０．１８〜０．３５５ｍｍの範囲内が９５％の粒状活性炭（太閤活性炭ＣＷ４８０ＰＧＲ、フタムラ化学社製）を１００ｍＬとを混合したこと以外は、実施例１と同様に行った。その結果を表１に示す。
(Comparative Example 2)
In an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm, 900 mL of Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.), a specific surface area of 1400 m 2 / g, and a particle size of 0.18 to 0. The same procedure as in Example 1 was carried out except that 100 mL of granular activated carbon (Taiko activated carbon CW480PGR, manufactured by Futamura Chemical Co., Ltd.) having a specific surface area of 355 mm was mixed. The results are shown in Table 1.
（比較例３）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、Ｎａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）を９００ｍＬのみを充填すること以外は、実施例１と同様に行った。その結果を表１に示す。
(Comparative Example 3)
The same procedure as in Example 1 was carried out except that only 900 mL of a Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) was filled in an acrylic column having an inner diameter of 4.6 cm and a height of 100 cm. The results are shown in Table 1.
（実施例２）
内径４．６ｃｍ、高さ１００ｃｍのアクリルカラム内に、Ｎａ形強酸性カチオン交換樹脂（アンバージェット １２２０Ｎａ、ダウケミカル社製）を９００ｍＬを上流側に、ポリアミン型のアニオン交換樹脂（ピュロライトＡ８３０Ｗ、ピュロライト社製）１８ｍＬと、粒状活性炭（太閤活性炭ＣＷ４８０ＰＧＲ、フタムラ化学社製）１８ｍＬと、の混合物を下流側に充填したこと以外は、実施例１と同様に行った。その結果を表１に示す。
(Example 2)
In an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm, 900 mL of Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) is placed upstream, and a polyamine-type anion exchange resin (Purolite A830W, Purolite). The same procedure as in Example 1 was carried out except that a mixture of 18 mL of granular activated carbon (Taiko activated carbon CW480PGR, manufactured by Futamura Chemical Co., Ltd.) was filled on the downstream side. The results are shown in Table 1.
軟化処理材が、塩形の強酸性カチオン交換樹脂からなる第一層とポリアミン型のアニオン交換樹脂層からなる第二層の積層物である実施例１は、通水再開後のホルムアルデヒドの溶出量が低減されており、且つ、充填領域の体積は、充填前のそれぞれの体積の合計（使用量の合計）と比べて、違いがなかった。また、塩形の強酸性カチオン交換樹脂からなる第一層とポリアミン型のアニオン交換樹脂層及び粒状活性炭の混合物からなる第二層との積層物である実施例２は、通水再開後のホルムアルデヒドの溶出量が低減されており、且つ、充填領域の体積は、充填前のそれぞれの体積の合計（使用量の合計）と比べて、粒状活性炭の影響により少し膨張しているものの、膨張量は少なく留まっている。一方、軟化処理材に、塩形の強酸性カチオン交換樹脂層とポリアミン型のアニオン交換樹脂層の混合物を充填したものを用いた比較例１では、通水再開後のホルムアルデヒドの溶出量は、実施例１及び２に比べ少ないものの、イオン交換樹脂同士のクランピングにより充填領域の体積が、充填前のそれぞれの体積の合計（使用量の合計）と比べて、膨張しており、その膨張は大きかった。
In Example 1, the softening material is a laminate of a first layer made of a salt-type strong acid cation exchange resin and a second layer made of a polyamine-type anion exchange resin layer, and the amount of formaldehyde elution after resumption of water flow is achieved. Was reduced, and the volume of the filling region was not different from the total volume of each before filling (total usage amount). Further, Example 2 which is a laminate of a first layer made of a salt-type strongly acidic cation exchange resin and a second layer made of a mixture of a polyamine type anion exchange resin layer and granular activated carbon is a formaldehyde after resumption of water flow. The elution amount of the electrolyte is reduced, and the volume of the filling region is slightly expanded due to the influence of the granular activated carbon compared to the total volume of each before filling (total amount used), but the expansion amount is It stays less. On the other hand, in Comparative Example 1 in which a softening material filled with a mixture of a salt-type strong acid cation exchange resin layer and a polyamine-type anion exchange resin layer was used, the elution amount of formaldehyde after resumption of water flow was carried out. Although it is smaller than in Examples 1 and 2, the volume of the filling region is expanded by clamping the ion exchange resins compared to the total volume of each before filling (total usage amount), and the expansion is large. rice field.
Claims (6)
該カートリッジ容器内の軟化処理材の充填領域に充填されている軟化処理材とを有し、
該軟化処理材は、上流側に積層されている第一層と、下流側に積層されている第二層と、で形成されており、該第一層は、基体がスチレン−ジビニルベンゼン共重合体であり且つＮａ形又はＫ形の強酸性カチオン交換樹脂からなり、該第二層は、ポリアミン型のアニオン交換樹脂からなること、
を特徴とする浄水器用カートリッジ。 A cartridge container in which a tap water supply port and a softened water discharge port are formed,
It has a softening material that is filled in the filling area of the softening material in the cartridge container.
The softened material is formed of a first layer laminated on the upstream side and a second layer laminated on the downstream side, and the substrate of the first layer has a styrene-divinylbenzene copolymer weight. It is a coalescence and is made of a Na-type or K-type strong acid cation exchange resin, and the second layer is made of a polyamine-type anion exchange resin.
A cartridge for a water purifier that features.
該浄水器用カートリッジを収納する筐体と、
を有することを特徴とする軟化用浄水器。 The water purifier cartridge according to any one of claims 1 to 5.
A housing for storing the water purifier cartridge and
A water purifier for softening, which is characterized by having.
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| JPH05220477A (en) * | 1992-02-10 | 1993-08-31 | Kurita Water Ind Ltd | Nitric acid ion removing apparatus |
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