JPH06271301A - Method for generating chlorine dioxide - Google Patents
Method for generating chlorine dioxideInfo
- Publication number
- JPH06271301A JPH06271301A JP5080286A JP8028693A JPH06271301A JP H06271301 A JPH06271301 A JP H06271301A JP 5080286 A JP5080286 A JP 5080286A JP 8028693 A JP8028693 A JP 8028693A JP H06271301 A JPH06271301 A JP H06271301A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- ion
- chlorine dioxide
- resin
- sodium chlorite
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/028—Separation; Purification
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、各種用水、下水、廃
水及びプ−ル水などに、消毒剤や酸化剤として、或いは
パルプ工業における漂白剤として用いられる二酸化塩素
の発生に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to generation of chlorine dioxide used as a disinfectant or an oxidizer in various kinds of water, sewage, waste water, and pool water, or as a bleaching agent in the pulp industry.
【０００２】[0002]
【従来の技術】二酸化塩素（ClO2）は、従来の水の塩素
消毒に起因する諸問題（カルキ臭、発癌性の懸念のある
トリハロメタンの発生、アンモニアの存在による所要量
の増大、高pH時の消毒効果の低下等）を解決する優れた
消毒剤であるが、化学的に不安定で、長期の保存ができ
ないため、使用現場で生成する必要がある。従来二酸化
塩素の生成には、主として以下の方法が用いられてき
た。 2. Description of the Related Art Chlorine dioxide (ClO 2 ) is associated with various problems caused by conventional chlorine sterilization of water (chlorine odor, generation of trihalomethane which may cause carcinogenicity, increase of required amount due to presence of ammonia, high pH). It is an excellent disinfectant that solves the problems such as the deterioration of the disinfectant effect), but it is necessary to generate it at the site of use because it is chemically unstable and cannot be stored for a long time. Conventionally, the following methods have been mainly used for producing chlorine dioxide.
【０００３】亜塩素酸ナトリウムを、酸の存在下で分
解する方法、すなわち、亜塩素酸ナトリウム（NaClO2）
の水溶液に、塩酸などの鉱酸を加え、溶液のpHを1.0以
下の強酸性にして、二酸化塩素を発生させる方法で、非
常に簡便な方法であるが、原料として用いる鉱酸の保存
や注入の操作に危険を伴なう。この方法で発生した二酸
化塩素水中には、副生成物として塩素酸イオン（ClO3 -)
が含まれる。A method of decomposing sodium chlorite in the presence of an acid, that is, sodium chlorite (NaClO 2 ).
A mineral acid such as hydrochloric acid is added to the above aqueous solution to make the pH of the solution strongly acidic to 1.0 or less and chlorine dioxide is generated, which is a very simple method. Operation is dangerous. The chlorine dioxide water generated in this way, chlorate ions as a by-product (ClO 3 -)
Is included.
【０００４】亜塩素酸ナトリウムを塩素ガスで酸化す
る方法、すなわち、水に塩素ガスを高濃度で溶解し、こ
れに亜塩素酸ナトリウム水溶液を混合して、二酸化塩素
を発生する方法である。この方法では、現場に塩素ガス
を保管する必要があり、地震等の非常時に、ガス漏洩等
の危険が伴なう。この方法で発生した二酸化塩素水中に
は、原料として用いた亜塩素酸イオンが、未反応のまま
残留することがある。A method of oxidizing sodium chlorite with chlorine gas, that is, a method of dissolving chlorine gas in water at a high concentration and mixing this with an aqueous solution of sodium chlorite to generate chlorine dioxide. With this method, it is necessary to store chlorine gas at the site, and there is a risk of gas leakage in an emergency such as an earthquake. In the chlorine dioxide water generated by this method, the chlorite ion used as a raw material may remain unreacted.
【０００５】次亜塩素酸ナトリウムを酸性にし、発生
する塩素ガスにより亜塩素酸ナトリウムを酸化する方
法、すなわち酸性下で次亜塩素酸ナトリウム溶液と亜塩
素酸ナトリウム溶液を反応させる方法で、発生装置が複
雑となり制御も難しくなる。この方法で発生した二酸化
塩素水中には、副生成物として塩素酸イオンが含まれ
る。A generator is produced by a method of acidifying sodium hypochlorite and oxidizing the sodium chlorite with chlorine gas generated, that is, a method of reacting a sodium hypochlorite solution and a sodium chlorite solution under acidic conditions. Becomes complicated and difficult to control. Chlorine ion is contained as a by-product in the chlorine dioxide water generated by this method.
【０００６】[0006]
【発明によつて解決しようとする課題】前項で示したよ
うに、従来の方法で二酸化塩素を発生させるには、原料
として鉱酸や塩素ガス等の、取り扱いや保管に危険を伴
なうものを使用せざるをえなかつたり、或いは装置が複
雑で制御が難しい等の問題があつた。またさらに大きな
問題は、副生成物として発生する塩素酸イオンや、未反
応のまま残留する亜塩素酸イオンには、健康障害の懸念
があることである。As described in the preceding paragraph, in order to generate chlorine dioxide by the conventional method, a mineral acid, chlorine gas or the like as a raw material is dangerous to handle and store. However, there are problems such as being forced to use the device, or the device being complicated and difficult to control. Further, an even bigger problem is that chlorate ions generated as by-products and chlorite ions that remain unreacted may cause health problems.
【０００７】この発明は、これらの問題を解決し、簡単
な装置で危険を伴なわず、しかも塩素酸イオンや亜塩素
酸イオンを含まない、安全性の高い二酸化塩素水を製造
する技術を提供するものである。The present invention solves these problems and provides a technique for producing highly safe chlorine dioxide water with a simple apparatus, which is not dangerous and does not contain chlorate ion or chlorite ion. To do.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、亜塩素酸
ナトリウム水溶液を、Ｈ型陽イオン交換樹脂と接触させ
ることにより、二酸化塩素が効率的に発生することを新
たに見いだした。その発生機構は、まだ明確ではない
が、亜塩素酸ナトリウムのNa+がイオン交換樹脂の作用
によりH+と置換され、次式の何れか（或いは両者）で示
される反応が進行しているものと考えられる。 4ClO2 - ＋2H+→2ClO2＋Cl- ＋ClO3 - ＋H2O (1) 5ClO2 - ＋4H+→4ClO2＋Cl- ＋2H2O (2)The present inventors have newly found that chlorine dioxide is efficiently generated by contacting an aqueous sodium chlorite solution with an H-type cation exchange resin. The generation mechanism is not yet clear, but Na + of sodium chlorite is replaced with H + by the action of the ion exchange resin, and the reaction represented by either (or both) of the following formulas is proceeding. Conceivable. 4ClO 2 - + 2H + → 2ClO 2 + Cl - + ClO 3 - + H 2 O (1) 5ClO 2 - + 4H + → 4ClO 2 + Cl - + 2H 2 O (2)
【０００９】すなわち、亜塩素酸ナトリウムは、水中で
ClO2 -とNa+イオンとに解離し、このNa+イオンが、H型陽
イオン交換樹脂の作用により、H+イオンと交換される。
そして、ClO2 -とH+の間で、上式に示された反応が進行
し、二酸化塩素が発生するものと考えられる。しかし、
上記反応式(1)からも分かるように、この方法では生成
した二酸化塩素水中には、副生成物として若干の塩素酸
イオン(ClO3 -)が含まれている。That is, sodium chlorite is
It dissociates into ClO 2 − and Na + ions, and these Na + ions are exchanged with H + ions by the action of the H-type cation exchange resin.
Then, it is considered that the reaction shown in the above formula proceeds between ClO 2 − and H + to generate chlorine dioxide. But,
As can be seen from the above reaction formula (1), the chlorine dioxide water produced by this method contains some chlorate ion (ClO 3 − ) as a by-product.
【００１０】本発明者らは更に、生成した二酸化塩素水
中の塩素酸イオンの除去に対し、Cl型の陰イオン交換樹
脂が有効に作用することを新たに知見した。すなわち、
Cl型の陰イオン交換樹脂に、この塩素酸イオンを含む二
酸化塩素水を接触させることにより、ClO3 -は無害な塩
素イオン(Cl-)に効率よく交換されることを見いだし
た。The present inventors have newly found that the Cl-type anion exchange resin effectively acts on the removal of chlorate ions in the produced chlorine dioxide water. That is,
It was found that ClO 3 − was efficiently exchanged to harmless chlorine ion (Cl − ) by contacting Cl type anion exchange resin with chlorine dioxide water containing this chlorate ion.
【００１１】[0011]
【作用】亜塩素酸ナトリウム水溶液とイオン交換樹脂の
接触方法は、亜塩素酸ナトリウム水溶液中に樹脂を添
加、攪拌した後、分離してもよく、或いは樹脂層中に溶
液を通過せしめてもよい。イオン交換樹脂は、H型陽イ
オン交換樹脂とCl型の陰イオン交換樹脂とを個別に用い
ても、或いは両者を混合して用いても差し支えない。樹
脂の再生に際しては、何れの樹脂とも塩酸で再生すれば
よく、これもこの発明の操作が簡単に行なえるという利
点の一つである。イオン交換樹脂としては、通常粒状の
ものを使用するが、膜状に成形されたイオン交換樹脂を
用い、所謂電気透析として使用してもよい。The method of contacting the sodium chlorite aqueous solution with the ion-exchange resin may be such that the resin is added to the sodium chlorite aqueous solution and stirred, and then separated, or the solution may be passed through the resin layer. . As the ion exchange resin, the H-type cation exchange resin and the Cl-type anion exchange resin may be used individually or both may be used in combination. When the resin is regenerated, any resin may be regenerated with hydrochloric acid, which is one of the advantages that the operation of the present invention can be easily performed. As the ion exchange resin, a granular one is usually used, but a membrane-shaped ion exchange resin may be used and may be used as so-called electrodialysis.
【００１２】[0012]
例(1):試薬亜塩素酸ナトリウム(NaClO2含量90W/V)を蒸
留水に溶解し、濃度3.9%の亜塩素酸ナトリウム水溶液を
調製した。この水溶液600mlを密栓付きガラス容器に入
れ、湿潤状態のH型陽イオン交換樹脂（三菱化成製、ダ
イヤイオンSK1B)を170g投入して密封し、常温で30分間
振とうした。振とう後の溶液中には、1.14%の二酸化塩
素(ClO2)が溶解しており、二酸化塩素の発生が確認され
た。また塩素酸イオン(ClO3 -)は、0.68%存在していた。Example (1): Reagent sodium chlorite (NaClO 2 content 90 W / V) was dissolved in distilled water to prepare a sodium chlorite aqueous solution having a concentration of 3.9%. 600 ml of this aqueous solution was placed in a glass container with a stopper, 170 g of a wet H-type cation exchange resin (manufactured by Mitsubishi Kasei Co., Ltd., Diaion SK1B) was added, sealed, and shaken at room temperature for 30 minutes. In the solution after shaking, 1.14% chlorine dioxide (ClO 2 ) was dissolved, and generation of chlorine dioxide was confirmed. The chlorate ion (ClO 3 -) was present 0.68%.
【００１３】例(2):塩素酸イオンを含む二酸化塩素水溶
液(ClO2濃度0.13%、ClO3 -濃度0.13%)800mlを、密栓付き
ガラス容器に入れ、これに湿潤状態のCl型陰イオン交換
樹脂(ダウケミカル社製、ダウエックスSAR)80gを投入し
て密封し、常温で20分間振とうした。振とう後の溶液中
の二酸化塩素及び塩素酸イオン濃度は、それぞれ0.12%
及び0.02%となり、塩素酸イオンの85%が除去できること
を確認した。[0013] Example (2): chlorine dioxide aqueous solution containing chlorate ions (ClO 2 concentration 0.13%, ClO 3 - concentration 0.13%) to 800 ml, placed in a stoppered glass container, Cl type anion exchange this wet 80 g of resin (Dow Chemicals Co., Ltd., Dowex SAR) was added, sealed, and shaken at room temperature for 20 minutes. The chlorine dioxide and chlorate ion concentrations in the solution after shaking were 0.12% each.
And 0.02%, and it was confirmed that 85% of chlorate ions could be removed.
【００１４】例(3):実施例(1)及び例(2)に用いた二種類
のイオン交換樹脂を等量混合し、これをイオン交換樹脂
の５倍量の２規定の塩酸を用いて再生した。内径2.5cm
のガラス筒に、再生したイオン交換樹脂を20cmの層厚で
詰め、この樹脂層に4.1%の亜塩素酸ナトリウム溶液を、
10ml/minのろ過速度で150ml透過した。ろ液中の二酸化
塩素及び塩素酸イオン濃度は、それぞれ0.8%及び0.08%
であつた。したがつて、H型陽イオン交換樹脂とCl型陰
イオン交換樹脂とを混合したろ層に、亜塩素酸ナトリウ
ム水溶液を透過することにより、塩素酸イオン濃度の極
めて低い二酸化塩素水溶液を得ることが確認できた。Example (3): The two kinds of ion exchange resins used in Examples (1) and (2) were mixed in equal amounts, and this was mixed with 5 times the amount of 2N hydrochloric acid of the ion exchange resin. Replayed. Inner diameter 2.5 cm
The regenerated ion-exchange resin is packed in a glass tube with a thickness of 20 cm, and a 4.1% sodium chlorite solution is added to the resin layer.
150 ml was permeated at a filtration rate of 10 ml / min. Chlorine dioxide and chlorate ion concentrations in the filtrate are 0.8% and 0.08%, respectively.
It was. Therefore, it is possible to obtain a chlorine dioxide aqueous solution having an extremely low chlorate ion concentration by permeating the sodium chlorite aqueous solution through the filter layer in which the H-type cation exchange resin and the Cl-type anion exchange resin are mixed. It could be confirmed.
【００１５】[0015]
【発明の効果】この発明により明らかにされた方法、す
なわち、亜塩素酸ナトリウム水溶液をH型陽イオン交換
樹脂及びCl型陰イオン交換樹脂で、順次に或いは同時に
処理することにより、健康障害の懸念のある塩素酸イオ
ンを著しく低減した二酸化塩素水を、簡単な装置で危険
を伴なわず得ることが可能となつた。EFFECTS OF THE INVENTION By the method disclosed by the present invention, that is, by treating an aqueous sodium chlorite solution with a H-type cation exchange resin and a Cl-type anion exchange resin sequentially or simultaneously, there is a risk of health problems. It became possible to obtain chlorine dioxide water with significantly reduced chlorate ions, which had a certain amount, without any danger, using a simple device.
【００１６】また、塩素酸イオンが悪影響を及ぼさない
用途（飲用以外等）に用いられる場合には、Cl型陰イオ
ン交換樹脂での処理が不要であること、或いは他の方法
で発生した二酸化塩素水中に不純物として存在する塩素
酸イオンや亜塩素酸イオンが、Cl型陰イオン交換樹脂で
除去できることは言うまでもない。When the chlorate ion is used for a purpose in which it does not adversely affect (other than drinking, etc.), treatment with a Cl type anion exchange resin is unnecessary, or chlorine dioxide generated by other methods is used. Needless to say, chlorate ions and chlorite ions present as impurities in water can be removed with a Cl-type anion exchange resin.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年３月２５日[Submission date] March 25, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】すなわち、亜塩素酸ナトリウムは、水中で
ＣｌＯ２ −とＮａ＋イオンとに解離し、このＮａ＋イオ
ンが、Ｈ型陽イオン交換樹脂の作用により、Ｈ＋イオン
と交換される。そして、ＣｌＯ２ −とＨの間で、上式に
示された反応が進行し、二酸化塩素が発生するものと考
えられる。しかし、上記反応式（１）からも分かるよう
に、この方法では生成した二酸化塩素水中には、副生成
物として若干の塩素酸イオン（ＣｌＯ３ −）が含まれて
いる。That is, sodium chlorite is dissociated into ClO 2 − and Na + ions in water, and the Na + ions are exchanged with H + ions by the action of the H-type cation exchange resin. Then, it is considered that the reaction represented by the above formula proceeds between ClO 2 − and H to generate chlorine dioxide. However, as can be seen from the above reaction formula (1), the chlorine dioxide water produced by this method contains some chlorate ion (ClO 3 − ) as a by-product.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】例（１）：試薬亜塩素酸ナトリウム（Ｎａ
ＣｌＯ２含量９０Ｗ／Ｖ％）を蒸留水に溶解し、濃度
３．９％の亜塩素酸ナトリウム水溶液を調製した。この
水溶液６００ｍｌを密栓付きガラス容器に入れ、湿潤状
態のＨ型陽イオン交換樹脂（三菱化成製、ダイヤイオン
ＳＫ１Ｂ）を１７０ｇ投入して密封し、常温で３０分間
振とうした。振とう後の溶液中には、１．１４％の二酸
化塩素（ＣｌＯ２）が溶解しており、二酸化塩素の発生
が確認された。また塩素酸イオン（ＣｌＯ３ −）は、
０．６８％存在していた。Example (1): Reagent sodium chlorite (Na
(ClO 2 content 90 W / V%) was dissolved in distilled water to prepare an aqueous sodium chlorite solution having a concentration of 3.9%. 600 ml of this aqueous solution was placed in a glass container with a tight stopper, 170 g of a wet H-type cation exchange resin (manufactured by Mitsubishi Kasei Co., Ltd., Diaion SK1B) was added, sealed, and shaken at room temperature for 30 minutes. 1.14% of chlorine dioxide (ClO 2 ) was dissolved in the solution after shaking, and generation of chlorine dioxide was confirmed. In addition, chlorate ion (ClO 3 − ) is
There was 0.68%.
───────────────────────────────────────────────────── 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 1/76 Ａ 9045−4Ｄ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // C02F 1/76 A 9045-4D
Claims (4)
化塩素を発生させる方法。1. A method of generating chlorine dioxide by using an ion exchange resin.
樹脂でＨ型である請求項１記載の方法。2. The method according to claim 1, wherein the ion-exchange resin used is a cation-exchange resin of H type.
含まれる塩素酸イオンあるいは亜塩素酸イオンを除去す
る方法を付加したことを特徴とする請求項１記載の方
法。3. The method according to claim 1, wherein a method for removing chlorate ions or chlorite ions contained as impurities in the generated chlorine dioxide water is added.
Cl型の陰イオン交換樹脂を用いる方法。4. A means for achieving the method of claim 3,
Method using Cl type anion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5080286A JPH06271301A (en) | 1993-03-16 | 1993-03-16 | Method for generating chlorine dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5080286A JPH06271301A (en) | 1993-03-16 | 1993-03-16 | Method for generating chlorine dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06271301A true JPH06271301A (en) | 1994-09-27 |
Family
ID=13714035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5080286A Pending JPH06271301A (en) | 1993-03-16 | 1993-03-16 | Method for generating chlorine dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06271301A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003011750A3 (en) * | 2001-08-02 | 2003-10-02 | Richard Sampson | Methods for making chlorous acid and chlorine dioxide |
| WO2007127478A2 (en) * | 2006-04-28 | 2007-11-08 | Sampson Richard L | Methods and apparatus for producing chlorine dioxide by ion exchange |
| JP2016183088A (en) * | 2015-03-27 | 2016-10-20 | セントラルフィルター工業株式会社 | Generator for chlorine dioxide-containing sterile water |
-
1993
- 1993-03-16 JP JP5080286A patent/JPH06271301A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003011750A3 (en) * | 2001-08-02 | 2003-10-02 | Richard Sampson | Methods for making chlorous acid and chlorine dioxide |
| WO2007127478A2 (en) * | 2006-04-28 | 2007-11-08 | Sampson Richard L | Methods and apparatus for producing chlorine dioxide by ion exchange |
| WO2007127478A3 (en) * | 2006-04-28 | 2008-08-28 | Richard L Sampson | Methods and apparatus for producing chlorine dioxide by ion exchange |
| JP2016183088A (en) * | 2015-03-27 | 2016-10-20 | セントラルフィルター工業株式会社 | Generator for chlorine dioxide-containing sterile water |
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