JPH07315804A - Processing of chlorine dioxide and processed product - Google Patents
Processing of chlorine dioxide and processed productInfo
- Publication number
- JPH07315804A JPH07315804A JP10695994A JP10695994A JPH07315804A JP H07315804 A JPH07315804 A JP H07315804A JP 10695994 A JP10695994 A JP 10695994A JP 10695994 A JP10695994 A JP 10695994A JP H07315804 A JPH07315804 A JP H07315804A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine dioxide
- aqueous solution
- water
- deterioration
- chlorine
- 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.)
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- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二酸化塩素の加工方法
及び該加工方法により得られる加工物に関する。TECHNICAL FIELD The present invention relates to a method for processing chlorine dioxide and a processed product obtained by the method.
【０００２】[0002]
【従来の技術】従来、二酸化塩素は気体の形態で又は二
酸化塩素を水に溶解した水溶液の形態で、漂白、殺菌等
の目的に使用されていた。2. Description of the Related Art Conventionally, chlorine dioxide has been used in the form of gas or in the form of an aqueous solution of chlorine dioxide dissolved in water for the purpose of bleaching, sterilization and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかし、二酸化塩素の
気体は爆発性のため保管することは危険であり、使用時
に二酸化塩素の気体を製造し、製造場所で直ちに使用す
る必要があった。そして水溶液とした場合においても二
酸化塩素の劣化（減少）が著しく長期間保管することは
できなかった。そこで本発明の課題は、一定期間安全に
保管可能とされる二酸化塩素の加工方法及び該加工方法
により得られる加工物を提供することにある。However, since chlorine dioxide gas is explosive, it is dangerous to store it, and it was necessary to produce chlorine dioxide gas at the time of use and immediately use it. Even when it was used as an aqueous solution, the deterioration (reduction) of chlorine dioxide was remarkable and it could not be stored for a long time. Therefore, an object of the present invention is to provide a method for processing chlorine dioxide that can be safely stored for a certain period of time, and a processed product obtained by the processing method.
【０００４】[0004]
【課題を解決するための手段】上記課題解決のために、
請求項１では二酸化塩素の気体を水に溶解し、二酸化塩
素水溶液を作成する工程及びその作成後前記二酸化塩素
水溶液を冷却し、固体とする工程を有することを特徴と
する二酸化塩素の加工方法を創作した。請求項２では二
酸化塩素の気体を純水に溶解し、二酸化塩素水溶液を作
成する工程及びその作成後１０日以内に前記二酸化塩素
水溶液を冷却し、固体とする工程を有することを特徴と
する二酸化塩素の加工方法を創作した。請求項３では前
記二酸化塩素水溶液を固体とする工程の前に前記二酸化
塩素水溶液をｐＨ６．０以上ｐＨ７．０以下に調整する
工程を有することを特徴とする請求項１又は請求項２に
記載の二酸化塩素の加工方法を創作した。請求項４では
二酸化塩素の気体を酸性イオン水に溶解し、二酸化塩素
水溶液を作成する工程及び前記二酸化塩素水溶液を冷却
し、固体とする工程を有することを特徴とする二酸化塩
素の加工方法を創作した。請求項５では請求項１ないし
請求項４の内のいずれか一つに記載の加工方法により得
られる固体であることを特徴とする二酸化塩素の加工物
を創作した。[Means for Solving the Problems] In order to solve the above problems,
According to claim 1, there is provided a method for processing chlorine dioxide, which comprises a step of dissolving chlorine dioxide gas in water to prepare an aqueous solution of chlorine dioxide and a step of cooling the aqueous solution of chlorine dioxide to form a solid after the preparation. Created. According to claim 2, the method comprises the steps of dissolving chlorine dioxide gas in pure water to prepare a chlorine dioxide aqueous solution and cooling the chlorine dioxide aqueous solution within 10 days after the production to solidify it. Created a chlorine processing method. Claim 3 has a step of adjusting the chlorine dioxide aqueous solution to pH 6.0 or more and pH 7.0 or less before the step of solidifying the chlorine dioxide aqueous solution. Created a chlorine dioxide processing method. In Claim 4, the method of processing chlorine dioxide is characterized by including the steps of dissolving chlorine dioxide gas in acidic ionized water to prepare an aqueous solution of chlorine dioxide and cooling the aqueous solution of chlorine dioxide to form a solid. did. In a fifth aspect, a processed product of chlorine dioxide is created, which is a solid obtained by the processing method according to any one of the first to fourth aspects.
【０００５】前記純水とは二酸化塩素と反応する不純物
を除去した水であり、不純物がより多く除去されている
ほどより望ましい。この純水は例えば水を濾過すること
により得ることができる。また請求項３においてｐＨ
６．０以上ｐＨ７．０以下に調整する方法としては例え
ば各種の無機酸又は有機酸、例えば塩酸、硫酸、蟻酸又
は酢酸等を二酸化塩素水溶液を作成する純水に添加する
か又は二酸化塩素水溶液に添加する方法を採ることがで
きる。一方請求項４において酸性イオン水とは、水道水
に0.05〜0.1 重量％ほどの少量のＮａＣｌ又はＫＣｌを
添加した溶液を電気分解して得られる陽極側の溶液であ
り、酸化還元電位900mV 〜1200mVでありｐＨ3.0 以下好
ましくはｐＨ2.3 以下の水を意味する。The pure water is water from which impurities that react with chlorine dioxide have been removed, and the more impurities are removed, the more desirable it is. This pure water can be obtained, for example, by filtering water. Further, in claim 3, pH
As a method for adjusting the pH to 6.0 or more and 7.0 or less, for example, various inorganic acids or organic acids such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid are added to pure water to prepare a chlorine dioxide aqueous solution, or to the chlorine dioxide aqueous solution. A method of adding can be adopted. On the other hand, in claim 4, the acidic ionized water is a solution on the anode side obtained by electrolyzing a solution obtained by adding a small amount of 0.05 to 0.1% by weight of NaCl or KCl to tap water, and has a redox potential of 900 mV to 1200 mV. And means water having a pH of 3.0 or less, preferably pH 2.3 or less.
【０００６】[0006]
【作用】二酸化塩素は沸点が１１℃と低いため、純水中
に溶解した場合においても沸騰して気体の状態であるこ
とが多く、劣化が促進されるが、請求項１ないし請求項
４に記載の二酸化塩素の加工方法においては、二酸化塩
素の気体を水、純水、又は酸性イオン水に溶解し、前記
二酸化塩素水溶液を冷却し、固体とするので、二酸化塩
素を固体（氷）中に封じ込めた液体とすることにより二
酸化塩素の劣化が良好に防止されると考えられる。請求
項２に記載の二酸化塩素の加工方法においては、さらに
二酸化塩素の気体を純水に溶解し、二酸化塩素水溶液を
作成後１０日以内に前記二酸化塩素水溶液を冷却し、固
体とするので、二酸化塩素の水溶液の状態における一日
の劣化は約１％であるため、固体とする前の劣化は約１
０％以下とされ、固体とした後はほとんど劣化しないた
め、二酸化塩素の劣化は約１０％以下とされ、実用的で
ある。また二酸化塩素と反応する不純物を除去した純水
を使用しているので二酸化塩素の劣化がより良好に防止
されると考えられる。請求項３に記載の二酸化塩素の加
工方法においては、ｐＨ６．０以上ｐＨ７．０以下とす
ることにより水素イオンが二酸化塩素と水とが反応して
生成するＨＣｌＯ2 と反応してＨＣｌＯ3 を生じると考
えられ、この反応は不過逆的であるため安定し、二酸化
塩素の劣化がより良好に防止されると考えられる。請求
項４に記載の二酸化塩素の加工方法においては、酸性イ
オン水中に含まれる塩素イオンが二酸化塩素と反応し、
二酸化塩素の濃度をたかめることにより二酸化塩素の劣
化がより良好に防止されると考えられる。請求項５に記
載の二酸化塩素の加工物においては、上記の請求項１、
２、３又は４の各作用により二酸化塩素の劣化が良好に
防止されると考えられる。Since chlorine dioxide has a low boiling point of 11 ° C., it often boils and remains in a gaseous state even when dissolved in pure water, which accelerates its deterioration. In the method for processing chlorine dioxide described above, chlorine dioxide gas is dissolved in water, pure water, or acidic ionized water, and the chlorine dioxide aqueous solution is cooled to form a solid, so that chlorine dioxide is dissolved in a solid (ice). It is considered that the use of a contained liquid will prevent the deterioration of chlorine dioxide. In the method for processing chlorine dioxide according to claim 2, further, a gas of chlorine dioxide is dissolved in pure water, and the chlorine dioxide aqueous solution is cooled within 10 days after the aqueous solution of chlorine dioxide is prepared to be solidified. Since the deterioration per day in the state of an aqueous solution of chlorine is about 1%, the deterioration before solidification is about 1%.
Since it is set to 0% or less and hardly deteriorates after being made solid, the deterioration of chlorine dioxide is set to about 10% or less, which is practical. Further, since pure water from which impurities that react with chlorine dioxide have been removed is used, it is considered that the deterioration of chlorine dioxide can be prevented better. In the chlorine dioxide processing method according to claim 3, by setting the pH to 6.0 or more and pH 7.0 or less, hydrogen ions react with HClO 2 generated by the reaction of chlorine dioxide and water to generate HClO 3 . It is thought that this reaction is stable because it is irreversible, and the deterioration of chlorine dioxide is better prevented. In the method for processing chlorine dioxide according to claim 4, chlorine ions contained in acidic ionized water react with chlorine dioxide,
It is considered that the deterioration of chlorine dioxide is better prevented by increasing the concentration of chlorine dioxide. In the processed product of chlorine dioxide according to claim 5, the above-mentioned claim 1,
It is considered that the effects of 2, 3 or 4 effectively prevent the deterioration of chlorine dioxide.
【０００７】[0007]
実施例１ リオリンダ社製ジェネレ−タにより二酸化塩素のｐＨ7.
0 の水溶液を作成した。このジェネレ−タは真空状態で
塩素ガスと亜塩素酸ナトリウムとをカラム内で反応させ
ることにより二酸化塩素の気体を作成する。（反応式
２ＮａＣｌ０2＋Ｃｌ2 →２Ｃｌ０2 （気体）＋２Ｎａ
Ｃｌ）塩素ガスと亜塩素酸ナトリウムの供給は真空エダ
クタ−を操作する水によってコントロ−ルされる。前記
ジェネレ−タによると塩素ガスと亜塩素酸ナトリウムは
カラム内で即座に反応し、９５％以上という非常に高い
変換効率でかつ安全な濃度の純粋な二酸化塩素ガスが製
造される。この二酸化塩素ガスは真空エダクタ−を操作
する純水の中に吸引され、溶解される。この純水のｐＨ
は約7.0 であった。前記ジェネレ−タにより生成された
二酸化塩素の純度は９９％以上になり、検出可能な遊離
塩素は含まず、亜塩素酸や塩素酸のような副生成物は極
微量しか含まれていなかった。Example 1 pH of chlorine dioxide of 7.
An aqueous solution of 0 was prepared. This generator produces chlorine dioxide gas by reacting chlorine gas and sodium chlorite in a column in a vacuum state. (Reaction formula
2NaCl0 2 + Cl 2 → 2Cl0 2 (gas) + 2Na
The supply of Cl) chlorine gas and sodium chlorite is controlled by water operating a vacuum eductor. According to the generator, chlorine gas and sodium chlorite react immediately in the column to produce pure chlorine dioxide gas having a very high conversion efficiency of 95% or more and a safe concentration. This chlorine dioxide gas is sucked and dissolved in pure water which operates a vacuum eductor. PH of this pure water
Was about 7.0. The chlorine dioxide produced by the generator had a purity of 99% or more, contained no detectable free chlorine, and contained only trace amounts of by-products such as chlorous acid and chloric acid.
【０００８】任意濃度及び任意量の二酸化塩素水溶液を
前記ジェネレ−タにより生成することができ、この二酸
化塩素水溶液の濃度は分光測分析により測定することが
できる。二酸化塩素の最大吸収は３６０ｎｍであり、11
00〜1450L/mol/cmの間に分布する。An arbitrary concentration and an arbitrary amount of an aqueous chlorine dioxide solution can be produced by the generator, and the concentration of the aqueous chlorine dioxide solution can be measured by spectroscopic analysis. The maximum absorption of chlorine dioxide is 360 nm, 11
It is distributed between 00 and 1450 L / mol / cm.
【０００９】前記ジェネレ−タにより濃度2000ppm の二
酸化塩素水溶液を得た。この二酸化塩素水溶液を作成
後、直ちに適量の純水に溶解し、続いてこの二酸化塩素
水溶液に水溶液のｐＨを測定しながら希塩酸を適量滴下
混合することにより、二酸化塩素濃度が300ppmであり、
各ｐＨが6.0,6.2,6.4, 6.6,6.8, 7.0 及び 7.2である各
二酸化塩素水溶液を迅速に作成し、作成後速やかにこの
各ｐＨの二酸化塩素水溶液を褐色のポリエチレン製の遮
光びんに各100 ミリリットルいれ、各３０個のサンプルを作成
した。これらのサンプルを速やかに−１０℃の冷凍庫に
入れて急速冷凍し、固体形状として７週間保管した。こ
の保管中、１週経過ごとに固体形状の二酸化塩素水溶液
を１０℃の冷暗所で徐々に溶解し、液体の状態となった
後、迅速に各水溶液中の二酸化塩素濃度を前記の分光測
分析により測定した。対照としては同時に同様に作成し
た二酸化塩素濃度300ppmであり、ｐＨ7.0 である二酸化
塩素水溶液を、作成後速やかに褐色のポリエチレン製の
遮光びんに各100 ミリリットル入れたサンプルを平均温
度２０℃の室内にて溶液形状にて７週間保管した二酸化
塩素水の濃度を１週経過ごとに前記の分光測分析により
測定した。この結果を表１に示す。An aqueous chlorine dioxide solution having a concentration of 2000 ppm was obtained from the generator. Immediately after preparing this chlorine dioxide aqueous solution, it is dissolved in an appropriate amount of pure water, and then an appropriate amount of dilute hydrochloric acid is added dropwise to this chlorine dioxide aqueous solution while measuring the pH of the aqueous solution to give a chlorine dioxide concentration of 300 ppm,
Promptly prepare each chlorine dioxide aqueous solution with each pH of 6.0, 6.2, 6.4, 6.6, 6.8, 7.0 and 7.2, and immediately after the preparation, add each chlorine dioxide aqueous solution of each pH to a brown polyethylene light-shielding bottle with 100 30 ml of each sample was prepared. These samples were immediately placed in a freezer at -10 ° C for quick freezing and stored as a solid form for 7 weeks. During this storage, the chlorine dioxide aqueous solution in solid form was gradually dissolved in a cool dark place at 10 ° C every 1 week to become a liquid state, and then the chlorine dioxide concentration in each aqueous solution was rapidly measured by the above-mentioned spectroscopic analysis. It was measured. As a control, chlorine dioxide concentration of 300 ppm and pH 7.0 were also prepared at the same time, and 100 ml of each was immediately put into a brown polyethylene shading bottle after preparation. The concentration of chlorine dioxide water stored in the solution form for 7 weeks was measured by the above-mentioned spectroscopic analysis every week. The results are shown in Table 1.
【００１０】[0010]
【表１】 [Table 1]
【００１１】表１中、数値単位はppm である。表１の結
果、ｐＨが6.0 〜7.2 の全ｐＨにおいて−１０℃の冷凍
庫に入れて急速冷凍し、固体形状の二酸化塩素の加工物
として保管した二酸化塩素水は７週間後においてもほと
んど劣化が認められなかった。一方、対照においては時
間の経過とともに著しい劣化が認められた。In Table 1, the numerical unit is ppm. As a result of Table 1, chlorine dioxide water stored in a freezer at -10 ° C and rapidly frozen at a total pH of 6.0 to 7.2 and stored as a processed product of chlorine dioxide in a solid form showed almost no deterioration even after 7 weeks. I couldn't do it. On the other hand, in the control, remarkable deterioration was observed with the passage of time.
【００１２】実施例２ 実施例１と同様にリオリンダ社製ジェネレ−タにより濃
度2000ppm の二酸化塩素水溶液を得た。この二酸化塩素
水溶液を速やかに酸性イオン水に溶解し300ppmの濃度の
二酸化塩素水溶液を得て、この二酸化塩素水溶液を速や
かに褐色のポリエチレン製の遮光びんに各100 ミリリッ
トルいれ、３０個のサンプルを作成した。なお酸性イオ
ン水としては0.8 重量％ＮａＣｌ濃度の水道水を電気分
解して得られた酸化還元電位1000mV、ｐＨ2.3 のものを
使用した。これらのサンプルは速やかに−１０℃の冷凍
庫に入れて急速冷凍し、固体形状として７週間保管し
た。この保管中、１週経過ごとに固体形状の二酸化塩素
水溶液を１０℃の冷暗所で徐々に溶解し液体状態となっ
た後、迅速に各水溶液中の二酸化塩素濃度を前記した分
光測分析により測定した。この結果は実施例１と同様で
あり７週間後においても二酸化塩素濃度は290 ppm であ
り、劣化はほとんどみとめられなかった。Example 2 In the same manner as in Example 1, a chlorine dioxide aqueous solution having a concentration of 2000 ppm was obtained with a generator manufactured by Rio Linda. This chlorine dioxide aqueous solution is rapidly dissolved in acidic ionized water to obtain a chlorine dioxide aqueous solution with a concentration of 300 ppm, and this chlorine dioxide aqueous solution is immediately added to a brown polyethylene shading bottle in an amount of 100 ml each to make 30 samples. did. The acidic ionized water used was one having a redox potential of 1000 mV and a pH of 2.3, which was obtained by electrolyzing tap water having a NaCl concentration of 0.8% by weight. These samples were immediately placed in a freezer at -10 ° C for quick freezing and stored in solid form for 7 weeks. During this storage, the chlorine dioxide aqueous solution in a solid form was gradually dissolved in a cool dark place at 10 ° C. into a liquid state every one week, and then the chlorine dioxide concentration in each aqueous solution was rapidly measured by the above-mentioned spectroscopic analysis. . This result was the same as in Example 1, and the chlorine dioxide concentration was 290 ppm even after 7 weeks, and deterioration was hardly found.
【００１３】以上の実施例より二酸化塩素の各溶液を冷
却して、固体形状の加工物とすることにより、二酸化塩
素の劣化が著しく防止されることが分かった。またｐＨ
６．０以上ｐＨ７．０以下である二酸化塩素水を冷却
し、固体形状とした加工物を溶解し、溶液状態として使
用する際には、ｐＨ６．０以上ｐＨ７．０以下、より好
ましくはｐＨ６．０以上ｐＨ６．８以下であることか
ら、水素イオンが作用して二酸化塩素の濃度を上昇さ
せ、二酸化塩素の殺菌効果が増強され得ると考えられ
る。また酸性イオン水に溶解した場合の固体形状の加工
物を溶解し、溶液状態として使用する際には、酸性イオ
ン水の作用により二酸化塩素の殺菌効果が増強され得る
と考えられる。From the above examples, it was found that by cooling each solution of chlorine dioxide to form a processed product in a solid form, the deterioration of chlorine dioxide was significantly prevented. Also pH
When chlorine dioxide water having a pH of 6.0 or higher and 7.0 or lower is cooled to dissolve the processed product in a solid form and used as a solution, pH 6.0 or higher and pH 7.0 or lower, more preferably pH 6.0 or lower. Since the pH is 0 or more and 6.8 or less, it is considered that hydrogen ions act to increase the concentration of chlorine dioxide and the sterilizing effect of chlorine dioxide can be enhanced. Further, it is considered that when the solid-form processed product when dissolved in acidic ionized water is dissolved and used as a solution, the action of acidic ionized water can enhance the bactericidal effect of chlorine dioxide.
【００１４】[0014]
【発明の効果】本発明の加工方法及び加工物によると二
酸化塩素の劣化を防止した状態で長期間、二酸化塩素を
保存できる。従って、二酸化塩素を作成後、作成場所に
て直ちに使用する必要はなく、二酸化塩素を作成後、輸
送及び保管できるため、二酸化塩素の利用の便宜が図ら
れる。例えば二酸化塩素を作成するプラントの設備がな
い場所においても二酸化塩素を手軽に使用できる。According to the processing method and processed product of the present invention, chlorine dioxide can be stored for a long period of time while preventing the deterioration of chlorine dioxide. Therefore, it is not necessary to use chlorine dioxide immediately after it has been created, and since chlorine dioxide can be transported and stored after it is created, it is convenient to use chlorine dioxide. For example, chlorine dioxide can be easily used even in a place where there is no facility for producing chlorine dioxide.
Claims (5)
塩素水溶液を作成する工程及びその作成後前記二酸化塩
素水溶液を冷却し、固体とする工程を有することを特徴
とする二酸化塩素の加工方法。1. A method for processing chlorine dioxide, comprising: a step of dissolving chlorine dioxide gas in water to prepare a chlorine dioxide aqueous solution; and a step of cooling the chlorine dioxide aqueous solution to solid after the preparation. .
化塩素水溶液を作成する工程及びその作成後１０日以内
に前記二酸化塩素水溶液を冷却し、固体とする工程を有
することを特徴とする二酸化塩素の加工方法。2. A method of dissolving chlorine gas in pure water to prepare an aqueous solution of chlorine dioxide, and cooling the aqueous solution of chlorine dioxide within 10 days after the production to solidify the aqueous solution. Chlorine dioxide processing method.
の前に前記二酸化塩素水溶液をｐＨ６．０以上ｐＨ７．
０以下に調整する工程を有することを特徴とする請求項
１又は請求項２に記載の二酸化塩素の加工方法。3. Before the step of solidifying the chlorine dioxide aqueous solution, the chlorine dioxide aqueous solution has a pH of 6.0 or more and a pH of 7.
The method for processing chlorine dioxide according to claim 1 or 2, further comprising a step of adjusting it to 0 or less.
し、二酸化塩素水溶液を作成する工程及び前記二酸化塩
素水溶液を冷却し、固体とする工程を有することを特徴
とする二酸化塩素の加工方法。4. A method for processing chlorine dioxide, which comprises the steps of dissolving chlorine dioxide gas in acidic ionized water to prepare an aqueous chlorine dioxide solution and cooling the aqueous chlorine dioxide solution to a solid state.
一つに記載の加工方法により得られる二酸化塩素の加工
物であって、固体であることを特徴とする二酸化塩素の
加工物。5. A processed product of chlorine dioxide obtained by the processing method according to any one of claims 1 to 4, which is a solid product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10695994A JPH07315804A (en) | 1994-05-20 | 1994-05-20 | Processing of chlorine dioxide and processed product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10695994A JPH07315804A (en) | 1994-05-20 | 1994-05-20 | Processing of chlorine dioxide and processed product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07315804A true JPH07315804A (en) | 1995-12-05 |
Family
ID=14446879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10695994A Pending JPH07315804A (en) | 1994-05-20 | 1994-05-20 | Processing of chlorine dioxide and processed product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07315804A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6328909B1 (en) | 1999-02-18 | 2001-12-11 | Alcide Corporation | Frozen chlorine dioxide-containing composition and methods related thereto |
-
1994
- 1994-05-20 JP JP10695994A patent/JPH07315804A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6328909B1 (en) | 1999-02-18 | 2001-12-11 | Alcide Corporation | Frozen chlorine dioxide-containing composition and methods related thereto |
| JP2002537235A (en) * | 1999-02-18 | 2002-11-05 | アルサイド コーポレーション | Composition containing frozen chlorine dioxide and related methods |
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