【０００１】[0001]
【発明の属する技術分野】この発明は、殺菌、消毒、脱
臭、脱色、防虫、異臭防止などの目的で広範囲に利用さ
れる二酸化塩素および二酸化塩素水の製造方法およびそ
の製造装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing chlorine dioxide and chlorine dioxide water which are widely used for sterilization, disinfection, deodorization, decolorization, insect repellency, and prevention of off-flavors.
【０００２】[0002]
【従来の技術】二酸化塩素は、融点−５９℃、沸点１１
℃の常温ではガス状の物質であって、強い酸化力と殺菌
性を有し、常温常圧下では水に対して約３０００ｐｐｍ
（ｍｇ／ｌ）の溶解度を持ち、空気中ではガス濃度１０
容積％以上で爆発性を有する。パルプ漂白などの大規模
な工業用途の二酸化塩素の製造には、塩素酸塩に鉱酸単
独あるいは過酸化水素、亜硫酸ガス、メタノールなどの
還元性物質を加える方法が用いられている。一方、飲料
水の殺菌、消毒、異臭防止；工業廃水などの脱臭、脱
色；農業ハウス内の防虫；冷却塔のスライム防止；原油
井戸の賦活などの中小規模の用途での二酸化塩素の製造
にはつぎの様な方法が用いられている。特許第２７９７
０７０号公報では、清水流中に所望量の亜塩素酸塩水溶
液、次亜塩素酸水溶液および塩酸溶液を注入して、静的
混合装置（ただし、ベンチュリー管形式の混合装置を除
く）中で反応させ二酸化塩素水を得る方法が開示されて
いる。特公平３−６２６４１号（ＵＳＰ４，２４７，５
３１）には、亜塩素酸塩水溶液と酸水溶液、亜塩素酸塩
水溶液と塩素ガス、あるいは亜塩素酸塩水溶液、次亜塩
素酸塩および酸を水エジェクターの作り出す減圧下に吸
引しながら反応させ、発生した二酸化塩素を水エジェク
ター中で水吸収と希釈を行う方法が示される。これらの
方法に共通した目標は装置運転上の安全性と得られる二
酸化塩素水の品質が不純物、特に塩素を極力含まない塩
素フリーな高純度品の製造にある。2. Description of the Related Art Chlorine dioxide has a melting point of -59.degree.
It is a gaseous substance at normal temperature of ℃, has strong oxidizing power and bactericidal property, and about 3000 ppm with respect to water under normal temperature and normal pressure.
(Mg / l) with a gas concentration of 10 in air.
Explosive at volume% or more. For the production of chlorine dioxide for large-scale industrial use such as pulp bleaching, a method of adding a mineral acid alone or a reducing substance such as hydrogen peroxide, sulfur dioxide or methanol to a chlorate is used. On the other hand, the production of chlorine dioxide for small and medium-scale applications such as sterilization, disinfection, and prevention of off-flavors; deodorization and decolorization of industrial wastewater; insect repellents in agricultural houses; Such a method is used. Patent No. 2797
In the publication No. 070, a desired amount of an aqueous solution of chlorite, an aqueous solution of hypochlorous acid and a solution of hydrochloric acid are injected into a fresh water stream, and the reaction is carried out in a static mixer (excluding a Venturi tube type mixer). A method for obtaining aqueous chlorine dioxide is disclosed. Japanese Patent Publication No. 3-62641 (USP 4,247,5)
In 31), a chlorite aqueous solution and an acid aqueous solution, a chlorite aqueous solution and chlorine gas, or a chlorite aqueous solution, hypochlorite and an acid are reacted while sucking under reduced pressure created by a water ejector. A method for absorbing and diluting chlorine dioxide generated in a water ejector is shown. The common goal of these methods is to produce a chlorine-free high-purity product in which the safety of the operation of the apparatus and the quality of the obtained chlorine dioxide water do not contain impurities, especially chlorine, as much as possible.
【０００３】塩素酸塩と酸を用いる方法は、紙パルプ工
業での漂白に用いられる二酸化塩素の工業的製造法で一
般的に二酸化塩素純分として１日１トン以上の製造に用
いられている。この反応は塩素が副生し常温では反応速
度が遅いために、加温や塩素生成抑制剤などの添加が必
須である。それ故、塩素化有機物質の生成を極端に嫌う
上水道水殺菌や食品工業向けの二酸化塩素水の製造には
不適当な方法とされている。亜塩素酸塩と酸とを用いる
方法は、亜塩素酸塩原料からの二酸化塩素への理論転換
率が８０％で経済的に不利なばかりでなく、実際に６０
％の転換率を達成するためには酸を理論量の３００％過
剰で反応させなければならず、得られる二酸化塩素水は
ｐＨ０．５以下の強酸性であり、使用上に種々不利を伴
う方法である。亜塩素酸塩水溶液に塩素ガスを吹き込む
方法では、反応を正確にコントロールし易いが、反応率
を高めるには過剰の塩素で反応させる必要があり塩素酸
塩法と同類の欠点がある。しかも毒性の強い塩素ガスを
取り扱うので危険性が高い欠点がある。亜塩素酸塩、次
亜塩素酸塩および酸のそれぞれの水溶液を反応させる３
液方法は、不純物である塩素含量を低く抑えることが可
能であるとともに、次亜塩素酸塩を還元剤とするので、
使用する酸の量も少なく、従って得られる二酸化塩素水
のｐＨが弱酸性〜中性付近であるという大きな特徴があ
る。更に、常温常圧で原料の転換効率が高く経済性と安
全性を兼ね備えた方法である。しかしながら次亜塩素酸
塩は常温においても濃度減少が著しい原料であるので、
塩素含有量を低く抑えるためには次亜塩素酸塩溶液の濃
度を常に検定して適正に保たねばならない。そのために
この製造法は高価な測定装置一式と専門知識のある技術
者が煩わしい濃度調整をしなければならないのが大きな
欠点となっている。The method using chlorate and acid is an industrial production method of chlorine dioxide used for bleaching in the pulp and paper industry, and is generally used for producing 1 ton or more of chlorine dioxide as a pure content per day. . In this reaction, chlorine is by-produced and the reaction rate is slow at room temperature, so that heating and addition of a chlorine production inhibitor and the like are essential. Therefore, it is regarded as an unsuitable method for disinfecting tap water and producing chlorine dioxide water for the food industry, which extremely dislikes the production of chlorinated organic substances. The method using a chlorite and an acid is not only economically disadvantageous in that the theoretical conversion rate from a chlorite raw material to chlorine dioxide is 80%, but it is actually 60%.
% Of the acid must be reacted in excess of the theoretical amount in order to achieve a% conversion, and the chlorine dioxide water obtained is strongly acidic at a pH of 0.5 or less, and has various disadvantages in use. It is. In the method of blowing chlorine gas into the aqueous chlorite solution, it is easy to control the reaction accurately, but in order to increase the reaction rate, it is necessary to carry out the reaction with excess chlorine, and there is a disadvantage similar to the chlorate method. Moreover, there is a drawback that the danger is high because highly toxic chlorine gas is handled. Reacting respective aqueous solutions of chlorite, hypochlorite and acid 3
Since the liquid method can keep the chlorine content as an impurity low and uses hypochlorite as a reducing agent,
There is a great feature that the amount of the acid used is small, and thus the pH of the obtained chlorine dioxide water is weakly acidic to near neutral. In addition, the method has a high conversion efficiency of raw materials at normal temperature and normal pressure, and has both economy and safety. However, since hypochlorite is a raw material whose concentration decreases remarkably even at room temperature,
In order to keep the chlorine content low, the concentration of the hypochlorite solution must always be verified and maintained properly. For this reason, this manufacturing method has a major drawback that an expensive measuring device set and a technician with specialized knowledge must perform cumbersome concentration adjustment.
【０００４】二酸化塩素水中の二酸化塩素は気体として
溶存しているので、極く弱いバブリングや撹拌でも容易
に揮散し、濃度が急速に低下し易い。上記の水エジェク
ターを利用する従来法による二酸化塩素連続発生法で
は、二酸化塩素水は比較的高濃度であり、水エジェクタ
ーの乱流で製造されるので、常温常圧下での使用に際し
ては、ガスが揮散し易く収率の低下が問題であった。ま
た、これらの方法で得られた二酸化塩素水を低濃度で殺
菌や脱臭に使用すると、希釈時にもガスの揮散が生じ、
不経済であるばかりか人体にも有害であり、比較的低濃
度の二酸化塩素水の簡便な製造方法が求められていた。
また、飲料水の殺菌、消毒、異臭防止のために、高純度
の二酸化塩素、特に塩素を含まない二酸化塩素が要求さ
れている。例えば、飲料水中のトリハロメタン前駆物質
量が高い場合には、その前駆物質と塩素が反応してトリ
ハロメタンを生成する量が多くなる。また、水中の汚染
物質であるフェノールなどの有機物が塩素と反応してを
クロロフェノールなどの塩素化有機物質が生成する。そ
のため水質基準値内に抑えるためには塩素フリーの二酸
化塩素水が必要であるが、我が国では、飲料用原水中の
トリハロ前駆体含有量が殆どの浄水場では、トリハロメ
タン規制値０．１（ｍｇ／リットル）以上にならないの
で、現状では二酸化塩素水の残存塩素が問題になるレベ
ルでないと認識されている。他方、液体塩素やガス塩素
消毒に代替して地震などの際周辺に塩素ガスの影響が発
生しない簡便である次亜塩素酸ナトリウム溶液が広く使
用されるようになった現状がある。しかい最近問題とな
ったクリプトスポリジウムなどの病原性原虫などには消
毒能力が低く、より消毒能力の高い電解次亜塩素（ＨＣ
ｌＯ）や二酸化塩素、やオゾンが望ましい。このような
背景から、塩素含有量を低く抑えるために常に次亜塩素
酸塩溶液の濃度を検定して適正に保たねばならない煩わ
しい従来の二酸化塩素の製造方法を改良して簡便な製造
方法が必要となっている。また、必ずしも塩素フリーの
純度の高い二酸化塩素水が望まれているわけでもなく、
消毒力の高い若干の塩素を含む二酸化塩素をより簡便に
製造する方法、メンテナンスフリーで使用可能な二酸化
塩素製造装置が望まれている。[0004] Since chlorine dioxide in chlorine dioxide water is dissolved as a gas, it is easily volatilized even with extremely weak bubbling or stirring, and the concentration tends to decrease rapidly. In the conventional method for continuously generating chlorine dioxide using the water ejector described above, chlorine dioxide water has a relatively high concentration and is produced by turbulent flow of the water ejector. It was easy to volatilize and the yield was a problem. In addition, when chlorine dioxide water obtained by these methods is used for sterilization or deodorization at a low concentration, gas is generated even during dilution,
Not only is it uneconomical but also harmful to the human body, and there has been a demand for a simple method for producing a relatively low concentration of chlorine dioxide water.
In addition, high-purity chlorine dioxide, particularly chlorine-free chlorine dioxide, is required for sterilization, disinfection, and prevention of off-flavor of drinking water. For example, when the amount of the trihalomethane precursor in the drinking water is high, the amount of the reaction between the precursor and chlorine to produce trihalomethane increases. In addition, chlorinated organic substances such as chlorophenol are generated by reaction of organic substances such as phenol, which is a pollutant in water, with chlorine. For this reason, chlorine-free chlorine dioxide water is required to keep the water quality within the standard. However, in Japan, most of the water purification plants that contain trihalo precursors in drinking water have a trihalomethane regulation value of 0.1 (mg). Per liter) or more, it is currently recognized that residual chlorine in chlorine dioxide water is not at a problematic level. On the other hand, there is a current situation in which, instead of liquid chlorine or gas chlorination, a simple sodium hypochlorite solution in which the influence of chlorine gas does not occur in the vicinity during an earthquake or the like has been widely used. However, pathogenic protozoa such as Cryptosporidium, which has recently become a problem, have a low disinfecting ability and have a higher disinfecting ability using electrolytic hypochlorite (HC)
10), chlorine dioxide, and ozone are desirable. Against this background, a simple and convenient method for improving the conventional chlorine dioxide production method, which must always maintain the concentration of the hypochlorite solution in order to keep the chlorine content low and maintain it properly, has been developed. Is needed. In addition, chlorine-free chlorine dioxide water with high purity is not always desired,
There is a demand for a method for easily producing chlorine dioxide containing a small amount of chlorine having a high disinfecting power, and a chlorine dioxide producing apparatus which can be used without any maintenance.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、亜塩
素酸塩水溶液、次亜塩素酸塩水溶液及び酸を原料とする
３液法による従来の二酸化塩素水の製造方法における欠
点を解決することである。すなわち、塩素含有量を低く
抑えるために高価な測定装置を用いて次亜塩素酸塩溶液
の煩わしい濃度調整濃度をしなければならない欠点を除
いた二酸化塩素水の製造方法およびその製造装置を提供
することにある。また、飲料用原水の消毒剤として消毒
能力の高い若干の塩素を含有する二酸化塩素をより簡便
に製造する方法、メンテナンスフリーで使用可能な二酸
化塩素製造装置を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of the conventional method for producing aqueous chlorine dioxide by a three-liquid method using an aqueous chlorite solution, an aqueous hypochlorite solution and an acid as raw materials. That is. In other words, the present invention provides a method for producing chlorine dioxide water and a production apparatus therefor, which eliminates the disadvantage that the concentration of the hypochlorite solution must be adjusted by using an expensive measuring device in order to keep the chlorine content low. It is in. Another object of the present invention is to provide a method for more easily producing chlorine dioxide containing a small amount of chlorine having a high disinfecting ability as a disinfectant for raw water for drinking, and a chlorine dioxide producing apparatus usable without maintenance.
【０００６】[0006]
【課題を解決するための手段】本発明者は上記の目的を
達成するため鋭意研究の結果、従来の純度を高めるため
に常にの検定するような必要以上の労力をさけ、従来の
思想と反対に次亜塩素酸塩溶液濃度を化学量論上過剰に
することにより、消毒能力の高い二酸化塩素をより簡便
に製造する方法、メンテナンスフリーで使用可能な二酸
化塩素製造方法を見出し本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, have avoided the need for extraordinary labor to constantly carry out a test in order to increase the purity of the conventional method. By making the hypochlorite solution concentration stoichiometrically excessive, a method for easily producing chlorine dioxide having a high disinfecting ability, a method for producing chlorine dioxide which can be used without maintenance, and the present invention are completed. Reached.
【０００７】本発明の二酸化塩素水の製造方法は、つぎ
の（１）〜（３）項で示される。 （１） 亜塩素酸塩水溶液、次亜塩素酸塩水溶液および
酸を原料とする二酸化塩素水の製造方法において、化学
量論的に次亜塩素酸塩の過剰条件で行うことを特徴とす
る二酸化塩素水の製造方法。 （２） 亜塩素酸塩水溶液、次亜塩素酸塩水溶液および
酸水溶液をそれぞれ定量ポンプにてラインミキサーに供
給し、一方、希釈水をラインミキサーに供給して、ライ
ンミキサーにて二酸化塩素に対して１５重量％以下の塩
素を含有する二酸化塩素水を得ることからなる（１）項
記載の二酸化塩素水の製造方法。 （３） 次亜塩素酸塩を理論反応量の３０％以下の過剰
量とし、ｐＨ２〜５の領域にて反応することからなる
（１）、（２）項のいずれか１項に記載の二酸化塩素水
の製造方法。The method for producing chlorine dioxide water of the present invention is described in the following items (1) to (3). (1) A method for producing chlorine dioxide water using an aqueous solution of chlorite, an aqueous solution of hypochlorite and an acid as a raw material, characterized in that it is carried out under stoichiometric excess conditions of hypochlorite. Chlorine water production method. (2) An aqueous chlorite solution, an aqueous hypochlorite solution and an aqueous acid solution are each supplied to a line mixer by a metering pump, while dilution water is supplied to the line mixer, and chlorine dioxide is supplied to the line mixer by the line mixer. (1). The method for producing chlorine dioxide water according to (1), comprising obtaining chlorine dioxide water containing 15% by weight or less of chlorine. (3) The carbon dioxide according to any one of (1) and (2), wherein the hypochlorite is reacted in a pH range of 2 to 5 in an excess amount of 30% or less of the theoretical reaction amount. Chlorine water production method.
【０００８】本発明の二酸化塩素水の製造装置は、つぎ
の（４）〜（７）項で示される （４） 亜塩素酸塩水溶液タンク、次亜塩素酸塩水溶液
タンクおよび酸水溶液タンクからそれぞれ定量ポンプを
介して各水溶液がラインミキサーに供給され、希釈水は
流量調節計を介してラインミキサーに供給され、ライン
ミキサーにて反応と希釈が同時に行われ二酸化塩素水が
得られることからなる二酸化塩素水製造装置。 （５） 次亜塩素酸塩が亜塩素酸塩に対して化学量論的
に過剰に供給され、生成する二酸化塩素に対して１５重
量％以下の塩素を含有してなる二酸化塩素水が得られる
ことからなる（４）項記載の二酸化塩素水製造装置 （６） 次亜塩素酸塩を理論反応量の３０％以下の過剰
量とし、ｐＨ２〜５の領域にて反応することからなる
（４）、（５）項のいずれか１項に記載の二酸化塩素水
の製造装置。 （７） ラインミキサーに供給する希釈水または各原料
液の流速が、管径３〜１５ｍｍでは０．５ｍ／ｓｅｃ．
未満；管径１５〜３０ｍｍでは０．５〜１ｍ／ｓｅ
ｃ．；管径３０〜１００ｍｍでは１〜２ｍ／ｓｅｃ．；
管径１００ｍｍ以上では２ｍ／ｓｅｃ以上であり、ニー
ドル弁と流量計との組み合わせもしくは定流量弁にて希
釈水量を設定し生成する二酸化塩素水中の二酸化塩素濃
度を１００〜３０００（ｍｇ／ｌ）にすることからなる
（４）〜（６）項のいずれか１項に記載の二酸化塩素水
の製造装置。[0008] The apparatus for producing chlorine dioxide water of the present invention comprises the following (4) to (7): (4) a chlorite aqueous solution tank, a hypochlorite aqueous solution tank, and an acid aqueous solution tank. Each aqueous solution is supplied to the line mixer via the metering pump, and the dilution water is supplied to the line mixer via the flow controller, and the reaction and the dilution are simultaneously performed in the line mixer to obtain chlorine dioxide. Chlorine water production equipment. (5) Hypochlorite is supplied in stoichiometric excess with respect to chlorite, and chlorine dioxide water containing 15% by weight or less of chlorine with respect to the generated chlorine dioxide is obtained. (6) The apparatus for producing chlorine dioxide water according to (4), wherein hypochlorite is used in an excess amount of 30% or less of the theoretical reaction amount, and is reacted in a pH range of 2 to 5 (4). The apparatus for producing chlorine dioxide water according to any one of items (5) and (5). (7) The flow rate of the dilution water or each raw material liquid supplied to the line mixer is 0.5 m / sec. For a pipe diameter of 3 to 15 mm.
Less than; 0.5 to 1 m / sec for a pipe diameter of 15 to 30 mm
c. 1-2 m / sec. For a pipe diameter of 30 to 100 mm. ;
When the pipe diameter is 100 mm or more, it is 2 m / sec or more, and the chlorine dioxide concentration in the chlorine dioxide water generated by setting the dilution water amount by a combination of a needle valve and a flow meter or a constant flow valve to 100 to 3000 (mg / l). The apparatus for producing chlorine dioxide water according to any one of the above items (4) to (6).
【０００９】本願発明における化学量論的に次亜塩素酸
塩の過剰条件とは、後述の反応式（１）により算出され
る次亜塩素酸塩の理論使用量より過剰に使用した場合を
いう。また、次亜塩素酸塩を理論反応量の３０％以下の
過剰量の意味は、後述の反応式（１）により算出される
亜塩素酸塩の理論使用量を１００％とした場合１３０％
以下の意味である（後述、実施例参照）。The stoichiometric excess condition of hypochlorite in the present invention means that hypochlorite is used in excess of the theoretical amount of hypochlorite calculated by the following reaction formula (1). . Further, the meaning of an excess amount of hypochlorite of 30% or less of the theoretical reaction amount means that the hypochlorite amount is 130% when the theoretical usage amount of chlorite calculated by the following reaction formula (1) is 100%.
This has the following meaning (see Examples below).
【００１０】[0010]
【発明の実施の形態】酸性や酸化性溶液の定量送液方法
として比較的安価である定量ポンプ方式を選定し、特に
その中でダイヤフラムポンプが好適であった。ダイヤフ
ラムポンプの最高吐出圧が、０．８〜１．０ＭＰａ（メ
ガパスカル）のものを選定使用すれば最高吐出圧より
０．２ＭＰａ低い背圧下でも運転できる優位性がある。
定量ポンプの他の種類には、これらの薬液を送液が可能
なものとして、チューブをしごいて送るタイプのローラ
ポンプやチューブポンプ、接液部を耐薬品性の樹脂でコ
ートできるマグネットポンプも使用可能である。ライン
ミキサーは、パイプの中に抵抗体を挿入することにより
パイプ中で液体の混合が容易にできるものであり、反応
による二酸化塩素の生成とその希釈水での希釈を行う装
置であり、市販のラインミキサーを使用できるが、”ス
タティクミキサー”（ノリタケカンパニー製）が好適で
ある。希釈水は、ポンプなどで圧送される水道水などを
使用する。そのためにニードル弁と流量計の組み合わ
せ、あるいは定流量弁にて一定量供給されるシステムと
した。二酸化塩素生成方法としては、理論収率が１００
％である３液法、すなわち亜塩素酸塩水溶液、次亜塩素
酸塩水溶液および酸水溶液を混合反応させる二酸化塩素
水の製造方法を採用した。そして、この原料３水溶液の
混合比率はｐＨ２〜５の酸性領域になる酸量と理論反応
量の３０％以下の過剰量である次亜塩素酸塩溶液を用い
ることを特徴とする。より具体的には、例えば２０リッ
トル入りの次亜塩素酸塩水溶液１本のタンクを使い切る
日数が３ヶ月以内であれば、スタート時の次亜塩素酸塩
濃度を１３０％以下｛反応式による理論反応量を１００
％として（すなわち３０％以下の過剰量）｝とすれば、
反応条件すなわちラインミキサーの条件が５〜３５℃に
おいて、二酸化塩素水は高収率で生成する。そして、生
成した二酸化塩素水は二酸化塩素に対して１５％以下、
通常５〜１０％の塩素を含む塩素過剰のものであり、亜
塩素酸イオンを含んでいない。反応率、安全性の面か
ら、ラインミキサーのより好ましい条件は１５〜３５℃
である。BEST MODE FOR CARRYING OUT THE INVENTION A relatively inexpensive metering pump method was selected as a method for quantitatively sending an acidic or oxidizing solution, and a diaphragm pump was particularly preferable. If a diaphragm pump having a maximum discharge pressure of 0.8 to 1.0 MPa (megapascal) is selected and used, there is an advantage that the diaphragm pump can be operated even under a back pressure 0.2 MPa lower than the maximum discharge pressure.
Other types of metering pumps include those that can send these chemicals, such as roller pumps and tube pumps that squeeze the tube and magnet pumps that can coat the wetted parts with chemical resistant resin. Can be used. A line mixer is a device that can easily mix liquids in a pipe by inserting a resistor into the pipe, and is a device for producing chlorine dioxide by a reaction and diluting the same with dilution water. A line mixer can be used, but "Static Mixer" (manufactured by Noritake Company) is preferable. As the dilution water, tap water or the like pumped by a pump or the like is used. For this reason, a system in which a fixed amount is supplied by a combination of a needle valve and a flow meter or a constant flow valve is adopted. As a method for producing chlorine dioxide, the theoretical yield is 100
%, That is, a method of producing aqueous chlorine dioxide by mixing and reacting an aqueous chlorite solution, an aqueous hypochlorite solution, and an aqueous acid solution. The mixing ratio of the aqueous solution of the raw material 3 is characterized by using a hypochlorite solution which is an excess amount of 30% or less of the amount of acid in the acidic region of pH 2 to 5 and the theoretical reaction amount. More specifically, for example, if the number of days for using one tank of 20 liters of hypochlorite aqueous solution is less than 3 months, the hypochlorite concentration at the start is 130% or less. 100 reaction
% (Ie, an excess of 30% or less)},
When the reaction conditions, that is, the line mixer conditions are 5 to 35 ° C., chlorine dioxide water is produced in high yield. And the generated chlorine dioxide water is 15% or less based on chlorine dioxide,
It is usually in excess of chlorine containing 5 to 10% chlorine and does not contain chlorite ions. From the viewpoint of reaction rate and safety, more preferable conditions of the line mixer are 15 to 35 ° C.
It is.
【００１１】本発明で用いる亜塩素酸塩とは、亜塩素酸
塩カリウム、亜塩素酸塩ナトリウム、亜塩素酸塩カルシ
ウムなどの亜塩素酸アルカリ金属塩あるいは亜塩素酸ア
ルカリ土類金属塩であるが、入手が容易で割安な点から
亜塩素酸塩ナトリウムが好ましく用いられる。亜塩素酸
塩水溶液中のこれら亜塩素酸塩の濃度は、０．１〜２５
重量％が好ましい。亜塩素酸塩の濃度が０．１重量％以
下では二酸化塩素生成速度が遅く、収率も低くなるため
好ましくない。また、２５重量％以上の亜塩素酸塩水溶
液は危険物第６類酸化性化合物に該当するので、原料の
貯蔵、取り扱いに特別な配慮が必要となり好ましくな
い。The chlorite used in the present invention is an alkali metal chlorite or an alkaline earth metal chlorite such as potassium chlorite, sodium chlorite and calcium chlorite. However, sodium chlorite is preferably used because it is easily available and inexpensive. The concentration of these chlorites in the aqueous chlorite solution is 0.1-25.
% By weight is preferred. If the concentration of chlorite is 0.1% by weight or less, the rate of chlorine dioxide generation is low and the yield is low, which is not preferable. Further, an aqueous chlorite solution of 25% by weight or more corresponds to the oxidizable compound of the sixth category, which is not preferable because special consideration is required for storage and handling of the raw material.
【００１２】本発明で用いる次亜塩素酸塩とは、次亜塩
素酸塩カリウム、次亜塩素酸塩ナトリウム、次亜塩素酸
塩カルシウムなどの次亜塩素酸アルカリ金属塩もしくは
次亜塩素酸アルカリ土類金属塩であるが、入手が容易で
品質が安定し、取り扱いが容易な点から次亜塩素酸塩ナ
トリウムが好ましい。次亜塩素酸塩水溶液中のこれら次
亜塩素酸塩の濃度は、経済性から０．１〜１２．５重量
％が好ましい。次亜塩素酸塩の濃度を１２．５重量％以
上にすると濃度低下が早くなるので好ましくない。ま
た、５％以下にすると濃度低下がこれ以上の濃度のもの
に比べて著しく小さくなるので特に好ましい。The hypochlorite used in the present invention is an alkali metal hypochlorite such as potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, or an alkali hypochlorite. Although it is an earth metal salt, sodium hypochlorite is preferred because it is easily available, has stable quality, and is easy to handle. The concentration of these hypochlorites in the aqueous hypochlorite solution is preferably 0.1 to 12.5% by weight from the viewpoint of economy. If the concentration of hypochlorite is 12.5% by weight or more, it is not preferable because the concentration decreases quickly. Further, it is particularly preferable that the concentration be 5% or less, since the decrease in concentration is significantly smaller than that at a concentration higher than 5%.
【００１３】本発明で用いる酸水溶液としては塩酸、硫
酸、リン酸などの鉱酸やクエン酸、酒石酸などの有機酸
の水溶液があるが、反応性と生成した二酸化塩素の安定
性の点から塩酸水溶液が好ましい。酸の濃度は０．１〜
３６重量％が好ましい。The acid aqueous solution used in the present invention includes aqueous solutions of mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and aqueous solutions of organic acids such as citric acid and tartaric acid. Aqueous solutions are preferred. Acid concentration is 0.1 ~
36% by weight is preferred.
【００１４】以下、添付した図面に基づいて本発明を説
明する。図１は本発明の二酸化塩素水製造装置の概念図
である。図において、０１は亜塩素酸ナトリウム用定量
ポンプ、０２は次亜塩素酸ナトリウム用定量ポンプ、０
３は酸用定量ポンプであり、それぞれダイヤフラム式定
量ポンプである。フート弁と注入弁材質はポリ塩化ビニ
ルハウジング、チャッキボールは高純度セラミックス、
弁座はフッ素ゴム（バイトン）、Ｏリングはフッ素ゴ
ム、ダイヤフラムはポリテトラフルオロエチレン（ＰＴ
ＦＥ）からなる。ストローク数およびストローク長を調
整することにより所定の吐出量に設定する。次亜塩素酸
塩溶液には自動エアー抜き機能付きを選定した。０４は
亜塩素酸塩水溶液タンク、０５は次亜塩素酸塩水溶液タ
ンク、０６は酸水溶液タンクでこれらのタンク材質はポ
リプロピレン、ポリエチレン、ＦＲＰの樹脂製タンクが
好適に使用できる。容積は二酸化塩素発生量〔Ｋｇ（Ｃ
ｌＯ２）／Ｄ〕と用いる原料液濃度の組み合わせにより
異なる。Hereinafter, the present invention will be described with reference to the accompanying drawings. FIG. 1 is a conceptual diagram of a chlorine dioxide water producing apparatus of the present invention. In the figure, 01 is a metering pump for sodium chlorite, 02 is a metering pump for sodium hypochlorite, 0
Reference numeral 3 denotes an acid metering pump, each of which is a diaphragm type metering pump. The foot valve and injection valve are made of polyvinyl chloride housing, the check ball is made of high-purity ceramic,
The valve seat is made of fluoro rubber (Viton), the O-ring is made of fluoro rubber, and the diaphragm is polytetrafluoroethylene (PT
FE). A predetermined discharge amount is set by adjusting the number of strokes and the stroke length. The hypochlorite solution was selected with an automatic air release function. 04 is a chlorite aqueous solution tank, 05 is a hypochlorite aqueous solution tank, 06 is an acid aqueous solution tank, and these tank materials can be suitably used resin tanks of polypropylene, polyethylene and FRP. The volume is the amount of chlorine dioxide generated [Kg (C
1O2) / D] and the concentration of the raw material liquid used.
【００１５】二酸化塩素発生量が０．１〜５０〔Ｋｇ
（ＣｌＯ2）／Ｄ〕の場合には、好ましい原料液濃度の
組み合わせは亜塩素酸ナトリウム溶液９．３重量％、次
亜塩素酸ナトリウム溶液４．５重量％、塩酸溶液４．４
重量％である。この好ましい濃度の組み合わせの理由
は、次亜塩素酸ナトリウム溶液の濃度が５重量％以下の
場合は塩素ガス発生による次亜塩素酸ナトリウムの濃度
低下が少ないので、次亜塩素酸ナトリウムの濃度は濃度
低下を抑える意味で４，５重量％とし、これを基準にし
て他の２液の使用量をほぼ同じに設定したことによる。
二酸化塩素発生量が５１〜１，０００〔Ｋｇ（Ｃｌ
Ｏ2）／Ｄ〕の場合には、好ましい原料液濃度の組み合
わせは亜塩素酸ナトリウム溶液２５重量％、次亜塩素酸
ナトリウム溶液１２．０重量％、酸溶液１３重量％であ
る。この好ましい原料液濃度の組み合わせは、市販品の
濃度のものをそのまま極力使用したことと３６重量％の
濃塩酸のハンドリング時の危険を小さくし、他の２液使
用量とのバランスを考慮したためである。通常、希釈水
口１２からの水は通常ポンプなどで圧送される水道水な
どが使用されるので、流量調節弁０７にはＳＵＳ製ニー
ドル弁が好適であり、流量計０８はアクリル樹脂製やＳ
ＵＳ製を好適に用いられる。希釈水の流速が２リットル
／minより大きい場合にはニードル弁／流量計の組み合
わせに換えてＢＳまたはＳＵＳ製の定流量弁を用いるこ
ともできる。逆止弁０９はポリ塩化ビニル製やテフロン
製のものが好適に使用される。ラインミキサー１０
は、”スタティクミキサー”（ノリタケカンパニー製）
が好適である。二酸化塩素水レシーバータンク１１は、
ポリ塩化ビニル製もしくはＦＲＰ製ではんのタンクレベ
ル計１４を有する構造が望ましい。ガス洗浄瓶１３は１
０％亜硫酸ナトリウム水溶液入りの樹脂製もしくはガラ
ス製であり、タンク内空気押し出しに伴い発生する二酸
化塩素ガスをトラップして無害化するものである。ちな
みに反応装置の運転を終了した場合にはガス洗浄瓶１３
を外して活性炭カラムに換えることが望ましい、特に二
酸化塩素水レシバータンク１１から二酸化塩素水を取り
出す際には、ガス洗浄瓶１３は空気取り入れ口兼微量の
発生ガスの逃げ口となるので活性炭カラムにする必要が
ある。The amount of chlorine dioxide generated is 0.1 to 50 [Kg
In the case of (ClO2 ) / D], the preferred combination of the raw material liquid concentrations is 9.3% by weight of sodium chlorite solution, 4.5% by weight of sodium hypochlorite solution, and 4.4% by weight of hydrochloric acid solution.
% By weight. The reason for this preferred combination of concentrations is that when the concentration of the sodium hypochlorite solution is 5% by weight or less, the concentration of sodium hypochlorite is small because the concentration of sodium hypochlorite decreases little due to the generation of chlorine gas. This is because the amount was set at 4.5% by weight in order to suppress the decrease, and the amounts of the other two liquids were set to be substantially the same based on this.
The amount of chlorine dioxide generated is 51 to 1,000 [Kg (Cl
O2 ) / D], a preferred combination of the raw material liquid concentrations is 25% by weight of sodium chlorite solution, 12.0% by weight of sodium hypochlorite solution, and 13% by weight of acid solution. This preferred combination of the raw material liquid concentrations is because the commercially available product concentration was used as it was, the risk of handling 36% by weight concentrated hydrochloric acid was reduced, and the balance with the other two liquid amounts was considered. is there. Usually, tap water or the like pumped by a pump or the like is used as the water from the dilution water port 12, so that a SUS needle valve is suitable for the flow rate control valve 07, and the flow meter 08 is made of acrylic resin or S
US-made is preferably used. When the flow rate of the dilution water is larger than 2 liter / min, a constant flow valve made of BS or SUS can be used instead of the combination of the needle valve / flow meter. The check valve 09 is preferably made of polyvinyl chloride or Teflon. Line mixer 10
Is “Static Mixer” (Noritake Company)
Is preferred. Chlorine dioxide water receiver tank 11,
A structure having a tank level gauge 14 made of polyvinyl chloride or FRP is desirable. Gas cleaning bottle 13 is 1
It is made of resin or glass containing a 0% sodium sulfite aqueous solution, and traps and renders harmless chlorine dioxide gas generated when air is pushed out of the tank. By the way, when the operation of the reactor is finished,
In particular, when taking out chlorine dioxide water from the chlorine dioxide water receiver tank 11, the gas washing bottle 13 serves as an air intake and a vent for a small amount of generated gas. There is a need to.
【００１６】本発明の二酸化塩素水製造装置は、一定流
量の希釈水中に所望の二酸化塩素の濃度に応じて原料液
を供給する構造であるので、希釈水の供給を停止した場
合には自動的に原料液供給が停止される機構を組み込ん
でおくことが望ましい。また、３基の原料液タンクのど
れか１基でも空になった場合には、すべての原料液供給
が停止する構造としておくことが望ましい。この機構を
有する部品としては、テフロン製の電磁弁と管内の流れ
を検出し得る検出器との組み合わせがよい。The chlorine dioxide water producing apparatus of the present invention has a structure in which a raw material liquid is supplied to a constant flow rate of dilution water in accordance with a desired concentration of chlorine dioxide. It is desirable to incorporate a mechanism for stopping the supply of the raw material liquid. In addition, it is preferable that the supply of all the raw material liquids is stopped when any one of the three raw material liquid tanks becomes empty. As a component having this mechanism, a combination of an electromagnetic valve made of Teflon and a detector capable of detecting a flow in a pipe is preferable.
【００１７】[0017]
【実施例】以下、参考例と実施例により本発明を更に具
体的に説明する。なお、二酸化塩素水の濃度測定はｐＨ
＝７でのチオ硫酸ナトリウム標準液を用いた酸化還元滴
定により、不純物の塩素濃度測定はアイーター法(E.Mar
co Aieta,P.V.Roberts,M.Hernanadez,Journal AWWA,Jan
uary 1984,P64-70)に準拠したｐＨ＝７とｐＨ＝２のそ
れぞれ２点でチオ硫酸ナトリウム標準液を用いた酸化還
元滴定により求めた。反応収率および純度つぎの式によ
り算出した。 反応収率(%)＝〔ＣｌＯ2測定値(mg/l)／ＣｌＯ2理論値
(mg/l)〕×１００ 純度(%)＝〔ＣｌＯ2測定値(mg/l)／ＣｌＯ2(mg/l)＋Ｃ
ｌ2(mg/l)＋ＣｌＯ2-(mg/l)〕×１００ なお、ＣｌＯ2理論値は次式（１）により、主原料Ｎａ
ＣｌＯ2を基準に計算した。 ２ＮａＣｌＯ2＋ＮａＣｌＯ＋２ＨＣｌ＝２ＣｌＯ2＋３ＮａＣｌ＋Ｈ2Ｏ ．．．．（１）EXAMPLES The present invention will be described more specifically below with reference examples and examples. The concentration measurement of chlorine dioxide water is pH
The redox titration using a standard solution of sodium thiosulfate at pH = 7 determines the chlorine concentration of impurities by the Eyter method (E. Mar.
co Aieta, PVRoberts, M.Hernanadez, Journal AWWA, Jan
uary 1984, P64-70) at two points, pH = 7 and pH = 2, respectively, by redox titration using a sodium thiosulfate standard solution. Reaction yield and purity were calculated by the following equations. Reaction yield (%) = [measured value of ClO2 (mg / l) / theoretical value of ClO2
(mg / l)] × 100 Purity (%) = [Measured value of ClO2 (mg / l) / ClO2 (mg / l) + C
l2 (mg / l) + ClO2− (mg / l)] × 100 Note that the theoretical value of ClO2 is calculated by the following formula (1).
Calculated based on ClO2 . 2NaClO2 + NaClO + 2HCl = 2ClO2 + 3NaCl + H2 O. . . . (1)
【００１８】（参考例） 濃度と保存温度の違いによる次亜塩素酸ナトリウム溶液
の安定性試験 遮光状態にて１２．２重量％と５．００重量％の次亜塩
素酸ナトリウム溶液をエアーオーブン加温（３０℃、３
５℃）あるいは循環恒温水槽（１５℃）中に静置して１
日〜数日おきに溶液をサンプリングして濃度測定した。
濃度はヨードメトリーによる酸化還元滴定法にて求め
た。得られた測定濃度値をプロットしたグラフを作成し
て、その濃度減少の傾きを求めた。参考例の式中、Ｙは
χ日での次亜塩素酸ナトリウム溶液濃度、χは溶液遮光
状態での静置日数を示す。(Reference Example) Stability test of sodium hypochlorite solution depending on difference in concentration and storage temperature In a light-shielded state, 12.2% by weight and 5.00% by weight of sodium hypochlorite solution were heated in an air oven. Temperature (30 ° C, 3
5 ℃) or circulating water bath (15 ℃)
The solution was sampled every day to several days to measure the concentration.
The concentration was determined by a redox titration method using iodometry. A graph was prepared by plotting the measured concentration values obtained, and the slope of the concentration decrease was determined. In the formula of the reference example, Y represents the concentration of the sodium hypochlorite solution in χ days, and χ represents the number of days of standing in the light-shielded state of the solution.
【００１９】参考例１． 市販次亜塩素酸ナトリウム水溶液（１２．２重量％）の
濃度減少、（０〜７日間での１５℃と３５℃の対比）； ３５℃ Ｙ＝−０．１９６χ＋１２．２ すなわち７日
間で約１．４％減少 １５℃ Ｙ＝−０．０３６χ＋１２．２ すなわち７日
間で約０．２５％減少Reference Example 1 Concentration reduction of commercially available aqueous sodium hypochlorite solution (12.2% by weight), (comparison between 15 ° C. and 35 ° C. in 0 to 7 days); 35 ° C. Y = −0.196 ° + 12.2, ie, about 1 in 7 days 0.4% decrease 15 ℃ Y = -0.036χ + 12.2 That is, about 0.25% decrease in 7 days
【００２０】参考例２． ５．００重量％に希釈された次亜塩素酸ナトリウム水溶
液の濃度減少、（０〜６０日間（３５℃）、０〜１５０
日間（１５℃）での対比）； ３５℃ Ｙ＝−０．０１１３χ＋５．００ すなわち７
日間で約０．０８％減少 １５℃ Ｙ＝−０．００２６χ＋５．００ すなわち７
日間で約０．０２％減少 市販濃度（１２．２重量％）および希釈濃度（５．００
重量％）の次亜塩素酸ナトリウム水溶液がそれぞれ最初
の濃度から３０％あるいは１５％減少する日数は、使用
環境の最高温度に薬剤を静置した場合に、市販品ではそ
れぞれ１８日目と９日目、希釈品では約１１９日目と６
０日目となる。 本発明の条件を満たし、塩素３０％過
剰での運転にて、市販品の次亜塩素酸ナトリウムを用い
る場合には、最悪の条件で二週間ごとに原料水溶液を入
れ替える必要がある。経済性や作業性を考慮すれば地下
タンク貯蔵など温度変化の少なくより低温な貯蔵場所か
らの供給が望ましい。１５℃静置では約４倍強、１０℃
以下では実に９倍以上長持ちすることが一般に知られて
いる。他方、５％以下に希釈した次亜塩素酸ナトリウム
溶液を本発明の条件にて使用する限りにおいて、約３ヶ
月強と十分に実用範囲にある。二酸化塩素発生の原料コ
ストの大半は亜塩素酸ナトリウム溶液であり、次亜塩素
酸ナトリウムのコストは亜塩素酸ナトリウムの数十分の
一であり、３０％増量のコスト影響は殆どないに等し
い。また、二酸化塩素中の塩素共存は原虫殺虫には有益
であるとの報告もある。(Environ.Sci.Technol.1997,3
1.,1992-1994)Reference Example 2 A decrease in the concentration of the aqueous sodium hypochlorite solution diluted to 5.00% by weight (0 to 60 days (35 ° C.), 0 to 150
Days (15 ° C.); 35 ° C. Y = −0.0113 ° + 5.00, ie, 7
About 0.08% reduction per day 15 ° C Y = -0.0026χ + 5.00 That is, 7
About 0.02% reduction per day Commercial concentration (12.2% by weight) and dilution concentration (5.00
(% By weight) of the sodium hypochlorite aqueous solution is reduced by 30% or 15% from the initial concentration, respectively, when the drug is allowed to stand at the maximum temperature of the use environment, and the commercially available product is the 18th and 9th days, respectively. Eyes, about 119 days and 6 for diluted products
Day 0. In the case where a commercial product of sodium hypochlorite is used in the operation satisfying the conditions of the present invention with an excess of 30% of chlorine, it is necessary to replace the raw material aqueous solution every two weeks under the worst conditions. In consideration of economy and workability, it is desirable to supply from a storage place with a lower temperature change and a lower temperature, such as an underground tank storage. Approximately 4 times stronger at 15 ° C standing, 10 ° C
In the following, it is generally known that the battery lasts 9 times or more. On the other hand, as long as a sodium hypochlorite solution diluted to 5% or less is used under the conditions of the present invention, it is a practically usable range of about 3 months or more. Most of the raw material cost of chlorine dioxide generation is sodium chlorite solution, the cost of sodium hypochlorite is several tenths of sodium chlorite, and the cost increase of 30% is almost negligible. It has also been reported that the coexistence of chlorine in chlorine dioxide is beneficial for protozoan insects. (Environ.Sci.Technol. 1997,3
1., 1992-1994)
【００２１】実施例１〜６ （反応装置）二酸化塩素製造に用いた反応装置は基本的
に概念図（図１）に準じて製作されたものを使用した。
すなわち、亜塩素酸塩水溶液タンク０４、次亜塩素酸塩
水溶液タンク０５および酸水溶液タンク０６は、それぞ
れポリエチレン製の角型容積２０リットルで繰り返し使
用が可能なものである。図に矢印で示した配管は硬質ポ
リ塩化ビニル製管（以下、硬質ＰＶＣ製管という）であ
る。前記各タンク０４、０５および０６と逆止弁０９と
の間は基本的に硬質ＰＶＣ製管１３Ａ（内径１３ｍｍ、
外径１５ｍｍ、）を用い。硬質ポリ塩化ビニル製逆止弁
０９の出口とラインミキサー１０の下部との接続は内径
６．５ｍｍの硬質ＰＶＣ製管を使用した。逆止弁０９に
は、テフロン系Ｏーリングが用られた。ラインミキサー
１０は硬質塩化ビニル製スタティクミキサー（ノリタケ
カンパニー製１／２−Ｎ５０−１７１１型）であり、１
／２インチ径×長さ１９０ｍｍ、６エレメントである。
希釈水口１２から注入される希釈水（清浄な水道水な
ど）は、ニードル弁付流量計０８｛流体工業製ＭＦ−Ｎ
型（ＳＵＳ製）｝で調節され、この希釈水の注入系統の
配管は１３Ａ硬質ＰＶＣ製管を用いた。原料タンクの０
４、０５および０６からの原料液の送出には、それぞれ
ダイヤフロムポンプ０１，０２および０３を用いた。亜
塩素酸ナトリウム溶液の送液ポンプ０１と塩酸溶液の送
液ポンプ０３はプロミネント社製ガンマーＧ／５ｂ１０
０６型ポンプ（最大吐出圧１ＭＰａ、平均吐出圧時吐出
量１１８ｍｌ／ｍｉｎ．）を用いた。また、次亜塩素酸
ナトリウム溶液の送液ポンプ０２には自動ガス抜き機構
を備えた同社製ガンマーＧ／５ｃｂ１３１０ポンプ（最
大吐出圧１．３ＭＰａ、平均吐出圧時吐出量１８０ｍｌ
／ｍｉｎ．）を用いた。いずれも表１の供給量になるよ
うにストローク数と幅で調整した。なお、希釈水量は流
体工業社ＳＵＳ３０４製定流量弁ＨＶＴ−3/4Ｂ（２０
Ａ）型を０７、０８流量調節弁と流量計に代替して用い
た。二酸化塩素水レシバータンク１１は容積１００リッ
トルの強化硬質塩化ビニル製であり、タンクレベル計１
４として透明硬質ＰＶＣ製管を用いた。Examples 1 to 6 (Reactor) The reactor used for the production of chlorine dioxide was basically manufactured according to the conceptual diagram (FIG. 1).
That is, the aqueous chlorite tank 04, the aqueous hypochlorite tank 05, and the aqueous acid tank 06 are each made of polyethylene and have a square volume of 20 liters and can be used repeatedly. The pipe indicated by an arrow in the figure is a hard polyvinyl chloride pipe (hereinafter, referred to as a hard PVC pipe). The space between the tanks 04, 05 and 06 and the check valve 09 is basically a rigid PVC pipe 13A (inner diameter 13 mm,
Outer diameter 15 mm). The connection between the outlet of the check valve 09 made of hard polyvinyl chloride and the lower part of the line mixer 10 used a hard PVC pipe having an inner diameter of 6.5 mm. For the check valve 09, a Teflon-based O-ring was used. The line mixer 10 is a hard vinyl chloride static mixer (1 / 2-N50-1711 type manufactured by Noritake Company).
/ 2 inch diameter × length 190 mm, 6 elements.
The dilution water (clean tap water or the like) injected from the dilution water port 12 is supplied to a flow meter with a needle valve 08 (MF-N manufactured by Fluid Industries).
The dilution system was adjusted by a mold (made of SUS)｝, and a 13A rigid PVC pipe was used as a pipe for the injection system of the dilution water. Raw material tank 0
Diaphragm pumps 01, 02, and 03 were used to feed the raw material liquids from 4, 05, and 06, respectively. The sodium chlorite solution feed pump 01 and the hydrochloric acid solution feed pump 03 were manufactured by Prominent Inc. Gamma G / 5b10.
A 06-type pump (maximum discharge pressure 1 MPa, discharge amount at average discharge pressure 118 ml / min.) Was used. The gamma G / 5cb1310 pump (with a maximum discharge pressure of 1.3 MPa and an average discharge pressure of 180 ml) equipped with an automatic degassing mechanism is provided as the sodium hypochlorite solution feed pump 02 with an automatic degassing mechanism.
/ Min. ) Was used. In each case, the number of strokes and the width were adjusted so that the supply amount was as shown in Table 1. In addition, the amount of dilution water is constant flow valve HVT-3 / 4B (20
A) Type 07 and 08 were used in place of flow control valves and flow meters. The chlorine dioxide water receiver tank 11 is made of reinforced hard vinyl chloride having a volume of 100 liters, and has a tank level meter 1
As No. 4, a transparent hard PVC pipe was used.
【００２２】次亜塩素酸ナトリウムの供給量が１００〜
１３０％｛前記（１）式から算出され理論量を１００％
として｝の場合の二酸化塩素水の製造：亜塩素酸塩とし
て亜塩素酸ナトリウム、次亜塩素酸塩として次亜塩素酸
ナトリウム、酸として塩酸を選び下記の濃度の原料液を
調製して使用した。 亜塩素酸ナトリウム水溶液（９．３重量％） １００ｇ／ｌ 次亜塩素酸ナトリウム水溶液（３．８重量％） ４１．５ｇ／ｌ 塩酸水溶液 （４．４重量％） ４４．６ｇ／ｌThe supply amount of sodium hypochlorite is 100 to
130% ｛100% of the theoretical amount calculated from the above formula (1)
Production of chlorine dioxide water in case of ①: Sodium chlorite as chlorite, sodium hypochlorite as hypochlorite, and hydrochloric acid as acid were prepared and used as a raw material solution having the following concentrations . Aqueous sodium chlorite solution (9.3% by weight) 100 g / l Aqueous sodium hypochlorite solution (3.8% by weight) 41.5 g / l Aqueous hydrochloric acid solution (4.4% by weight) 44.6 g / l
【００２３】表１に示した希釈水（水道水、残留塩素２
ｐｐｍ）の流量と各原料液の供給流量とにより二酸化塩
素水を製造した。次亜塩素酸ナトリウム（ＮａＣｌＯ）
水溶液供給量欄の括弧内の数字は、前記（１）式を基準
にして算出される亜塩素酸ナトリウム（ＮａＣｌＯ2）
の理論量を１００％として示した。表１に示すように、
生成した二酸化塩素水はすべて収率９０％以上で亜塩素
酸イオンを含まず塩素を含む純度８５％以上の品質であ
った。ｐＨも弱酸性〜酸性であった。実施例６の次亜塩
素酸ナトリウム３０％過剰条件（ＮａＣｌＯ添加量１３
０％）の場合、液温度３５℃以下の環境下で運転すれ
ば、約３ヶ月間次亜塩素酸ナトリウム濃度減少に配慮す
る必要がない。このように、本発明の製造法方法と装置
により、メンテナンスフリーな二酸化塩素水製造が可能
となった。表１の条件によれば、１，０００ｐｐｍの二
酸化塩素水を約４４０リットル／ｈｒ（ＣｌＯ2４４０
ｇ／ｈｒ）製造できるので、例えば飲料水消毒におい
て、水道原水に対する二酸化塩素の添加量を１ｐｐｍで
処理すれば、水道原水４４０ｍ３／ｈｒの消毒ができ
る。なお、実施例１は、次亜塩素酸ナトリウム濃度を、
反応式（１）による理論量（１００％）にしたものであ
る。The dilution water shown in Table 1 (tap water, residual chlorine 2
ppm) and the supply flow rate of each raw material liquid to produce chlorine dioxide water. Sodium hypochlorite (NaClO)
The number in parentheses in the aqueous solution supply amount column is sodium chlorite (NaClO2 ) calculated based on the above formula (1).
Is shown as 100%. As shown in Table 1,
All the produced chlorine dioxide water had a yield of 90% or more and a quality not containing chlorite ions but containing chlorine of 85% or more. The pH was also slightly acidic to acidic. 30% excess condition of sodium hypochlorite of Example 6 (NaClO added amount 13
0%), there is no need to consider the decrease in the sodium hypochlorite concentration for about three months if operated in an environment at a liquid temperature of 35 ° C. or less. As described above, the production method and apparatus according to the present invention enabled maintenance-free production of chlorine dioxide water. According to the conditions in Table 1, 1,000 ppm of chlorine dioxide water is supplied at about 440 liters / hr (ClO2 440).
g / hr). For example, in drinking water disinfection, if the amount of chlorine dioxide added to tap water is treated at 1 ppm, 440 m 3 / hr of tap water can be disinfected. In Example 1, the sodium hypochlorite concentration was
It is a theoretical amount (100%) according to the reaction formula (1).
【００２４】実施例７〜１２： (反応措置)実施例１〜６と同様の製造装置を使用した。
ただし、長時間運転するために、亜塩素酸塩水溶液タン
ク０４、次亜塩素酸塩水溶液タンク０５および酸水溶液
タンク０６を、それぞれ耐圧１ＭＰａの容積５００リッ
トルガラス繊維強化プラスチック（ＦＲＰ）製とした。
また、亜塩素酸ナトリウム溶液の送液ポンプ０１はプロ
ミネント社製ガンマーＧ／４ｂ０８０６型（最大吐出圧
０．８ＭＰａ、平均吐出圧時吐出量９３ｍｌ／ｍｉ
ｎ．）、次亜塩素酸ナトリウム溶液の送液ポンプ０２は
自動ガス抜き機構を備えた同社製ガンマーＧ／４ｃｂ１
２０３（最大吐出圧１．２ＭＰａ、平均吐出圧時吐出量
４８ｍｌ／ｍｉｎ．）、酸溶液の送液ポンプ０３はプロ
ミネント社製ガンマーＧ／４ｂ１２０３（最大吐出圧
１．２ＭＰａ、平均吐出圧時吐出量４８ｍｌ／ｍｉ
ｎ．）をそれぞれ用いた。ラインミキサー１０は、”ス
タティクミキサー”（ノリタケカンパニー製１−Ｎ５０
−１７１−０型）とした。さらに、流量調節弁０７,流
量計０８を、定流量弁｛ 流体工業製ＨＶＴ−１Ｂ型
（ＳＵＳ３０４製）｝とし、硬質ＰＶＣ製管の径を２５
Ａ（内径２５ｍｍ）に代替した。Examples 7 to 12 (Reaction Measures) The same production apparatus as in Examples 1 to 6 was used.
However, in order to operate for a long time, the aqueous chlorite tank 04, the aqueous hypochlorite tank 05, and the aqueous acid tank 06 were each made of 500 liter glass fiber reinforced plastic (FRP) with a pressure resistance of 1 MPa.
The sodium chlorite solution sending pump 01 is a gamma G / 4b0806 type manufactured by Prominent (maximum discharge pressure 0.8 MPa, discharge amount at average discharge pressure 93 ml / mi).
n. ), The sodium hypochlorite solution feed pump 02 is a gamma G / 4cb1 manufactured by the company equipped with an automatic degassing mechanism.
203 (maximum discharge pressure 1.2 MPa, discharge amount at average discharge pressure 48 ml / min.), Acid solution feed pump 03 was manufactured by Prominent Gamma G / 4b1203 (maximum discharge pressure 1.2 MPa, discharge amount at average discharge pressure). 48ml / mi
n. ) Were used. The line mixer 10 is a “Static Mixer” (1-N50 manufactured by Noritake Company)
-171-0 type). Further, the flow rate control valve 07 and the flow meter 08 are constant flow valves {HVT-1B type (manufactured by Fluid Industries, SUS304)}, and the diameter of the rigid PVC pipe is 25.
A (inner diameter 25 mm).
【００２５】（市販の原料液による二酸化塩素水の製造
例）市販の亜塩素酸ナトリウム水溶液｛２５．０重量％
(比重１．２２、２５℃）｝、次亜塩素酸ナトリウム水
溶液｛１２．５重量％（比重１．２２、２０℃）｝をそ
のまま使用し、市販塩酸３６重量％を１５．０重量％
（比重１．０７、２５℃）｝に希釈して使用した。各原
料液のｇ／ｌ表示の濃度はつぎのとおりである。 亜塩素酸ナトリウム水溶液 ３０５ｇ／ｌ 次亜塩素酸ナトリウム水溶液 １５２ｇ／ｌ 塩酸水溶液 １６０ｇ／ｌ 表１の条件によれば、２，１００ｐｐｍの二酸化塩素水
を約２．４ｍ３／ｈｒ（ＣｌＯ2５．０４Ｋｇ／ｈｒ）
製造できるので、例えば飲料水消毒において、水道原水
に対する二酸化塩素の添加量を１ｐｐｍで処理すれば、
水道原水５０４０ｍ３／ｈｒの消毒ができる。１日１人
の平均水道水使用量が０．５ｍ３とすれば、給水人口約
２４万人の都市に給水する浄水消毒設備に相当する。以
上のように、市販原料水溶液を用いた連続運転において
も収率９０％以上で亜塩素酸イオンを含まず塩素を含む
純度８５％以上のｐＨも弱酸性〜酸性の二酸化塩素水が
得られた。なお、実施例７は、次亜塩素酸ナトリウム濃
度を、反応式（１）による理論量（１００％）にしたも
のである。(Example of Production of Chlorine Dioxide Water Using Commercially Available Raw Material Liquid) Commercially available aqueous solution of sodium chlorite 塩 素 25.0% by weight
(Specific gravity 1.22, 25 ° C.)}, an aqueous solution of sodium hypochlorite {12.5% by weight (specific gravity 1.22, 20 ° C.)} is used as it is, and 36% by weight of a commercially available hydrochloric acid is added to 15.0% by weight.
(Specific gravity: 1.07, 25 ° C.). The concentration in g / l of each raw material liquid is as follows. Aqueous solution of sodium chlorite 305 g / l Aqueous solution of sodium hypochlorite 152 g / l Aqueous solution of hydrochloric acid 160 g / l According to the conditions in Table 1, 2,100 ppm of chlorine dioxide water was added to about 2.4 m3 / hr (5.04 kg of ClO2 ). / Hr)
Since it can be manufactured, for example, in drinking water disinfection, if the amount of chlorine dioxide added to tap water is treated at 1 ppm,
5040m3 / hr of raw tap water can be disinfected. If the average daily tap water consumption per person is 0.5m3, this is equivalent to a water purification facility that supplies water to a city with a population of approximately 240,000. As described above, even in a continuous operation using a commercially available raw material aqueous solution, a chlorine dioxide water having a yield of 90% or more and a pH of 85% or more containing chlorine without containing chlorite ions and having a weak acidic to acidic pH was obtained. . In Example 7, the concentration of sodium hypochlorite was set to the theoretical amount (100%) according to the reaction formula (1).
【００２６】[0026]
【表１】[Table 1]
【００２７】[0027]
【発明の効果】本発明の製造法および製造装置は、メン
テナンスフリーで月単位の長期運転可能で簡便であり、
従来のように塩素含有量を低く抑えるために高価な測定
装置を用いて次亜塩素酸塩溶液の煩わしい濃度調整の必
要はない。また、本発明は、支障のない若干量の塩素を
含む二酸化塩素イオンの存在しない飲料用原水の消毒剤
として消毒能力の高い二酸化塩素水を提供できる。Industrial Applicability The production method and production apparatus of the present invention are maintenance-free, can be operated for a long term on a monthly basis, and are simple.
There is no need to use an expensive measuring device to control the concentration of chlorine in the hypochlorite solution as in the related art. Further, the present invention can provide chlorine dioxide water having a high disinfecting ability as a disinfectant of drinking water for drinking water which does not contain chlorine dioxide ions containing a small amount of chlorine without any problem.
【図１】本願発明の二酸化塩素水発生装置の一例であ
る。FIG. 1 is an example of a chlorine dioxide water generator of the present invention.
０１ 亜塩素酸塩水溶液定量ポンプ ０２ 次亜塩素酸塩水溶液定量ポンプ ０３ 酸水溶液定量ポンプ ０４ 亜塩素酸塩水溶液タンク ０５ 次亜塩素酸塩水溶液タンク ０６ 酸水溶液タンク ０７ 流量調節弁 ０８ 流量計 ０９ 逆止弁 １０ ラインミキサー １１ 二酸化塩素水レシーバータンク １２ 希釈口 １３ ガス洗浄瓶 １４ タンクレベル計 01 Chlorite aqueous solution metering pump 02 Hypochlorite aqueous solution metering pump 03 Acid aqueous solution metering pump 04 Hypochlorite aqueous solution tank 05 Hypochlorite aqueous solution tank 06 Acid aqueous solution tank 07 Flow control valve 08 Flowmeter 09 Reverse Stop valve 10 Line mixer 11 Chlorine dioxide water receiver tank 12 Dilution port 13 Gas washing bottle 14 Tank level meter
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11076217AJP2000264606A (en) | 1999-03-19 | 1999-03-19 | Method and apparatus for producing chlorine dioxide water |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11076217AJP2000264606A (en) | 1999-03-19 | 1999-03-19 | Method and apparatus for producing chlorine dioxide water |
| Publication Number | Publication Date |
|---|---|
| JP2000264606Atrue JP2000264606A (en) | 2000-09-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11076217AWithdrawnJP2000264606A (en) | 1999-03-19 | 1999-03-19 | Method and apparatus for producing chlorine dioxide water |
| Country | Link |
|---|---|
| JP (1) | JP2000264606A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004002883A1 (en)* | 2002-06-28 | 2004-01-08 | Sk Aquatech Co., Ltd. | Method and apparatus for producing chlorine dioxide useful in water purification plants |
| WO2005007281A1 (en)* | 2003-07-11 | 2005-01-27 | E.I. Dupont De Nemours And Company | Apparatus and process therewith |
| EP3017865A1 (en)* | 2014-11-07 | 2016-05-11 | Jürgen Löhrke GmbH | Chlorine dioxide installation |
| JP2017512758A (en)* | 2014-02-26 | 2017-05-25 | ディスインフェクション リサーチ リミティッド ライアビリティ カンパニーＤｉｓｉｎｆｅｃｔｉｏｎ Ｒｅｓｅａｒｃｈ Ｌｌｃ | Wide-area disinfectant |
| KR102279087B1 (en)* | 2020-11-17 | 2021-07-21 | 주식회사알라딘 | Apparatus for generating chlorine dioxide gas |
| KR20210142899A (en)* | 2020-05-19 | 2021-11-26 | 유숙정 | Aqueous chlorine dioxide having high purity and the manufacturing method thereof |
| KR102461248B1 (en)* | 2021-11-05 | 2022-11-01 | 서승훈 | System of Chloride Dioxide Gas Continuous Production Equipment With Have Series-Parallel connection Reaction Vessel And Method of Operation Thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004002883A1 (en)* | 2002-06-28 | 2004-01-08 | Sk Aquatech Co., Ltd. | Method and apparatus for producing chlorine dioxide useful in water purification plants |
| WO2005007281A1 (en)* | 2003-07-11 | 2005-01-27 | E.I. Dupont De Nemours And Company | Apparatus and process therewith |
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| Date | Code | Title | Description |
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| A621 | Written request for application examination | Free format text:JAPANESE INTERMEDIATE CODE: A621 Effective date:20060127 | |
| A761 | Written withdrawal of application | Free format text:JAPANESE INTERMEDIATE CODE: A761 Effective date:20080618 |