JPH1081503A - Production of chlorine dioxide water and device therefor - Google Patents
Production of chlorine dioxide water and device thereforInfo
- Publication number
- JPH1081503A JPH1081503A JP25393596A JP25393596A JPH1081503A JP H1081503 A JPH1081503 A JP H1081503A JP 25393596 A JP25393596 A JP 25393596A JP 25393596 A JP25393596 A JP 25393596A JP H1081503 A JPH1081503 A JP H1081503A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine dioxide
- water
- column
- aqueous solution
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は殺菌・消毒、脱臭、
脱色、防虫、異臭味改善等広範囲の用途に利用される二
酸化塩素及び二酸化塩素水の連続的な製造方法及びその
製造装置に関する。さらに詳しくは反応カラム及びこれ
に連結する希釈カラムが、混合・攪拌効果のあるスタテ
ィックミキサー、充填剤としてラッシヒリング、多孔
体、粒状体、網状体、繊維フィルター等を単体もしく
は、２種類以上を組み合わせて内装した混合・反応のカ
ラム装置を使用することで、連続で高効率（亜塩素酸塩
の二酸化塩素への転換率が高い）、高純度（不純物塩
素、亜塩素酸イオン等）な二酸化塩素水を製造するに際
して、ブロワーの静圧を利用した貯圧タンク方式の原料
薬液供給システム採用で少流量無脈動を特徴とし、低濃
度から高濃度の広範囲に適応可能であり、種々用途にタ
イムリーな対応ならしめた製造方法及びその装置に関す
る。TECHNICAL FIELD The present invention relates to sterilization / disinfection, deodorization,
The present invention relates to a continuous production method of chlorine dioxide and chlorine dioxide water used for a wide range of uses such as decolorization, insect repellent, and improvement of off-flavor taste, and an apparatus for producing the same. More specifically, the reaction column and the dilution column connected to the reaction column may be a static mixer having a mixing / stirring effect, a Raschig ring, a porous material, a granular material, a mesh material, a fiber filter, or the like as a filler alone or in combination of two or more. Continuously high efficiency (high conversion rate of chlorite to chlorine dioxide) and high purity (impurity chlorine, chlorite ion, etc.) chlorine dioxide water by using the built-in mixing and reaction column device In the production of, it is characterized by a low flow rate and no pulsation by adopting the raw material chemical supply system of the storage tank type using the static pressure of the blower, it can be applied in a wide range from low concentration to high concentration, and it is timely for various applications The present invention relates to a corresponding manufacturing method and apparatus.
【０００２】[0002]
【従来の技術】二酸化塩素は化学式ＣｌＯ2で表される
物質で、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する。 ガス濃
度１０％以上で爆発性、ガス濃度８％、２０℃では水に
対して約７０００ｐｐｍ（ｍｇ／ｌ）の溶解度を持つ。
二酸化塩素の製造方法としては従来、パルプ漂白等の大
規模な工業利用では塩素酸塩に鉱酸単独あるいは過酸化
水素、亜硫酸ガス、メタノール等の還元性物質を加え製
造する方法が行われている。飲料水の殺菌・消毒、異臭
味改善、工業廃水等の脱臭、脱色、農業ハウス内の防
虫、冷却塔のスライム防止、油井賦活等の中規模利用や
生活関連用途では亜塩素酸塩水溶液と酸水溶液あるいは
亜塩素酸塩水溶液と塩素ガス（次亜塩素酸塩と酸を含
む）を反応させ、発生した二酸化塩素をポンプ送水のエ
ジェクター下流の背圧下に水吸収と希釈を行う方法があ
るが、これ等はいずれも二酸化塩素をクローズドシステ
ムで発生、利用するのに適した方法であって、原料から
二酸化塩素への高転換率も加圧下の条件のものであり、
常温常圧下に開放すると転換率は十数％から数十％それ
より低下する。 2. Description of the Related Art Chlorine dioxide is a substance represented by the chemical formula ClO 2 , which is a gaseous substance at a normal temperature of a melting point of −59 ° C. and a boiling point of 11 ° C., and has strong oxidizing power and bactericidal properties. Explosive at a gas concentration of 10% or more, having a gas concentration of 8% and a solubility of about 7000 ppm (mg / l) in water at 20 ° C.
Conventionally, as a method for producing chlorine dioxide, in a large-scale industrial use such as pulp bleaching, a method of producing a chlorate by adding a mineral acid alone or a reducing substance such as hydrogen peroxide, sulfur dioxide, methanol or the like has been performed. . Sterilization and disinfection of drinking water, improvement of off-flavors, deodorization of industrial wastewater, decolorization, insect repellent in agricultural houses, prevention of slime in cooling towers, oil well activation, etc. There is a method in which an aqueous solution or aqueous chlorite solution is reacted with chlorine gas (including hypochlorite and acid), and the generated chlorine dioxide is absorbed and diluted under the back pressure downstream of the ejector for pumping water. All of these methods are suitable for generating and utilizing chlorine dioxide in a closed system, and the high conversion rate from raw materials to chlorine dioxide is also under pressure.
When released under normal temperature and normal pressure, the conversion rate drops from tens of percents to tens of percents or less.
【０００３】原料薬液の供給をポンプ送水等で得られた
水流エジェクターが作り出す減圧を利用して吸引する方
式のものはシンプルな装置である利点はあるが、減圧下
で発生する二酸化塩素ガスと水溶液を同時に吸引するた
め運転時の薬液流量が不安定である、また薬液吸引の為
の最低限の減圧度が必要であり、毎分１０リッター以下
の小容量の製造は出来ない。一方この不安定さを解消し
て、小容量製造を可能にする為にエジェクターに送るそ
れぞれの薬液をわざわざ高価な定量ポンプで行う方式の
装置も発明されているが、この場合でもエジェクターを
使う以上、小容量化に限界があるのと不安定さは付きも
のである。常温、常圧下での反応で亜塩素酸塩を原料と
した方法では、亜塩素酸塩と次亜塩素酸塩および酸の３
薬液を反応させる方法がある。特願０７−１９４３４６
の記載の如く、この３薬液法はそれぞれの薬液を正確に
コントロールして混合・撹拌すれば、高転換率、高純
度、高範囲な濃度に対応可能な優れた方法である。しか
しながら、次亜塩素酸ソーダは市販濃度である１０〜１
２．５％で、特に夏場の温度の高い時には短期日に大幅
な濃度ダウンが生じる事は良く知られている。また、比
較的に濃度ダウンの小さな６％以下であっても徐々に塩
素が飛んでしまうので、高転換率、高純度をキープする
のが難しくなる。これらのキープには、運転毎に次亜塩
素酸ソーダ薬液濃度のチェックと製造した二酸化塩素水
の純度を測定して３薬液のバランスがとれているか、検
定（キャリブレーション）しなければならない等の煩わ
しさがある。[0003] A system in which the supply of a raw material chemical solution is suctioned by utilizing the reduced pressure created by a water jet ejector obtained by pumping water or the like is advantageous in that it is a simple device, but chlorine dioxide gas generated under reduced pressure and an aqueous solution are used. Are simultaneously sucked, the flow rate of the chemical solution during operation is unstable, and a minimum degree of decompression is required for sucking the chemical solution, so that a small volume of less than 10 liters per minute cannot be manufactured. On the other hand, in order to eliminate this instability and to enable small-volume manufacturing, an apparatus has been invented that uses an expensive metering pump to send each chemical solution sent to the ejector. However, there is a limit to miniaturization and instability is inherent. In a method using chlorite as a raw material in a reaction under normal temperature and pressure, three methods of chlorite, hypochlorite and acid are used.
There is a method of reacting a chemical solution. Japanese Patent Application No. 07-194346
As described in the above, the three-chemical method is an excellent method capable of coping with a high conversion rate, a high purity, and a high concentration range when the respective chemicals are accurately controlled and mixed and stirred. However, sodium hypochlorite has a commercial concentration of 10-1.
It is well known that at 2.5%, especially when summer temperatures are high, significant reductions in concentration occur on short days. In addition, even if the concentration is relatively small, that is, 6% or less, chlorine gradually flies, so that it is difficult to keep high conversion and high purity. In these keeps, it is necessary to check the concentration of the sodium hypochlorite solution and measure the purity of the produced chlorine dioxide solution at each operation to make sure that the three solutions are balanced and to carry out a test (calibration). There is annoyance.
【０００４】亜塩素酸塩水溶液に塩素ガスを吹き込む１
液１ガス法は反応の正確なコントロールがし易いので、
発癌性のトリハロメタン（ＴＨＭと略す）生成の原因に
なる不純物塩素含量を極端に少なく出来る利点と、ペー
ハーを中性付近で二酸化塩素を発生出来る利点も有して
いる、しかしながら毒性の強い危険な塩素ガスボンベを
取り扱う関係で浄水場等従来より扱い慣れた事業所に限
られる。本発明で採用した亜塩素酸塩と酸とを反応させ
る２薬液法は、従来より良く知られた方法である。例え
ば、セルローズ系繊維の漂白では亜塩素酸ソーダの活性
化剤として無機酸または有機酸あるいは緩衝剤を用いて
ｐＨを２．５から４．０に下げ、生成した二酸化塩素や
亜塩素酸で酸化漂白が行われている。この例ではステン
レス槽等の腐食性を抑える為に適度な二酸化塩素生成率
で漂白効果の高い領域を選定して使用されるので、必ず
しも亜塩素酸塩の二酸化塩素への転換効率の高い条件で
はない。Blowing chlorine gas into chlorite aqueous solution 1
Since the liquid 1 gas method makes it easy to control the reaction accurately,
It has the advantage of extremely reducing the chlorine content of impurities that cause carcinogenic trihalomethane (abbreviated to THM) and the advantage of generating chlorine dioxide near neutral pH. It is limited to establishments that are used to handling gas cylinders, such as water treatment plants. The two-chemical method of reacting a chlorite and an acid employed in the present invention is a well-known method. For example, in the bleaching of cellulosic fibers, the pH is lowered from 2.5 to 4.0 using an inorganic or organic acid or a buffer as an activator of sodium chlorite and oxidized with the generated chlorine dioxide or chlorite. Bleaching is taking place. In this example, a region with an appropriate chlorine dioxide generation rate and a high bleaching effect is selected and used in order to suppress the corrosiveness of a stainless steel tank, etc., so it is not necessarily required that the conversion efficiency of chlorite to chlorine dioxide be high. Absent.
【０００５】二酸化塩素の使用直前の発生方法は種々の
方法が知られているが、化学反応速度が常温で速く、し
かも亜塩素酸塩の二酸化塩素への転換効率が８０％以上
で、かつ添加する酸量の変動で発生する二酸化塩素濃度
に影響しないことが重要である。また、殺菌・消毒を必
要とする場所に二酸化塩素水の発生機を設置するのであ
るから装置自体がコンパクトで簡便に操作できることも
実用上、重要事項である。そして、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、極弱いバブリ
ングや攪拌でも極端なガスアウトが生じて濃度が大幅に
低下する。従来法ではこの飛散を防ぐ必要がありクロー
ズドシステムでないと効率的な適応が出来ない為に、常
温常圧下での使用が制限されて来た。特に二酸化塩素水
を低濃度で殺菌や脱臭に適応する場合、従来法による二
酸化塩素連続発生では二酸化塩素水は高濃度、乱流で得
られるので、ガスアウトし易くかつ、使用に適した希釈
液を作る希釈混合操作でもガスアウトが生じて、使用以
前に無視できない量の高価な二酸化塩素が空気中に飛散
するので経済上著しく不利であるばかりでなく危険も伴
っていた。Various methods are known for generating chlorine dioxide immediately before use, but the chemical reaction rate is high at normal temperature, the conversion efficiency of chlorite to chlorine dioxide is 80% or more, It is important that the change in the amount of acid produced does not affect the concentration of chlorine dioxide generated. In addition, since the generator of chlorine dioxide water is installed in a place where sterilization / disinfection is required, it is also important in practical use that the apparatus itself is compact and can be easily operated. Since chlorine dioxide in the chlorine dioxide water is dissolved as a gas, even extremely weak bubbling or stirring causes an extreme gas out, resulting in a significant decrease in concentration. In the conventional method, it is necessary to prevent this scattering, and efficient adaptation cannot be performed unless a closed system is used. Therefore, use under normal temperature and normal pressure has been limited. In particular, when chlorine dioxide water is used for sterilization and deodorization at a low concentration, continuous generation of chlorine dioxide according to the conventional method produces a high concentration of chlorinated water in a turbulent flow. The diluting / mixing operation which produces the gas produced gas out, and was not only economically disadvantageous but also dangerous because a considerable amount of expensive chlorine dioxide was scattered in the air before use.
【０００６】[0006]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、従来知られていた二酸化塩素水の製造方法
で問題となっていたガスアウトによる濃度低下を起こさ
ない、操作が簡便で濃度の安定した二酸化塩素水の製造
方法およびそのための製造装置を提供することである。The problem to be solved by the present invention is that the operation is simple and the concentration is not reduced by gas out which is a problem in the conventionally known method for producing chlorine dioxide water. It is an object of the present invention to provide a stable method for producing chlorine dioxide water and a production apparatus therefor.
【０００７】[0007]
【課題を解決するための手段】本発明らは、常温での反
応速度が速く、かつ亜塩素酸塩からの二酸化塩素収率
（転換率）を８０％以上にする為に、亜塩素酸塩中の亜
塩素酸イオンモル比に対して用いる鉱酸モル濃度を少な
くとも３倍以上で３０倍以下、望ましくは５倍以上、１
０倍以下となし、しかも用いた亜塩素酸塩溶液量に対し
て鉱酸溶液量をほぼ同等とする条件を選定した。本発明
者らは、これらを考慮して、二酸化塩素発生原料薬液の
２種を反応カラムにて混合して反応させ、濃厚な反応溶
液を、これに連結した希釈カラムにて連続かつ静的に混
合反応せしめる方法、これを実現させる装置を発明し
た。DISCLOSURE OF THE INVENTION The present invention provides a chlorite compound which has a high reaction rate at room temperature and a chlorine dioxide yield (conversion) from chlorite of 80% or more. The molar concentration of the mineral acid used is at least 3 times and up to 30 times, preferably at least 5 times and up to 1 times the molar ratio of chlorite ions in the solution.
The conditions were set at 0 times or less, and the amount of the mineral acid solution was almost equal to the amount of the chlorite solution used. In view of these, the present inventors mixed and reacted two kinds of chlorine dioxide generating raw material chemicals in a reaction column, and continuously and statically concentrated a concentrated reaction solution in a dilution column connected thereto. We have invented a method for performing the mixing reaction and an apparatus for realizing the method.
【０００８】すなわち、本発明は、それぞれ別のタンク
に入れた鉱酸水溶液と亜塩素酸塩水溶液とを、液面に加
えた空気圧により連続的に静的混合装置を具備した反応
カラム中に導き、該反応カラム中で生成した１．０から
４．０％の二酸化塩素溶液を該反応カラムに連結した静
的混合装置を具備した混合カラム中で水により希釈し、
１０ｍｇ／ｌから３，０００ｍｇ／ｌ濃度の二酸化塩素
水となす、二酸化塩素水の製造方法に関する。That is, according to the present invention, a mineral acid aqueous solution and a chlorite aqueous solution, which are respectively stored in separate tanks, are continuously introduced into a reaction column equipped with a static mixing device by air pressure applied to the liquid surface. Diluting the 1.0 to 4.0% chlorine dioxide solution formed in the reaction column with water in a mixing column equipped with a static mixing device connected to the reaction column;
The present invention relates to a method for producing chlorine dioxide water, wherein the concentration of chlorine dioxide water is from 10 mg / l to 3,000 mg / l.
【０００９】本発明の具体的な態様は、鉱酸が塩酸であ
り、亜塩素酸塩が亜塩素酸ソーダであり、かつ塩酸の量
が亜塩素酸ソーダ量に対して３倍モルから３０倍モルで
ある上記の二酸化塩素水の製造方法である。In a specific embodiment of the present invention, the mineral acid is hydrochloric acid, the chlorite is sodium chlorite, and the amount of hydrochloric acid is 3 to 30 times the amount of sodium chlorite. This is the method for producing chlorine dioxide water described above, which is a mole.
【００１０】本発明の更に別な具体的な態様は、反応カ
ラム及び水希釈カラムが、スタティツクミキサー、ラッ
シヒリング、多孔体、粒状体、網状体、繊維フィルター
から選ばれる充填材の１種または２種類以上を組み合わ
せて内装した静的混合装置を具備したカラムであり、か
つ反応カラムに供給する鉱酸水溶液および亜塩素酸塩水
溶液の流速が０．０１ｍ／ｓｅｃ〜０．５ｍ／ｓｅｃで
あり、水希釈カラムに供給する清水の流速が０．０１ｍ
／ｓｅｃ〜０．５ｍ／ｓｅｃであることを特徴とする上
記いずれかの二酸化塩素水の製造方法である。[0010] In another specific embodiment of the present invention, the reaction column and the water dilution column each include one or more of a filler selected from a static mixer, a Raschig ring, a porous material, a granular material, a mesh material, and a fiber filter. A column equipped with a static mixing device equipped with a combination of two or more kinds, and a flow rate of a mineral acid aqueous solution and a chlorite aqueous solution supplied to the reaction column is 0.01 m / sec to 0.5 m / sec. The flow rate of fresh water supplied to the water dilution column is 0.01 m
/ Sec to 0.5 m / sec.
【００１１】本発明の更に別な具体的な態様は、タンク
中の鉱酸水溶液および亜塩素酸塩水溶液の液面を加圧す
るためにブロワーの静圧を利用した貯圧タンクを使用
し、少流量無脈動により鉱酸水溶液および亜塩素酸塩水
溶液を反応カラム中に導くことを特徴とする上記いずれ
かの二酸化塩素の製造方法である。[0011] Still another specific embodiment of the present invention uses a pressure storage tank utilizing the static pressure of a blower to pressurize the liquid surface of a mineral acid aqueous solution and a chlorite aqueous solution in the tank. The method for producing chlorine dioxide according to any one of the above, wherein the aqueous solution of mineral acid and the aqueous solution of chlorite are introduced into the reaction column without flow pulsation.
【００１２】本発明はまた、ブロワーにより加圧される
貯圧タンク、鉱酸水溶液タンクおよび亜塩素酸塩水溶液
タンク、静的混合装置を具備した反応カラム、静的混合
装置を具備した混合カラムからなり、貯圧タンクから出
る均圧管は各薬液タンクの上部に連結され、各薬液タン
クの下部より該反応カラムの入口に各薬液供給管が連結
され、該反応カラムの出口より出る管は該混合カラムの
入口に連結され、また該混合カラムの入口には清水供給
管が連結されており、該混合カラムの出口から配された
管より二酸化塩素水を取り出すことを特徴とする二酸化
塩素水の製造装置に関する。The present invention also relates to a storage tank pressurized by a blower, a mineral acid aqueous solution tank and a chlorite aqueous solution tank, a reaction column equipped with a static mixing device, and a mixing column equipped with a static mixing device. A pressure equalizing pipe coming out of the pressure storage tank is connected to the upper part of each chemical liquid tank, each chemical liquid supply pipe is connected to the inlet of the reaction column from the lower part of each chemical liquid tank, and a pipe coming out of the outlet of the reaction column is mixed with the mixing liquid. A water supply pipe connected to an inlet of the column, and a fresh water supply pipe connected to an inlet of the mixing column, wherein chlorine water is taken out from a pipe provided from an outlet of the mixing column; Related to the device.
【００１３】本発明の二酸化塩素の製造装置において好
ましい態様は、タンクおよび配管の材質が塩化ビニール
樹脂、塩素化塩化ビニール樹脂、硝子、テフロン、ステ
ンレススチールまたはチタン合金よりなるか、あるいは
これらの材質でライニングされている装置である。In a preferred embodiment of the chlorine dioxide producing apparatus of the present invention, the material of the tank and the pipe is made of vinyl chloride resin, chlorinated vinyl chloride resin, glass, Teflon, stainless steel or titanium alloy, or made of these materials. It is a lined device.
【００１４】[0014]
【発明の実施の形態】二酸化塩素発生の原料として用い
る水溶液は１種が亜塩素酸塩を含む水溶液である。この
塩の具体的化合物としては好適には亜塩素酸ソーダが用
いられるが、例えば亜塩素酸カリ、亜塩素酸カルシウム
等のアルカリまたはアルカリ土類金属の亜塩素酸塩等も
用いる事が出来る。原料薬液のもう１種は酸を含む水溶
液である。好適に用いられる酸としては塩酸、硫酸、燐
酸の様な鉱酸が好適で、特に希釈熱発生が小さく、二酸
化塩素類縁である塩酸が特に好ましい。クエン酸、酒石
酸等の様な弱酸性の有機酸はも使用可能であるが、反応
効率が小さく実用上不利である。BEST MODE FOR CARRYING OUT THE INVENTION An aqueous solution used as a raw material for generating chlorine dioxide is an aqueous solution containing one kind of chlorite. As a specific compound of this salt, sodium chlorite is preferably used. For example, chlorite of an alkali or alkaline earth metal such as potassium chlorite and calcium chlorite can also be used. Another type of the raw chemical solution is an aqueous solution containing an acid. Mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid are preferably used as the acid, and hydrochloric acid, which has a low heat of dilution and is similar to chlorine dioxide, is particularly preferable. Although a weakly acidic organic acid such as citric acid or tartaric acid can be used, the reaction efficiency is small and disadvantageous in practical use.
【００１５】本発明では、用いた亜塩素酸ソーダの理論
量に対して塩酸量を少なくも３倍以上、好ましくは５倍
以上の過剰で反応させる事を、８０％以上の収率をキー
プする為に必要とする。塩酸の過剰量はこれより多くて
も反応上は構わないが、酸性度が高いのは、用いる装置
材質の制限やコスト面等で不利な点ばかりであるから、
出来る限り低い倍率で８０％以上の収率がキープ出来る
倍率を選ぶべきである。本発明の方法を実現する具体的
な装置として、採用した方法は反応カラム及びこれに連
結した希釈カラムに混合、攪拌効果のあるスタティック
ミキサー、ラッシヒリング、多孔体、粒状体、網状体、
繊維フィルター等を単体もしくは２種類以上を組み合わ
せて内装した混合・反応の装置を用する事である。In the present invention, the reaction is carried out in excess of at least 3 times, preferably 5 times or more the amount of hydrochloric acid with respect to the theoretical amount of sodium chlorite used, while keeping the yield of 80% or more. Needed for An excess amount of hydrochloric acid may be used in the reaction even if it is larger than this, but the acidity is high because there are only disadvantages in terms of restrictions on equipment materials used and costs.
A magnification should be selected so that a yield of 80% or more can be kept at the lowest possible magnification. As a specific apparatus for realizing the method of the present invention, the method adopted is mixing into a reaction column and a dilution column connected thereto, a static mixer having a stirring effect, Raschig ring, porous body, granular body, reticulated body,
A mixing / reaction apparatus in which a fiber filter or the like is used alone or in combination of two or more kinds is used.
【００１６】本発明の装置例は第１図に示した。エアー
フイルターを通った空気はオイルレスブロワー（１）に
より貯圧タンク（２）に吹き込まれる。圧力調節弁
（３）の開度により貯圧タンク（２）内の静圧力を調節
する。貯圧タンク（２）は原料薬液タンク（４）、
（５）と均圧管によって結ばれ、原料薬液を押し出す働
きをする。原料薬液の減量分だけ貯圧タンクの空気が原
料薬液タンクへ移動し、原料薬液の多少によらず均圧を
保つことが出来る。押し出された薬液は、流量調節弁
（６）、流量計（７）、逆止弁（８）を通って、それぞ
れ反応カラム（９）へ送られる。反応カラム内で混合さ
れ反応して濃厚な二酸化塩素溶液が生成する。この濃厚
な二酸化塩素溶液は希釈カラム（１０）入り口直前で水
道水等（１２）の清水と合流し、希釈カラム（１０）に
導かれ希釈混合される。そして、希釈された二酸化塩素
水としてレシーバータンク（１１）に溜められる。An example of the apparatus of the present invention is shown in FIG. The air that has passed through the air filter is blown into the pressure storage tank (2) by the oilless blower (1). The static pressure in the pressure storage tank (2) is adjusted by the opening of the pressure control valve (3). The storage tank (2) is a raw material chemical tank (4),
It is connected to (5) by an equalizing tube, and works to push out the raw material chemical. The air in the pressure storage tank moves to the raw material chemical tank by the reduced amount of the raw material chemical, and the pressure can be maintained regardless of the amount of the raw material chemical. The extruded chemical solution is sent to the reaction column (9) through the flow control valve (6), the flow meter (7), and the check valve (8). It is mixed and reacted in the reaction column to form a concentrated chlorine dioxide solution. This concentrated chlorine dioxide solution joins with fresh water such as tap water (12) immediately before the entrance of the dilution column (10), and is led to the dilution column (10) to be diluted and mixed. Then, it is stored in the receiver tank (11) as diluted chlorine dioxide water.
【００１７】貯圧タンクの圧力は装置の高さ以上（水
柱）あれば良いが配管抵抗及び主反応器以後の抵抗を考
慮して装置高さプラス数メーター（水柱）とすれば良
い。ブロワー圧力は圧力調節弁を閉じた時、前記の装置
高さプラス数ｍ（水柱）以上であれば良い。貯圧タンク
容量は大きい方が圧力変動は少ないが、現実的には２薬
液タンク容量の合計と同等以上あれば支障ない。ブロワ
ー風量は２薬液の減る量の１００〜１０００倍あれば貯
圧タンクの圧力変動率は１〜０.１％位となり、充分に
安定運転が出来る。厳密には圧力調節弁から出る空気量
が２薬液の減る量の１００倍以上であれば圧力変動率は
１％以下になる。均圧管は空気流量が少ないため、１／
２〜２（インチ）あれば充分である。The pressure of the pressure storage tank may be higher than the height of the apparatus (water column), but may be set to the height of the apparatus plus several meters (water column) in consideration of the pipe resistance and the resistance after the main reactor. The blower pressure may be at least the height of the apparatus plus several meters (water column) when the pressure control valve is closed. The larger the pressure storage tank capacity, the smaller the pressure fluctuation. However, in reality, there is no problem if the capacity is equal to or more than the sum of the two chemical liquid tank capacities. If the blower air volume is 100 to 1000 times the reduced amount of the two chemicals, the pressure fluctuation rate of the pressure storage tank will be about 1 to 0.1%, and a sufficiently stable operation can be performed. Strictly speaking, if the amount of air flowing out of the pressure control valve is 100 times or more the amount of reduction of the two chemicals, the pressure fluctuation rate will be 1% or less. Since the equalizing tube has a small air flow, 1 /
Two to two inches is sufficient.
【００１８】圧力調節弁はボール弁、ブローブ弁、仕切
弁等が良く、ダンパーでは調節し難い。２薬液の流量調
節弁は微細調節の可能なニードル弁が良い。流量計は液
流量が広範囲、且つ正確に計れるものが良く、ローター
メーターやボールタイプのものが使える。又、自動制御
用の流量計とニードル弁を組み合わせる方法もある。２
薬液及び清水のラインには混合液が逆流しないように逆
防止弁が必要である。清水はポンプ送水による圧水又は
水道水で、圧力変動が少ないことが要求される。主反応
器は２薬液と水を静的に混合、反応させることを目的と
し、静かに混合しながら２薬液の分子がまんべん無く接
触することが好ましく、スタティックミキサー、ラッシ
ヒリング、多孔体、粒状体、網状体、繊維フィルターな
どの液の流路を細分し、また、合流して、これを複数回
繰り返すような構造が必要である。これらは単体でも良
いが２種類以上を組み合わせて混合、反応効果を向上さ
せることが出来る。例えば、スタティックミキサーで、
まず荒混合をさせた後、微細な繊維フィルターを通すこ
とにより分子間接触の機会を増やすことが出来る。The pressure control valve is preferably a ball valve, a probe valve, a gate valve, or the like, and is difficult to adjust with a damper. The two chemical liquid flow control valves are preferably needle valves capable of fine adjustment. The flow meter preferably has a wide range of liquid flow rate and can accurately measure the liquid flow rate, and a rotor meter or a ball type can be used. There is also a method of combining a flow meter for automatic control and a needle valve. 2
A check valve is required in the chemical and fresh water lines to prevent the mixture from flowing back. Fresh water is pressurized water or tap water by pumping water, and is required to have low pressure fluctuation. The main reactor is intended to statically mix and react the two chemicals and water, and it is preferable that the molecules of the two chemicals come into contact evenly while gently mixing. Static mixer, Raschig ring, porous material, granular material It is necessary to have a structure in which liquid flow paths such as a net, a fiber filter and the like are subdivided and merged, and this is repeated a plurality of times. These may be used alone or in combination of two or more kinds to improve the mixing and reaction effects. For example, with a static mixer,
First, after rough mixing, the chance of intermolecular contact can be increased by passing through a fine fiber filter.
【００１９】本発明の方法では、貯圧タンク方式の原料
薬液供給システムによりいずれも小流量の上述の亜塩素
酸塩水溶液と鉱酸水溶液を鉱酸の量が亜塩素酸塩に対し
て３倍モルから３０倍モル、好ましくは５倍モルから１
０倍モルの比率で反応カラムに、０．０１〜０．５ｍ／
ｓｅｃで無脈動にて定量的に注入する。反応カラムに流
入する薬液の流速が０．０１ｍ／ｓｅｃ未満であると撹
拌混合効果が期待できなくなるので好ましくない。ま
た、薬液の反応カラム内の流速が０．５ｍ／ｓｅｃを越
すと、反応液が乱流となり溶液中に溶解している二酸化
塩素ガスが気泡となり揮散し、二酸化塩素濃度が低下す
るので好ましくない。本流速範囲は、反応カラム内で生
成した二酸化塩素溶液を清水にて希釈する希釈カラムに
ついてもそのまま当てはまることである。In the method of the present invention, the above-mentioned aqueous chlorite solution and the aqueous mineral acid solution having a small flow rate are each reduced by three times the amount of the mineral acid by the raw material chemical supply system of the storage tank type. Mole to 30 times mole, preferably 5 times to 1 mole
The reaction column was added at a molar ratio of 0 to 0.01 to 0.5 m /
Quantitative injection without pulsation in sec. If the flow rate of the chemical solution flowing into the reaction column is less than 0.01 m / sec, it is not preferable because the stirring and mixing effect cannot be expected. On the other hand, if the flow rate of the chemical solution in the reaction column exceeds 0.5 m / sec, the reaction solution becomes turbulent and chlorine dioxide gas dissolved in the solution becomes bubbles and volatilizes, and the chlorine dioxide concentration decreases, which is not preferable. . This flow rate range is also applicable to a dilution column for diluting a chlorine dioxide solution generated in the reaction column with fresh water.
【００２０】なお、二酸化塩素発生装置は水道水の様な
清水の一定流量に一定流量の薬液を供給して発生濃度を
決める仕組みである、そこで安全上、清水停止の場合に
は薬液供給バルブが閉まる構造としておく事が望まし
い。 同じく２薬液量をレベルゲージ等で検知して、空
になった場合には安全上、全ての薬液供給が停止する構
造としておく事が望ましい。かくして、水道水等の０．
０１〜０．５ｍ／ｓｅｃ．の清水流中に上述の２種原料
溶液をほぼ反応理論量で貯圧タンク方式の原料薬液供給
システムにより少流量無脈動で定量的に送り、連続で高
効率（亜塩素酸塩の二酸化塩素への転換率が高い）の二
酸化塩素水を製造することができる。Incidentally, the chlorine dioxide generator is a mechanism for determining the concentration of generated water by supplying a constant flow rate of a chemical solution to a constant flow rate of fresh water such as tap water. It is desirable to have a closed structure. Similarly, it is desirable to detect the amount of the two chemicals with a level gauge or the like, and to completely stop the supply of the chemicals when they become empty, for safety reasons. Thus, 0.1% of tap water etc.
01 to 0.5 m / sec. The above-mentioned two raw material solutions are sent quantitatively in a fresh water stream at a low flow rate and no pulsation by a storage tank type raw material chemical supply system with almost the theoretical amount of reaction, and continuously high efficiency (to chlorine dioxide of chlorite) (A high conversion rate of chlorine dioxide) can be produced.
【００２１】[0021]
【発明の効果】本発明により、経済性と安全性が高く、
簡単な操作で二酸化塩素を製造する事が出来る。そし
て、殺菌や脱臭目的に合わせた濃度の二酸化塩素水をそ
の場で必要な時に得られる方法を提供出来る。本発明は
低濃度に好適であるばかりでなく、種々用途に応じた広
範囲の濃度にもタイムリーに対応可能である。According to the present invention, economic efficiency and safety are high,
Chlorine dioxide can be produced with a simple operation. In addition, a method can be provided in which chlorine dioxide water having a concentration suitable for the purpose of sterilization and deodorization can be obtained on the spot when needed. The present invention is not only suitable for a low concentration, but also can timely respond to a wide range of concentrations according to various uses.
【００２２】[0022]
【実施例】以下、実施例により本発明をより詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００２３】実施例１ フラスコ法による二酸化塩素水
製造時の薬液供給量の決定 亜塩素酸塩として亜塩素酸ソーダ、酸として塩酸を選ん
だ。各薬液濃度は次のものを使用した。 亜塩素酸ソーダ水溶液 ８．００重量／容積％ 塩酸水溶液 １８．００重量／容積％ 反応式 ５ＮａＣｌＯ2＋４ＨＣｌ＝４ＣｌＯ2＋５Ｎ
ａＣｌ＋２Ｈ2ＯExample 1 Determination of Supply Rate of Chemical Solution During Production of Chlorine Dioxide Water by Flask Method Sodium chlorite was selected as chlorite and hydrochloric acid was selected as acid. The following concentrations were used for the respective drug solutions. Sodium chlorite aqueous solution 8.00 wt / vol% Hydrochloric acid aqueous solution 18.00 wt / vol% Reaction formula 5NaClO 2 + 4HCl = 4ClO 2 + 5N
aCl + 2H 2 O
【００２４】２００ミリリッター容積の硝子製メスフラ
スコに上述の亜塩素酸ソーダ溶液を４．８ｍｌ採ったも
のを数本準備する。これに上述の塩酸水溶液を式−１の
化学式で示した化学量論量の１倍から３５倍添加、混合
して反応せしめ、メスアップしてからヨー化カリ／チオ
硫酸ソーダ標準液による酸化還元滴定法により、二酸化
塩素濃度を求めた。なお、使用した亜塩素酸ソーダ量か
ら理論二酸化塩素転換濃度は１４４０ｍｇ／ｌであっ
た。その結果、塩酸添加量と二酸化塩素発生量の関係
は、表１と図１に示した通り、亜塩素酸ソーダ量に対し
て化学量論量の０から５倍までは直線的に収率が増加
し、５倍以上であれば酸量に関係せず収率は一定とな
る。８２〜８３％と高収率であった。Several 4.8 ml of the above-mentioned sodium chlorite solution are prepared in a 200 ml glass measuring flask having a capacity of glass and several are prepared. The above-mentioned aqueous hydrochloric acid solution was added to the mixture in an amount of 1 to 35 times the stoichiometric amount represented by the chemical formula (1), mixed and reacted, and the amount was reduced, followed by oxidation reduction using potassium iodide / sodium thiosulfate standard solution. The chlorine dioxide concentration was determined by a titration method. From the amount of sodium chlorite used, the theoretical chlorine dioxide conversion concentration was 1440 mg / l. As a result, as shown in Table 1 and FIG. 1, the relationship between the amount of added hydrochloric acid and the amount of generated chlorine dioxide shows that the yield is linear from 0 to 5 times the stoichiometric amount with respect to the amount of sodium chlorite. If it increases and is 5 times or more, the yield becomes constant regardless of the acid amount. The yield was as high as 82 to 83%.
【００２５】[0025]
【表１】 [Table 1]
【００２６】別に３．００(w/v%)、６．００(w/v%)、１
０(w/v%)、３０(w/v%)亜塩素酸ソーダ溶液を用いて同様
な塩酸倍率にて試験した結果、８．００(w/v%)と同様に
収率８０％以上で発生二酸化塩素濃度カーブも図１と同
様のものとなった。Separately, 3.00 (w / v%), 6.00 (w / v%), 1
As a result of a test using a 0 (w / v%) and 30 (w / v%) sodium chlorite solution at the same hydrochloric acid magnification, the yield was 80% or more as with 8.00 (w / v%). The resulting chlorine dioxide concentration curve was the same as that in FIG.
【００２７】実施例２ 二酸化塩素製造装置による製造
例 原料薬液濃度は次の濃度のものを使用した。なお亜塩素
酸ソーダ溶液供給に対して塩酸溶液のフィードが多少変
動しても得られる二酸化塩素水の濃度が計画したものと
なる様な、亜塩素酸ソーダに対する塩酸倍率６．０を選
択した。 亜塩素酸ソーダ水溶液 ８．００重量／容積％ 塩酸水溶液 １５．５重量／容積％Example 2 Production Example Using Chlorine Dioxide Production Apparatus The concentration of the raw material chemical solution was as follows. A hydrochloric acid magnification of 6.0 with respect to sodium chlorite was selected so that the concentration of chlorine dioxide water obtained would be as planned even if the feed of the hydrochloric acid solution fluctuated somewhat with respect to the supply of the sodium chlorite solution. Sodium chlorite aqueous solution 8.00 wt / vol% Hydrochloric acid aqueous solution 15.5 wt / vol%
【００２８】二酸化塩素水の製造装置は基本的に図２に
示したものを採用した。ブロワーは５Ｎｍ3／ｍｉｎ．
×３０００ｍｍＡｑのターボブロワーを使用し、貯圧タ
ンクは１００リッターの硬質ＰＶＣ製タンクとし圧力計
を設けた。圧力調節弁はＰＶＣ製ボール弁（４０Ａ）を
使用した。貯圧タンクの圧力は１８０ｍｍＡｑで運転し
た。２薬液のタンクは２０リッターのＰＶＣ缶を使用
し、蓋には均圧管と液の押し上げ管を取り付け、密閉を
保てるようにした。均圧管は６Ａのテフロン管とし、２
薬液の流量調節弁はテフロン製ニードル弁（６Ａ）を、
流量計は０から最大２００ミリリッター毎分を計れるロ
ーターメーターを使用した。逆止弁は市販のプラスチッ
ク製（６Ａ）を、２薬液の供給配管はテフロンチューブ
（６Ａ）とした。反応カラムは１３ＡのＰＶＣ管を使用
し、６０ｃｍ長さとして、中に外径２ｍｍのガラス管を
２ｍｍ長さにカットしたピースをラッシヒリングの様に
多数個充填したものを使用した。これに接続した希釈カ
ラムには、スタティクミキサー（ノリタケカンパニー製
１−Ｎ１０−３２１−Ｎ型）を使用した。このカラムの
下部よりは、水道水をニードルバルブ−流量計−逆止弁
を通して供給、カラム下部に接続したＴ字管より反応カ
ラムで混合・反応した濃厚な二酸化塩素を流入させ、直
ちに希釈カラム内で混合・希釈されて目的濃度の二酸化
塩素水として連続的にレシバータンクに流入した。得ら
れた二酸化塩素水の分析は実施例１と同様に行った。水
道水流量と各薬液流量の比率及びこの条件で得られた二
酸化塩素水の分析値を表２に示した。表から明らかな様
に広範囲濃度の二酸化塩素水を高収率、連続的で簡易に
製造出来た。The chlorine dioxide water producing apparatus basically employs the apparatus shown in FIG. The blower is 5 Nm 3 / min.
A 3,000 mmAq turbo blower was used, the pressure storage tank was a 100 liter hard PVC tank, and a pressure gauge was provided. As the pressure control valve, a PVC ball valve (40A) was used. The pressure in the storage tank was operated at 180 mmAq. The tank for the two chemicals used a 20-liter PVC can, and the lid was equipped with a pressure equalizing tube and a liquid push-up tube so that the lid could be kept airtight. The pressure equalizing tube shall be a 6A Teflon tube, 2
The Teflon needle valve (6A)
The flow meter used was a rotor meter capable of measuring from 0 to a maximum of 200 milliliters per minute. The check valve was a commercially available plastic (6A), and the supply pipe for the two chemicals was a Teflon tube (6A). The reaction column used was a 13A PVC tube having a length of 60 cm, a glass tube having an outer diameter of 2 mm cut into a length of 2 mm, and a number of pieces filled like a Raschig ring. A static mixer (1-N10-321-N, manufactured by Noritake Company) was used for the dilution column connected to this. From the lower part of this column, tap water is supplied through a needle valve-flow meter-return valve, and the concentrated chlorine dioxide mixed and reacted in the reaction column flows from the T-tube connected to the lower part of the column, and immediately into the dilution column. , And continuously flowed into a receiver tank as chlorine dioxide water having a desired concentration. The obtained chlorine dioxide water was analyzed in the same manner as in Example 1. Table 2 shows the ratio between the flow rate of tap water and the flow rate of each chemical solution, and the analysis value of chlorine dioxide water obtained under these conditions. As is clear from the table, a wide range of concentrations of chlorine dioxide water could be produced continuously, easily and with high yield.
【００２９】[0029]
【表２】 [Table 2]
【図１】亜塩素酸ソーダに対する塩酸のモル比と、生成
する二酸化塩素の濃度の関係を示した図である。FIG. 1 is a diagram showing the relationship between the molar ratio of hydrochloric acid to sodium chlorite and the concentration of generated chlorine dioxide.
【図２】連続二酸化塩素水発生装置の一例を示した図で
ある。FIG. 2 is a diagram showing an example of a continuous chlorine dioxide water generator.
（１）オイルレスブロワー （２）貯圧タンク （３）圧力調節弁 （４）亜塩素酸塩水溶液タンク （５）酸水溶液タンク （６）流量調節弁 （７）流量計 （８）逆止弁 （９）反応カラム （10）希釈カラム （11）二酸化塩素水レシーバータンク （12）希釈水入口 (1) Oilless blower (2) Pressure storage tank (3) Pressure control valve (4) Chlorite aqueous solution tank (5) Acid aqueous solution tank (6) Flow control valve (7) Flow meter (8) Check valve (9) Reaction column (10) Dilution column (11) Chlorine dioxide water receiver tank (12) Dilution water inlet
Claims (6)
亜塩素酸塩水溶液とを、液面に加えた空気圧により連続
的に静的混合装置を具備した反応カラム中に導き、該反
応カラム中で生成した１．０から４．０％の二酸化塩素
溶液を該反応カラムに連結した静的混合装置を具備した
混合カラム中で水により希釈し、１０ｍｇ／ｌから３，
０００ｍｇ／ｌ濃度の二酸化塩素水となす、二酸化塩素
水の製造方法。An aqueous solution of mineral acid and an aqueous solution of chlorite, which are respectively contained in separate tanks, are continuously introduced into a reaction column equipped with a static mixing device by air pressure applied to the liquid surface. The 1.0 to 4.0% chlorine dioxide solution produced in the above was diluted with water in a mixing column equipped with a static mixing device connected to the reaction column, and 10 mg / l to 3,
A method for producing chlorine dioxide water, wherein the chlorine dioxide water has a concentration of 000 mg / l.
ソーダであり、かつ塩酸の量が亜塩素酸ソーダ量に対し
て３倍モルから３０倍モルである請求項１に記載した二
酸化塩素水の製造方法。2. The method according to claim 1, wherein the mineral acid is hydrochloric acid, the chlorite is sodium chlorite, and the amount of hydrochloric acid is 3 to 30 times the molar amount of the sodium chlorite. The method for producing chlorine dioxide water described.
ツクミキサー、ラッシヒリング、多孔体、粒状体、網状
体、繊維フィルターから選ばれる充填材の１種または２
種類以上を組み合わせて内装した静的混合装置を具備し
たカラムであり、かつ反応カラムに供給する鉱酸水溶液
および亜塩素酸塩水溶液の流速が０．０１ｍ／ｓｅｃ〜
０．５ｍ／ｓｅｃであり、水希釈カラムに供給する清水
の流速が０．０１ｍ／ｓｅｃ〜０．５ｍ／ｓｅｃである
ことを特徴とする請求項１または請求項２に記載した二
酸化塩素水の製造方法。3. The method according to claim 1, wherein the reaction column and the water dilution column are one or two of a packing material selected from a static mixer, a Raschig ring, a porous material, a granular material, a mesh material, and a fiber filter.
It is a column equipped with a static mixing device equipped with a combination of more than one kind, and a flow rate of a mineral acid aqueous solution and a chlorite aqueous solution supplied to a reaction column is 0.01 m / sec or more.
3. The chlorine dioxide water according to claim 1 or 2, wherein the flow rate of the fresh water supplied to the water dilution column is 0.5 m / sec, and the flow rate of the fresh water is 0.01 m / sec to 0.5 m / sec. Production method.
溶液の液面を加圧するためにブロワーの静圧を利用した
貯圧タンクを使用し、少流量無脈動により鉱酸水溶液お
よび亜塩素酸塩水溶液を反応カラム中に導くことを特徴
とする請求項１から請求項３のいずれかに記載した二酸
化塩素の製造方法。4. A storage tank using a static pressure of a blower for pressurizing the liquid surface of a mineral acid aqueous solution and a chlorite aqueous solution in a tank, and the mineral acid aqueous solution and the chlorine suboxide are pulsated at a small flow rate without pulsation. The method for producing chlorine dioxide according to any one of claims 1 to 3, wherein an aqueous acid salt solution is introduced into the reaction column.
酸水溶液タンクおよび亜塩素酸塩水溶液タンク、静的混
合装置を具備した反応カラム、静的混合装置を具備した
混合カラムからなり、貯圧タンクから出る均圧管は各薬
液タンクの上部に連結され、各薬液タンクの下部より該
反応カラムの入口に各薬液供給管が連結され、該反応カ
ラムの出口より出る管は該混合カラムの入口に連結さ
れ、また該混合カラムの入口には清水供給管が連結され
ており、該混合カラムの出口から配された管より二酸化
塩素水を取り出すことを特徴とする二酸化塩素水の製造
装置。5. A storage tank pressurized by a blower, a mineral acid aqueous solution tank and a chlorite aqueous solution tank, a reaction column equipped with a static mixing device, and a mixing column equipped with a static mixing device. The pressure equalizing pipe coming out of the pressure tank is connected to the upper part of each chemical liquid tank, each chemical liquid supply pipe is connected to the inlet of the reaction column from the lower part of each chemical liquid tank, and the pipe coming out of the outlet of the reaction column is connected to the inlet of the mixing column. A fresh water supply pipe is connected to an inlet of the mixing column, and chlorine water is taken out from a pipe provided from an outlet of the mixing column.
脂、塩素化塩化ビニール樹脂、硝子、テフロン、ステン
レススチールまたはチタン合金よりなるか、あるいはこ
れらの材質でライニングされていることを特徴とする請
求項５に記載の二酸化塩素の製造装置。6. The tank and the pipe are made of vinyl chloride resin, chlorinated vinyl chloride resin, glass, Teflon, stainless steel or titanium alloy, or are lined with these materials. 6. The apparatus for producing chlorine dioxide according to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25393596A JPH1081503A (en) | 1996-09-04 | 1996-09-04 | Production of chlorine dioxide water and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25393596A JPH1081503A (en) | 1996-09-04 | 1996-09-04 | Production of chlorine dioxide water and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1081503A true JPH1081503A (en) | 1998-03-31 |
Family
ID=17258068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25393596A Pending JPH1081503A (en) | 1996-09-04 | 1996-09-04 | Production of chlorine dioxide water and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1081503A (en) |
Cited By (10)
| 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 |
| JP2007143907A (en) * | 2005-11-29 | 2007-06-14 | Daisen Sangyo Kk | Air mat |
| JP2008178823A (en) * | 2007-01-25 | 2008-08-07 | Dowa Technology Kk | Plural fluids reaction method and plural fluids reaction apparatus using it |
| KR100937065B1 (en) | 2003-08-04 | 2010-01-15 | 다이꼬 야꾸힝 가부시끼가이샤 | Equipment for producing chlorine dioxide |
| KR101045062B1 (en) * | 2009-02-19 | 2011-06-29 | 김철원 | A reaction of a manufacturing device numerical sterilization water |
| KR101162536B1 (en) | 2009-10-23 | 2012-07-05 | 주식회사 에코시아 | Generator and process for aqueous solution of chlorine dioxide |
| JP2014530169A (en) * | 2011-10-14 | 2014-11-17 | インフラコアゲゼルシャフト ミット ベシュレンクテルハフツングＩｎｆｒａｃｏｒ ＧｍｂＨ | Improved method of treating water with chlorine dioxide |
| US20150140126A1 (en) * | 2008-05-26 | 2015-05-21 | Taiko Pharmaceutical Co., Ltd. | Repelling agent, bite repelling agent and arthropod-borne disease preventive agent |
| KR102041132B1 (en) * | 2019-06-24 | 2019-11-06 | 주식회사 이노푸스 | Chlorine dioxide manufacturing device and manufacturing method for removed from explosion dangeri with power-free decompression material supply and reaction |
| CN112390336A (en) * | 2019-08-13 | 2021-02-23 | 中国石油化工股份有限公司 | Negative pressure type chlorine dioxide adding device suitable for pipeline with pressure |
-
1996
- 1996-09-04 JP JP25393596A patent/JPH1081503A/en active Pending
Cited By (14)
| 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 |
| KR100456483B1 (en) * | 2002-06-28 | 2004-11-09 | (주)에스케이 아쿠아테크 | Method and apparatus for producing chlorine dioxide useful in water filtration plant |
| KR100937065B1 (en) | 2003-08-04 | 2010-01-15 | 다이꼬 야꾸힝 가부시끼가이샤 | Equipment for producing chlorine dioxide |
| JP2007143907A (en) * | 2005-11-29 | 2007-06-14 | Daisen Sangyo Kk | Air mat |
| JP4670114B2 (en) * | 2005-11-29 | 2011-04-13 | 大扇産業株式会社 | Air mat |
| JP2008178823A (en) * | 2007-01-25 | 2008-08-07 | Dowa Technology Kk | Plural fluids reaction method and plural fluids reaction apparatus using it |
| US20150140126A1 (en) * | 2008-05-26 | 2015-05-21 | Taiko Pharmaceutical Co., Ltd. | Repelling agent, bite repelling agent and arthropod-borne disease preventive agent |
| KR101045062B1 (en) * | 2009-02-19 | 2011-06-29 | 김철원 | A reaction of a manufacturing device numerical sterilization water |
| KR101162536B1 (en) | 2009-10-23 | 2012-07-05 | 주식회사 에코시아 | Generator and process for aqueous solution of chlorine dioxide |
| JP2014530169A (en) * | 2011-10-14 | 2014-11-17 | インフラコアゲゼルシャフト ミット ベシュレンクテルハフツングＩｎｆｒａｃｏｒ ＧｍｂＨ | Improved method of treating water with chlorine dioxide |
| US9743670B2 (en) | 2011-10-14 | 2017-08-29 | Infracor Gmbh | Method of treating water with chlorine dioxide |
| KR102041132B1 (en) * | 2019-06-24 | 2019-11-06 | 주식회사 이노푸스 | Chlorine dioxide manufacturing device and manufacturing method for removed from explosion dangeri with power-free decompression material supply and reaction |
| WO2020262798A1 (en) * | 2019-06-24 | 2020-12-30 | 주식회사 이노푸스 | Apparatus and method for producing aqueous chlorine dioxide eliminating risk of explosion by supplying and reacting raw material using power source-free decompression method |
| CN112390336A (en) * | 2019-08-13 | 2021-02-23 | 中国石油化工股份有限公司 | Negative pressure type chlorine dioxide adding device suitable for pipeline with pressure |
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