JP2000239003A - Method and apparatus for producing chlorine dioxide water - Google Patents
Method and apparatus for producing chlorine dioxide waterInfo
- Publication number
- JP2000239003A JP2000239003A JP11040824A JP4082499A JP2000239003A JP 2000239003 A JP2000239003 A JP 2000239003A JP 11040824 A JP11040824 A JP 11040824A JP 4082499 A JP4082499 A JP 4082499A JP 2000239003 A JP2000239003 A JP 2000239003A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine dioxide
- reactor
- water
- dioxide water
- 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.)
- Withdrawn
Links
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 87
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 230000003068 static effect Effects 0.000 claims abstract description 44
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 37
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 37
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 35
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 239000013505 freshwater Substances 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000003085 diluting agent Substances 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- -1 chlorite ions Chemical class 0.000 description 8
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 7
- 229960002218 sodium chlorite Drugs 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000011260 aqueous acid Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 description 2
- 229940005993 chlorite ion Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
(57)【要約】
【課題】連続かつ静的で高効率、高純度、高経済性な二
酸化塩素水の製造方法およびその製造装置の提供
【解決手段】亜塩素酸塩、次亜塩素酸塩及び酸を反応さ
せて二酸化塩素を製造する際、予備混合反応装置を通し
た直後に静的混合効果のあるスタティツクミキサー等を
内装した静的混合反応装置器を用い、貯圧タンクの空気
圧を利用した原料薬液供給装置を用いた二酸化塩素水の
製造装置およびそれを用いた二酸化塩素水の製造方法。PROBLEM TO BE SOLVED: To provide a method for continuously and statically producing chlorine dioxide water with high efficiency, high purity, and high cost and to provide an apparatus for producing the same. [Solution] Chlorite, hypochlorite When producing chlorine dioxide by reacting with acid and acid, immediately after passing through the premixing reactor, use a static mixing reactor equipped with a static mixer with static mixing effect, etc. A chlorine dioxide water producing apparatus using a raw material chemical supply device utilizing a method and a chlorine dioxide water producing method using the same.
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
酸化塩素水の製造方法およびそれに用いる製造装置に関
する。さらに詳しくは、反応装置として、予備混合反応
装置と静的混合効果のある静的混合反応装置を使用する
事で静的かつ連続に転換率良く、高純度な二酸化塩素水
を製造する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 method for producing chlorine dioxide water used for a wide range of purposes such as decolorization, insect repellent, and improvement of off-flavor taste, and a production apparatus used therefor. More specifically, a method for producing high-purity chlorine dioxide water statically and continuously at a high conversion rate by using a premixing reactor and a static mixing reactor having a static mixing effect as a reactor, and its method. Related to the device.
【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／リットル）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。 該二酸化塩素の
製造方法としては、パルプ漂白等の工業用の大規模な用
途では塩素酸塩に鉱酸を単独でもしくは過酸化水素、亜
硫酸ガス、メタノール等の還元性物質を加えて二酸化塩
素を発生させる製造方法が用いられている。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 / liter) and explosive in air at a gas concentration of 10% by volume or more. As a method for producing the chlorine dioxide, in a large-scale industrial application such as pulp bleaching, a mineral acid is used alone or a reducing substance such as hydrogen peroxide, sulfur dioxide, methanol or the like is added to chlorate to produce chlorine dioxide. Production methods have been used.
【０００３】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、油井賦活等の中小規模の用途では次の様な方
法が提案されている。特開平９−２０５０２号公報に
は、静的混合装置下部の清水中に亜塩素酸塩溶液、次亜
塩素酸溶液、塩酸溶液を注入して、混合、反応、希釈し
て二酸化塩素水を得ている。この方法は高効率、高純度
で高経済性であるが亜塩素酸塩から二酸化塩素への転換
効率（ここでは、これを収率と定義する）を安定的に９
０重量％以上とする事が出来ないといった問題点があ
る。すなわち、収率が９０重量％以上で塩素や亜塩素酸
イオンの不純物が発生二酸化塩素に対して５重量％以下
の高純度二酸化塩素水の要求を満たす事が出来ない。The following methods are proposed for small and medium-sized applications such as sterilization and disinfection of drinking water, improvement of off-flavor taste, deodorization of industrial wastewater, decolorization, insect control in agricultural houses, prevention of slime in cooling towers, oil well activation, and the like. Have been. Japanese Patent Application Laid-Open No. 9-20502 discloses that a chlorine dioxide solution is obtained by injecting a chlorite solution, a hypochlorous acid solution, and a hydrochloric acid solution into fresh water below a static mixing device, mixing, reacting, and diluting. ing. This method is highly efficient, highly pure and economical, but can stably control the conversion efficiency of chlorite to chlorine dioxide (this is defined as yield here).
There is a problem that it cannot be 0% by weight or more. That is, it is impossible to satisfy the requirement of high-purity chlorine dioxide water having a yield of 90% by weight or more and chlorine or chlorite ion impurities of 5% by weight or less based on the generated chlorine dioxide.
【０００４】また、特開平９−２６８２２１号公報に
は、塩素を含まない高純度で高収率で二酸化塩素が得ら
れているが、未反応として、亜塩素酸イオンが生成二酸
化塩素水に残留する可能性がある。塩素と亜塩素酸イオ
ンの両方が少ない高純度の二酸化塩素水が飲料水の殺菌
用途等では求められているのが現状である。また、製造
装置のメンテナンス面から装置の運転を長時間休止する
場合、高濃度の二酸化塩素水が反応器や希釈器に残留す
る事は装置材質への影響やマイグレートによる薬液劣化
の原因となり好ましくないが、該公報の提案には高濃度
二酸化塩素水を押し出して洗う機構が考慮されていない
といった問題点を有している。In Japanese Patent Application Laid-Open No. 9-268221, chlorine dioxide is obtained in high purity and high yield without chlorine, but chlorite ions remain in the chlorine dioxide water as unreacted. there's a possibility that. At present, high-purity chlorine dioxide water, which contains both low amounts of chlorine and chlorite ions, is demanded for sterilizing drinking water and the like. Also, when the operation of the equipment is suspended for a long time from the viewpoint of the maintenance of the manufacturing equipment, it is preferable that high concentration chlorine dioxide water remains in the reactor or dilutor because it may affect the equipment material and cause chemical deterioration due to migration. However, there is a problem in that the proposal in this publication does not consider a mechanism for extruding and washing high-concentration chlorine dioxide water.
【０００５】その他に、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、次亜塩素酸塩及び酸を反応させ、発生した二酸化塩
素を水エジェクターの下流の背圧下に水吸収と希釈を行
う方法が知られている（特開平３−６２６４１号公報、
ＵＳＰ４，２４７，５３１）。これら原料薬液の供給を
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薬液を同時に吸引するため
運転時の薬液流量が不安定になるといった問題点があ
り、また薬液吸引の為の最低限の減圧度を保つために、
毎分１０リットル以下の小容量の二酸化塩素水の製造は
出来ないという問題点を有している。[0005] In addition, chlorite aqueous solution and acid aqueous solution,
A known method involves reacting a chlorite aqueous solution with chlorine gas, or a chlorite aqueous solution, hypochlorite and an acid, and absorbing and diluting the generated chlorine dioxide under a back pressure downstream of a water ejector. (JP-A-3-62641,
USP 4,247,531). The method of sucking the supply of these raw chemicals using the reduced pressure created by the water jet ejector has the advantage of being a simple device, but it has the advantage that the chlorine dioxide gas generated under the reduced pressure and the chemical are sucked simultaneously, so the chemical during operation is sucked. There is a problem that the flow rate becomes unstable, and in order to maintain the minimum degree of decompression for the suction of the drug solution,
There is a problem that a small volume of chlorine dioxide water having a volume of 10 liters or less per minute cannot be produced.
【０００６】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工業的な方法であり、一般的に
二酸化塩素純分として１日１トン以上の用途に用いられ
ている。反応は塩素を伴い常温では反応速度が遅く、加
温や反応促進助剤の添加が必須である。それ故、塩素化
有機物生成を極端に嫌う上水殺菌や食品工業向けには不
適当である。The method using a chlorate and an acid is an industrial method used for bleaching in the pulp and paper industry, and is generally used for applications of 1 ton or more per day as pure chlorine dioxide. The reaction is accompanied by chlorine and the reaction rate is slow at room temperature, and it is essential to heat and add a reaction promoting aid. Therefore, it is unsuitable for water sterilization or the food industry, which extremely dislikes the production of chlorinated organic substances.
【０００７】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重量％
と低く、経済的に不利なばかりでなく、実際に６０重量
％の転換率を達成する為には、用いる酸の量を理論量の
３００重量％過剰で反応させなければならず、得られる
二酸化塩素水は強酸性であり、使用上に種々不利を伴
う。In the method using chlorite and acid, the theoretical conversion rate from chlorite raw material to chlorine dioxide is 80% by weight.
Not only is it economically disadvantageous, but in order to actually achieve a conversion of 60% by weight, the amount of acid used must be reacted in excess of 300% by weight of the theoretical amount, and the resulting dioxide Chlorine water is strongly acidic and has various disadvantages in use.
【０００８】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
高めるには過剰塩素で反応させる必要あり、亜塩素酸塩
と酸とを用いる方法と同様の欠点を有している。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という
欠点がある。In the method of blowing chlorine gas into a chlorite aqueous solution, it is easy to control the reaction accurately, but it is necessary to react with excess chlorine to increase the reaction rate. It has similar disadvantages. In addition, there is a drawback that danger is high because highly toxic chlorine gas is handled.
【０００９】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やすく、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製造方法
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
殺菌や脱臭に使用しようとすると、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
れているのが現状である。[0009] Since chlorine dioxide in chlorine dioxide water is dissolved as a gas, it is easily volatilized even with extremely weak bubbling or stirring, and its concentration is liable to decrease rapidly. The chlorine dioxide obtained by the conventional method using the above-mentioned water ejector is used. In the continuous production method, chlorine dioxide water has a relatively high concentration and is produced in a turbulent flow of a water ejector, so when used under normal temperature and normal pressure, the gas is easily volatilized, and the reduction in yield was a problem. .
Also, if the chlorine dioxide water obtained by these methods is used for sterilization or deodorization at a low concentration, gas volatilization also occurs at the time of dilution, which is not only uneconomical but also harmful to the human body,
At present, there is a demand for a simple method for producing chlorine dioxide water having a relatively low concentration.
【００１０】[0010]
【発明が解決しようとする課題】本発明者らは従来の技
術が有する問題点を解決した二酸化塩素水の製造方法お
よびその装置について鋭意研究した。その結果、希釈剤
として清水を添加しながら亜塩素酸塩水溶液、次亜塩素
酸塩水溶液および酸水溶液を反応させる二酸化塩素水の
製造方法において、予備混合反応器を通した薬液をこれ
の直後に接続した静的混合効果を有する静的混合反応装
置中に注入することにより、化学反応速度が常温でも速
く、しかも亜塩素酸塩の二酸化塩素への転換効率が９０
重量％以上と高く、不純物である塩素及び亜塩素酸イオ
ンの含有量が５重量％以下と低く、運転操作が簡単で、
高圧ガスや有害化合物を原料とせず、装置材質の劣化を
配慮した、得られる二酸化塩素水のｐＨが弱酸性〜中性
付近であるような二酸化塩素水の製造方法およびこの方
法に用いる装置を提供することにある。DISCLOSURE OF THE INVENTION The present inventors have intensively studied a method and an apparatus for producing chlorine dioxide water which have solved the problems of the prior art. As a result, in a method for producing a chlorine dioxide aqueous solution in which a chlorite aqueous solution, a hypochlorite aqueous solution, and an acid aqueous solution are reacted while adding fresh water as a diluent, a chemical solution passed through a premixing reactor is immediately after this. By injecting into the connected static mixing reactor having a static mixing effect, the chemical reaction rate is high even at room temperature, and the conversion efficiency of chlorite to chlorine dioxide is 90%.
% By weight and the content of impurities such as chlorine and chlorite ions is as low as 5% by weight or less.
Provided is a method for producing chlorine dioxide water in which the pH of the obtained chlorine dioxide water is weakly acidic to near neutral without considering high-pressure gas or harmful compounds as raw materials and the material of the apparatus is considered, and an apparatus used in this method. Is to do.
【００１１】[0011]
【課題を解決するための手段】本発明は以下に示され
る。 （１）反応器として、予備混合反応装置および静的混合
反応装置を用いることを特徴とする二酸化塩素水製造装
置。The present invention is described below. (1) An apparatus for producing chlorine dioxide water, wherein a premixing reactor and a static mixing reactor are used as the reactor.
【００１２】（２）薬液供給装置として、タンク内の薬
液面に加えた空気圧によりタンクより薬液を予備混合反
応装置へ送り出す圧送装置を備えた前記第１項記載の二
酸化塩素水製造装置。(2) The chlorine dioxide water producing apparatus according to the above (1), further comprising a pressure feeding device for feeding the chemical solution from the tank to the premixing reaction device by air pressure applied to the surface of the chemical solution in the tank as the chemical solution supply device.
【００１３】（３）亜塩素酸塩水溶液、次亜塩素酸塩水
溶液及び塩酸を原料とする二酸化塩素水の製造方法であ
って、予備混合反応装置中に所望量の亜塩素酸塩水溶
液、次亜塩素酸塩水溶液及び塩酸を注入し、清水流量計
を通り静的混合反応装置までの間で分岐させた清水の一
部を該予備混合反応器の最上部より該予備混合反応装置
中へ導入し、予備混合反応装置底部から流出した混合反
応希釈液を、静的混合反応装置直下より清水主流中に注
入し、該静的混合装置中へ導入して、反応と希釈を行わ
せることを特徴とする二酸化塩素水の製造方法。(3) A method for producing aqueous chlorite, aqueous hypochlorite, and aqueous chlorine dioxide using hydrochloric acid as raw materials, wherein a desired amount of aqueous chlorite is added to a premix reactor. A chlorite aqueous solution and hydrochloric acid are injected, and a portion of fresh water branched to a static mixing reactor through a fresh water flow meter is introduced into the premix reactor from the top of the premix reactor. Then, the mixed reaction diluent flowing out from the bottom of the premixing reaction device is injected into the mainstream of fresh water from immediately below the static mixing reaction device, and introduced into the static mixing device to cause reaction and dilution. Method for producing chlorine dioxide water.
【００１４】（４）亜塩素酸塩水溶液、次亜塩素酸塩水
溶液及び塩酸をタンク内の薬液面に加えた空気圧によ
り、タンクから予備混合反応装置に供給する前記第３項
記載の二酸化塩素水の製造方法。(4) The chlorine dioxide water according to the above (3), wherein the aqueous solution of chlorite, aqueous solution of hypochlorite and hydrochloric acid are supplied from the tank to the premixing reactor by air pressure applied to the surface of the chemical in the tank. Manufacturing method.
【００１５】（５）分岐させた清水の流量が、静的混合
反応装置に導入する流量の１／１０００〜１／２の流量
である前記第３項記載の二酸化塩素水の製造方法。(5) The method for producing chlorine dioxide water according to the item (3), wherein the flow rate of the branched fresh water is 1/1000 to 1/2 of the flow rate introduced into the static mixing reactor.
【００１６】（６）静的混合反応装置に供給する清水の
流速が０．０１ｍ／秒〜０．５ｍ／秒であり、得られる
二酸化塩素水中の二酸化塩素濃度が０．５ｐｐｍ（ｍｇ
／リットル）〜３０００ｐｐｍ（ｍｇ／リットル）であ
ることを特徴とする前記第３項〜第５項のいずれか１項
記載の二酸化塩素水の製造方法。(6) The flow rate of fresh water supplied to the static mixing reactor is 0.01 m / sec to 0.5 m / sec, and the chlorine dioxide concentration in the obtained chlorine dioxide water is 0.5 ppm (mg
6. The method for producing chlorine dioxide water according to any one of the above items 3 to 5, wherein the amount of chlorine dioxide water is from 3000 to 3000 ppm (mg / liter).
【００１７】[0017]
【発明の実施の形態】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
塩カルシウム等の亜塩素酸のアルカリ金属塩あるいは亜
塩素酸の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い。亜塩素酸
塩水溶液中のこれら亜塩素酸塩の濃度は、０．１重量％
から２５重量％が好ましい。亜塩素酸塩の濃度が０．１
重量％未満では二酸化塩素生成速度が遅く、収率も低く
なる。また、２５重量％を超えると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る。BEST MODE FOR CARRYING OUT THE INVENTION The chlorite used in the present invention is
It is an alkali metal salt of chlorite such as potassium chlorite, sodium chlorite, calcium chlorite or the like, or an alkaline earth metal salt of chlorite. Sodium citrate is preferred. The concentration of these chlorites in the aqueous chlorite solution is 0.1% by weight.
To 25% by weight is preferred. Chlorite concentration of 0.1
If it is less than% by weight, the chlorine dioxide production rate is low and the yield is low. If the content exceeds 25% by weight, the aqueous chlorite solution falls under the category 6 oxidizing compounds of dangerous substances, so that special consideration is required for storage and handling of raw materials.
【００１８】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
塩カルシウム等の次亜塩素酸のアルカリ金属塩もしくは
亜塩素酸の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、経済性の点から０．１重量％〜１
２．５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。The hypochlorite used in the present invention is an alkali metal salt of hypochlorous acid such as potassium hypochlorite, sodium hypochlorite, calcium hypochlorite or the like. Although it is an alkaline 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 0.1 wt% to 1 wt.
2.5% by weight is preferred. The concentration of hypochlorite is 12.
When the content is 5% by weight or more, the concentration is reduced quickly.
【００１９】本発明で用いる酸水溶液としては塩酸、硫
酸、リン酸等の鉱酸やクエン酸、酒石酸等の有機酸の水
溶液があるが、反応性と生成した二酸化塩素の安定性の
点から塩酸が好ましい。酸の濃度は、０．１重量％〜２
５重量％が好ましい。Examples of the aqueous acid solution used in the present invention include 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. Is preferred. The acid concentration ranges from 0.1% by weight to 2%.
5% by weight is preferred.
【００２０】希釈剤として清水を加えながら上記の亜塩
素酸塩水溶液、次亜塩素酸塩水溶液および酸水溶液を反
応させるための反応器として用いる静的混合効果を有す
る混合反応装置としては、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
等の１種類もしくは２種類以上を組み合わせて充填した
装置である。また、該静的混合反応装置の大きさとして
は、内径１５〜１００ｍｍ、長さ１５０〜５００ｍｍ程
度の容器で、その容量としては約２５〜４０００ｍｌ程
度の容器が用いられる。このとき、該静的混合反応装置
に圧入される薬液と清水の混合液の流量を５リットル／
分とすれば、その滞留時間は約０．３〜５０秒程度にな
る。As a mixing reactor having a static mixing effect, which is used as a reactor for reacting the aqueous chlorite solution, the aqueous hypochlorite solution and the aqueous acid solution while adding fresh water as a diluent, a static mixer is used. , A Raschig ring, a porous body, a granular body, a net-like body, a fiber filter, or the like, or a combination thereof. The size of the static mixing reaction apparatus is a container having an inner diameter of 15 to 100 mm and a length of about 150 to 500 mm, and a capacity of about 25 to 4000 ml. At this time, the flow rate of the mixed solution of the chemical solution and the fresh water injected into the static mixing reaction device was 5 liter / liter.
In minutes, the residence time is about 0.3 to 50 seconds.
【００２１】静的混合効果を有する反応混合装置の前に
接続する予備混合反応装置は高い反応率を得る為に重要
である。すなわち、３種類の薬液を濃度の高い状態で接
触、混合させ、かつ予備混合反応器中の二酸化塩素濃度
が３重量％、望ましくは２重量％を越えないようにする
ことが爆発などを考慮して安全上重要である。更に製造
装置停止後に予備混合反応装置中の高濃度二酸化塩素水
がマイグレート等により拡散し、薬液を劣化させない為
に該予備混合反応装置中に残さない工夫も安全性を高め
る上で重要である。該予備混合反応装置の容量は、あま
り大きくする必要はなく、むしろ静的混合反応装置の性
能を発揮させる為には滞留時間はせいぜい静的混合反応
装置と同程度かもしくはそれ以下の短時間の滞留時間が
確保できる容量であればよい。該予備混合反応装置中に
は混合を助けるラスヒリング等の充填物を入れる事も可
能であるが、圧力損失を考慮すると入れなくてもよい。A premix reactor connected before a reactor having a static mixing effect is important for obtaining a high conversion. In other words, it is necessary to contact and mix the three types of chemicals in a high concentration state, and to keep the chlorine dioxide concentration in the premixing reactor from exceeding 3% by weight, preferably 2% by weight, in consideration of explosions and the like. Important for safety. In addition, after the production equipment is stopped, high-concentration chlorine dioxide water in the premixing reaction device is diffused by migration or the like, and in order to prevent the chemical solution from deteriorating, it is important to improve the safety by not leaving it in the premixing reaction device. . The capacity of the premix reactor does not need to be so large, but rather, the residence time is at most as short as or shorter than that of the static mixer in order to exhibit the performance of the static mixer. Any capacity that can secure the residence time may be used. Although it is possible to put a filler such as lath hilling which assists mixing in the premixing reaction device, it is not necessary to put it in consideration of pressure loss.
【００２２】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１において、１はオイルレスベビ−コンピレ
ッサ−、２は薬液タンクの加圧、常圧切換の為の空気三
方弁、３は貯圧タンク（図示していない）の圧力調整
弁、４、５、６は薬液タンク、１０は静的混合反応装
置、１４は予備混合反応装置、１１は二酸化塩素水レシ
ーバータンクである。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 FIG. 1, reference numeral 1 denotes an oilless baby complier, 2 denotes a three-way air valve for pressurizing a chemical tank and switching between normal pressures, and 3 denotes a pressure adjusting valve for a storage tank (not shown). Is a chemical solution tank, 10 is a static mixing reactor, 14 is a preliminary mixing reactor, and 11 is a chlorine dioxide water receiver tank.
【００２３】予備混合反応器１４は、３種類の薬液と比
較的少量の清水を予備混合反応させて混合液を調製し、
静的混合反応装置１０の下部から該静的反応装置１０へ
該混合液を注入する。該静的混合反応装置１０は、３種
類の薬液と水とを静的に均質に混合、反応させることを
目的とし、スタティックミキサー、ラッシヒリング、焼
結金属等の多孔体、粒状体、ステンレス金網等の網状
体、繊維フィルター等を充填した容器である。これらの
充填物は１種類のみを用いても良いが、２種類以上を組
み合わせて用いることにより混合をより均質なものと
し、反応効率を向上させることが出来る。例えば、入口
側に粗混合をさせるためのスタティックミキサーを６段
充填し、出口側に均質な混合を得るために微細な繊維フ
ィルターを充填（充填層の長さ１〜２００ｍｍ）したも
のを例示できる。The premixing reactor 14 performs a premixing reaction of three kinds of chemicals and a relatively small amount of fresh water to prepare a mixed solution,
The mixed solution is injected into the static reaction device 10 from the lower part of the static mixing reaction device 10. The static mixing reactor 10 is for statically and homogeneously mixing and reacting three kinds of chemicals and water, and includes a static mixer, a Raschig ring, a porous material such as a sintered metal, a granular material, a stainless steel mesh, and the like. Container filled with a net-like body, a fiber filter or the like. Only one type of these fillers may be used, but by using two or more types in combination, the mixing becomes more homogeneous and the reaction efficiency can be improved. For example, a mixer in which six stages of static mixers for rough mixing are filled at the inlet side and a fine fiber filter is filled at the outlet side (length of the packed layer is 1 to 200 mm) to obtain uniform mixing can be exemplified. .
【００２４】亜塩素酸塩水溶液、次亜塩素酸塩水溶液お
よび酸水溶液はそれぞれ原料薬液タンク４、５、６に貯
蔵される。オイルレスベビーコンプレッサーからの空気
は原料薬液タンク４、５、６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。押し出された薬液は、
７の流量調節弁、８の流量計、９の逆止弁を通って、そ
れぞれ予備混合反応装置１４へ送られる。この時、亜塩
素酸塩水溶液と次亜塩素酸水溶液は予備混合反応装置１
４に入る直前で合流する。酸水溶液は上記２液の合流点
の下流で予備混合反応装置に入る。予備混合反応装置上
部からは清水用の流量計を通った清水が分岐され、水量
を絞られて流入する。流入した清水は３薬液の若干の希
釈と搬送する役割を持っている、更には製造装置停止後
の予備混合反応器１４からレシーバータンク１１への経
路（配管）の洗浄にも使用出来る。予備混合反応器１４
から出た混合溶液は静的混合反応装置１０の直下で清水
の主流と合流し、静的混合反応装置１０に導かれる。該
反応装置１０から出た二酸化塩素水はレシーバータンク
１１に貯えられる。The aqueous chlorite solution, the aqueous hypochlorite solution, and the aqueous acid solution are stored in the raw material chemical tanks 4, 5, and 6, respectively. The air from the oilless baby compressor is connected to the raw chemical tanks 4, 5, and 6 by pressure equalizing tubes.
It works to push out the raw chemical solution. The extruded chemical solution
The liquid is sent to the premixing reaction device 14 through a flow control valve 7, a flow meter 8, and a check valve 9. At this time, the chlorite aqueous solution and the hypochlorous acid aqueous solution
Merge just before entering 4. The aqueous acid solution enters the premixing reactor downstream of the junction of the two solutions. From the upper part of the premixing reactor, fresh water passing through a fresh water flow meter is branched, and the amount of fresh water is reduced and flows into the fresh water. The inflowing fresh water has the role of slightly diluting and transporting the three chemicals, and can also be used for cleaning the path (piping) from the premixing reactor 14 to the receiver tank 11 after the production equipment is stopped. Premix reactor 14
The mixed solution that has come out of the tank merges with the main stream of fresh water immediately below the static mixing reactor 10 and is guided to the static mixing reactor 10. Chlorine dioxide water discharged from the reactor 10 is stored in a receiver tank 11.
【００２５】ベビーコンプレッサー付属の貯圧タンク
（図示していない）の圧力は、水柱圧表示で、装置の地
上高さ以上が必要であり、配管及び反応器における液体
の抵抗を考慮すれば装置高さプラス数メートル（水柱）
とすれば良い。貯圧タンク容量は大きい方が圧力変動が
少なくて好ましいが、現実的には３薬液タンク容量の合
計と同等以上あれば支障ない。オイルレスベビ−コンプ
レッサ−は、３薬液の減る量の１００〜１０００倍の風
量が得られ、貯圧タンクの圧力調節弁を閉じた状態で、
前記貯圧タンクの圧力以上の圧力が得られるものであれ
ば、貯圧タンクの圧力変動率は１〜０.１％程度とな
り、充分安定運転が出来る。The pressure of the storage tank (not shown) attached to the baby compressor is required to be higher than the height of the apparatus above the height of the apparatus in water column pressure display. Plus a few meters (water column)
It is good. It is preferable that the pressure storage tank capacity is large because the pressure fluctuation is small. The oil-less baby-compressor has a flow rate of 100 to 1000 times the reduced amount of the three chemicals, and the pressure control valve of the storage tank is closed.
If a pressure equal to or higher than the pressure of the pressure storage tank can be obtained, the pressure fluctuation rate of the pressure storage tank will be about 1 to 0.1%, and a sufficiently stable operation can be performed.
【００２６】均圧管 は、ここを通過する空気流量（＝
薬液の送出し量）が少ないため、内径が１／２〜２イン
チあれば充分である。圧力調節弁にはボール弁、ブロー
ブ弁、仕切弁等が良い。３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。流量計は広範囲の流量を且
つ正確に計れることから、ローターメーターやボールタ
イプのものが好ましい。３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流防止弁が必要である。The equalizing pipe has a flow rate of air passing therethrough (=
Since the amount of the chemical solution delivered is small, it is sufficient if the inner diameter is 1/2 to 2 inches. As the pressure control valve, a ball valve, a probe valve, a gate valve, and the like are preferable. A needle valve that can finely adjust the flow rate of the three chemicals is preferable. Since the flow meter can accurately measure a wide range of flow rate, a rotor meter or a ball type is preferable. (3) A check valve is required in the line of the chemical and the fresh water to prevent the mixture from flowing back.
【００２７】清水は圧力変動が少ないことが要求され、
ポンプ送水による圧水又は水道水が使用できる。[0027] Shimizu is required to have a small pressure fluctuation,
Pressurized water from tap water or tap water can be used.
【００２８】本発明の二酸化塩素水製造装置は、一定流
量の清水中に発生させるべき二酸化塩素の所望の濃度に
応じた流量の薬液を供給する構造であるので、清水の供
給が停止した場合には自動的に薬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基の薬液
タンクのどれか１基でも空になった場合には、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。The chlorine dioxide water producing apparatus of the present invention has a structure for supplying a chemical solution at a flow rate corresponding to a desired concentration of chlorine dioxide to be generated in a constant flow of fresh water. It is desirable to incorporate a mechanism for automatically stopping the supply of the chemical solution. In addition, it is preferable that the supply of all the liquid chemicals is stopped when any one of the three liquid chemical tanks becomes empty.
【００２９】原料薬液タンクは原料薬液の多少によらず
常に一定の空気圧により原料薬液を送り出すので、無脈
動で定量的な送液ができる。The raw chemical tank always sends out the raw chemical at a constant air pressure irrespective of the amount of the raw chemical, so that non-pulsating and quantitative liquid supply is possible.
【００３０】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、いずれも少流量の上述の亜塩
素酸塩水溶液、次亜塩素酸塩水溶液および酸水溶液をほ
ぼ化学量論とおりの比率で、予備混合反応装置へ注入
し、分岐された清水で希釈、混合されたのち、該混合液
を０．０１〜０．５ｍ／秒の清水流中に無脈動で定量的
に注入する。清水の流速が０．０１ｍ／秒未満であると
攪拌混合効果が期待できなくなり、また、清水の流量が
０．５ｍ／秒を超えると、反応液が乱流になり溶液中に
溶解している二酸化塩素ガスが気泡となって揮散し、二
酸化塩素濃度が低下することがある。In the method of the present invention, the above-mentioned aqueous solution of chlorite, aqueous solution of hypochlorite, and aqueous solution of acid are all supplied at a substantially stoichiometric ratio by the raw material chemical supply system of the storage tank type. Then, after diluting and mixing with the branched fresh water, the mixed solution is quantitatively injected into a 0.01 to 0.5 m / sec fresh water flow without pulsation. If the flow rate of the fresh water is less than 0.01 m / sec, the effect of stirring and mixing cannot be expected. If the flow rate of the fresh water exceeds 0.5 m / sec, the reaction liquid becomes turbulent and is dissolved in the solution. Chlorine dioxide gas may evaporate as bubbles, resulting in a decrease in chlorine dioxide concentration.
【００３１】予備混合反応装置中に導かれる清水の流量
は静的混合反応装置の流入量の千分の１以上、２分の１
以下の範囲にすることが好ましいが、かかる流入量にコ
ントロ−ルする方法としては予備混合反応装置１４の入
口径を、流量計から静的混合反応装置間の管径と同径以
下で、１００分の１以上にする方法が挙げられる。予備
混合反応装置１４への清水の流入量は、０でなく、限り
なく小量で構わないが、現実的に可能な量は千分の１以
上であり、上限は分岐等量の２分の１以下である。同様
に管径を絞る方法で実用性ある範囲は１００分の１以
上、導管径と同径以下である。予備混合反応装置１４は
もっぱら主反応装置器１０の前に装備して３薬液が濃い
状態で接触混合され、反応率を高める為のものであり、
３薬液の反応は常温に於いても著しく早いので滞留時間
を出来るだけ短時間とするのが好ましく、混合率を高め
るためのラスヒリング等の充填はしなくて良いがしても
構わない。The flow rate of fresh water introduced into the premixing reactor is at least one-thousandth and one-half the inflow of the static mixing reactor.
It is preferable to set the inlet diameter of the premixing reactor 14 to the following range. There is a method of reducing the number by a factor of 1 or more. The flow rate of fresh water into the premixing reactor 14 is not limited to zero, and may be as small as possible. However, a practically possible amount is one thousandth or more, and the upper limit is a half of the equivalent amount of branching. 1 or less. Similarly, the practical range of the method for reducing the pipe diameter is 1/100 or more and equal to or less than the pipe diameter. The pre-mixing reactor 14 is provided solely in front of the main reactor 10 and is used to increase the reaction rate by contact-mixing the three chemicals in a concentrated state,
Since the reaction of the three chemicals is remarkably fast even at room temperature, the residence time is preferably as short as possible, and it is not necessary to fill in Rashilling or the like to increase the mixing ratio.
【００３２】清水流中に注入する３種類の原料薬液の量
は、得ようとする二酸化塩素水の濃度に依存するが、例
えば１０００ｐｐｍの二酸化塩素水を得るには、０．３
重量％の亜塩素酸ソーダ水溶液、０．２重量％の次亜塩
素酸ソーダ水溶液および０．２重量％の塩酸をそれぞれ
２０〜２５０ｍｌ／分の流量で圧送する。かくして、流
速が０．０１〜０．５ｍ／秒の清水流中に、ほぼ化学量
論量（反応理論量）の比率の上述の３種の原料溶液を均
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、収率９０重量％以上で塩素や亜塩素
酸イオン不純物が生成二酸化塩素量に対して５重量％以
下である二酸化塩素水が得られる。The amounts of the three kinds of raw material chemicals to be injected into the fresh water stream depend on the concentration of chlorine dioxide water to be obtained.
A weight percent aqueous solution of sodium chlorite, a 0.2 weight percent aqueous solution of sodium hypochlorite and a 0.2 weight percent hydrochloric acid are pumped at a flow rate of 20 to 250 ml / min. Thus, in the fresh water stream having a flow rate of 0.01 to 0.5 m / sec, the above three kinds of raw material solutions having a ratio of substantially stoichiometric amount (theoretical amount of reaction) are supplied by the raw material chemical supply system of the equalizing tank system. It is sent quantitatively with a small flow rate and no pulsation to obtain chlorine dioxide water with a yield of 90% by weight or more and chlorine or chlorite ion impurities of 5% by weight or less based on the generated chlorine dioxide.
【００３３】[0033]
【実施例】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ｐＨ７でのチオ硫
酸ソーダ標準液を用いた酸化還元滴定法により求めた。 反応収率（重量％）＝（ClO2測定値(ppm)／ClO2理論値
(ppm)）×１００ なお、ClO2理論値は次式より、主原料NaClO2を基準に計
算した。 2NaClO2＋NaClO＋2HCl＝2ClO2＋3NaCl＋H2O 純度（重量％）＝（ClO2測定値(ppm)／ClO2測定値(ppm)
＋Cl2(ppm)＋ClO2 -(ppm)）×１００ Cl2とClO2 -の濃度はｐＨ７とｐＨ２の２点でチオ硫酸ソ
−ダ標準液を用いた酸化還元滴定法による滴定値より計
算で求めた。EXAMPLES The present invention will be described more specifically with reference to examples. The concentration of chlorine dioxide water was measured by a redox titration method using a sodium thiosulfate standard solution at pH 7. Reaction yield (% by weight) = (measured value of ClO 2 (ppm) / theoretical value of ClO 2
(ppm)) × 100 The theoretical value of ClO 2 was calculated from the following formula based on the main raw material NaClO 2 . 2NaClO 2 + NaClO + 2HCl = 2ClO 2 + 3NaCl + H 2 O Purity (% by weight) = (ClO 2 measured value (ppm) / ClO 2 measured value (ppm)
+ Cl 2 (ppm) + ClO 2 - (ppm)) × 100 Cl 2 and ClO 2 - concentrations thiosulfate source at two points pH7 and pH 2 - by calculation from the titration value by redox titration with da standard solution I asked.
【００３４】反応装置 薬液タンクとして、３個の５０リットル容積の塩化ビニ
ール樹脂製で耐圧０．６メガパスカルの円筒容器を用
い、０．４９−０．６９メガパスカルの圧力調節弁、１
５リットル貯圧タンク付のオイルフリーレシプロコンプ
レッサー（岩田塗装機工業製）を用いた。均圧管と空気
搬送チューブは耐圧０．７メガパスカルのナイロン製フ
レキシブルチューブ使用した。静的混合反応装置は塩化
ビニル樹脂製のスタテイックミキサ−（ノリタケ社製１
／２−Ｎ５０−１７１１型）を、予備混合反応装置とし
て管径１３Ａ、長さ２５ｍｍの円筒状容器を用い、分岐
した清水が流入する該予備混合反応装置の最上部は口径
６．５Ａのパイプで接続されている。塩化ビニル樹脂製
の逆止弁、空気減圧弁（岩田塗装機製）、塩化ビニル樹
脂製ボールバルブ、溶液配管は管径１３Ａの塩化ビニル
樹脂製の管を用い、図１に例示した反応装置を使用し
た。パネル前面での操作は薬液用ＰＶＣ製流量計３本
（流体工業製）、清水用ＳＵＳ製流量計（流体工業
製）、空気三方弁（スエジロック製）で行う。薬液タン
クから本体への輸送はＰＴＦＥ製フレキシブルチューブ
を使用した。Reactor As a chemical liquid tank, three 50 liter cylindrical containers made of vinyl chloride resin and having a pressure resistance of 0.6 megapascal were used, and a pressure control valve of 0.49 to 0.69 megapascal was used.
An oil-free reciprocating compressor (manufactured by Iwata Paint Co., Ltd.) equipped with a 5-liter storage tank was used. As the pressure equalizing tube and the air conveying tube, a nylon flexible tube having a pressure resistance of 0.7 megapascal was used. The static mixing reactor is a static mixer made of vinyl chloride resin (1 manufactured by Noritake Co., Ltd.).
/ 2-N50-1711 type) was used as a premixing reactor, a cylindrical vessel having a tube diameter of 13A and a length of 25 mm, and a pipe having a diameter of 6.5 A was provided at the top of the premixing reactor into which branched fresh water flows. Connected by A check valve made of vinyl chloride resin, an air pressure reducing valve (manufactured by Iwata Coating Machine), a ball valve made of vinyl chloride resin, and a solution pipe using a pipe made of vinyl chloride resin having a diameter of 13A, using the reactor illustrated in FIG. did. The operation on the front of the panel is performed with three PVC flowmeters for chemicals (manufactured by Fluid Industries), SUS flowmeters for fresh water (manufactured by Fluid Industries), and a three-way air valve (manufactured by Swediroc). A flexible tube made of PTFE was used for transportation from the chemical solution tank to the main body.
【００３５】実施例１〜６ 二酸化塩素水の製造 亜塩素酸塩として亜塩素酸ソーダ、次亜塩素酸塩として
次亜塩素酸ソーダ、酸として塩酸を選び下記の濃度の原
料薬液を調製した。 亜塩素酸ソーダ水溶液 １０．００重量％ 次亜塩素酸ソーダ水溶液 ４．１６重量％ 塩酸水溶液 ４．４８重量％ 後述の表１に示した水道水流量と各薬液供給流量で二酸
化塩素水をそれぞれ製造した。表１の結果の如く、生成
した二酸化塩素水は全て収率９０重量％以上で純度９５
重量％以上であった、ｐＨも弱酸性〜酸性であった。Examples 1 to 6 Production of Chlorine Dioxide Water Sodium chlorite was used as a chlorite, sodium hypochlorite was used as a hypochlorite, and hydrochloric acid was used as an acid. Aqueous sodium chlorite solution 10.00% by weight Aqueous sodium hypochlorite solution 4.16% by weight Hydrochloric acid aqueous solution 4.48% by weight Chlorine dioxide water is produced at the tap water flow rate and the chemical solution supply flow rate shown in Table 1 below. did. As shown in Table 1, all the produced chlorine dioxide water had a yield of 90% by weight or more and a purity of 95%.
The pH was also slightly acidic to acidic.
【００３６】[0036]
【表１】 [Table 1]
【００３７】比較例１〜４ 製造装置として、特開平９−２０５０２号公報に示され
た装置に準拠した静的混合装置を用いて、後述の表２に
示した水道水流量と各薬液供給量で二酸化塩素水の製造
を行った。亜塩素酸塩として亜塩素酸ソ−ダ、次亜塩素
酸塩として次亜塩素酸ソ−ダ、酸として塩酸を選び下記
の濃度の薬液を調製した。 亜塩素酸ソ−ダ水溶液 ２５．０重量％ 次亜塩素酸ソ−ダ水溶液 １２．５重量％ 塩酸水溶液 １２．６重量％ なお、二酸化塩素水の濃度の測定と不純物塩素量の測定
は、ｐＨ７とｐＨ２でのチオ硫酸ソ−ダ標準液を用いた
酸化還元滴定法により行った。その結果を表２に示し
た。表２から明らかなように、同じ薬液量と希釈水量で
１０分間間隔で２回繰り返し運転した結果では再現性は
良かったが、常に収率９０重量％を達成できてなく、純
度も常に９５重量％以上を達成できていないことがわか
る。COMPARATIVE EXAMPLES 1-4 As a production apparatus, a static mixing apparatus based on the apparatus disclosed in Japanese Patent Application Laid-Open No. 9-20502 was used. Produced chlorine dioxide water. Sodium chlorite was used as the chlorite, sodium hypochlorite was used as the hypochlorite, and hydrochloric acid was used as the acid to prepare a chemical solution having the following concentrations. Sodium chlorite aqueous solution 25.0% by weight Sodium hypochlorite aqueous solution 12.5% by weight Hydrochloric acid aqueous solution 12.6% by weight The measurement of the concentration of chlorine dioxide water and the measurement of the amount of impurity chlorine were performed at pH7. And a redox titration method using a standard solution of sodium thiosulfate at pH 2. The results are shown in Table 2. As is evident from Table 2, reproducibility was good as a result of repeating the operation twice at 10-minute intervals with the same amount of chemical solution and dilution water, but the yield was not always 90% by weight and the purity was always 95% by weight. % Can not be achieved.
【００３８】[0038]
【表２】 [Table 2]
【００３９】比較例５，６ 原料薬液の供給を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特開平３−６２６４１号公報に開
示の装置に準拠した装置を用いて二酸化塩素水の製造を
行った。すなわち、リオリンダ社製の二酸化塩素水発生
機Ｔ１４０ＷＭ型を用いて、エゼクタ−ノズル径０．１
４インチ、水流ポンプの水量２０リットル／分、吐出圧
力０．６ＭＰａ、の条件で、二酸化塩素水１００リット
ルを製造した。その結果を表３に示した。なお、用いた
薬液の濃度は以下の通り。 亜塩素酸ソ−ダ水溶液 ２５．０重量％ 次亜塩素酸ソ−ダ水溶液 １２．０重量％ 塩酸水溶液 １５．０重量％ 表３から明らかなように、収率が低く、純度も９５重量
％未満であることがわかる。Comparative Examples 5 and 6 Production of chlorine dioxide water was carried out using an apparatus based on the apparatus disclosed in Japanese Patent Application Laid-Open No. 3-62641, in which the supply of the raw material chemical solution was carried out using the reduced pressure created by a water jet ejector. went. That is, an ejector-nozzle diameter of 0.1 using a chlorine dioxide water generator T140WM manufactured by Riolinda.
100 liters of chlorine dioxide water was manufactured under the conditions of 4 inches, a water flow rate of a water flow pump of 20 liters / minute, and a discharge pressure of 0.6 MPa. Table 3 shows the results. The concentrations of the used chemicals are as follows. Sodium chlorite aqueous solution 25.0% by weight Sodium hypochlorite aqueous solution 12.0% by weight Hydrochloric acid aqueous solution 15.0% by weight As is clear from Table 3, the yield is low and the purity is 95% by weight. It turns out that it is less than.
【００４０】[0040]
【表３】 [Table 3]
【００４１】[0041]
【発明の効果】本発明の製造方法は、予備混合反応器を
通した薬液をこれの直後に接続した静的混合効果を有す
る静的混合反応装置中に注入することにより、化学反応
速度が常温でも速く、しかも亜塩素酸塩の二酸化塩素へ
の転換効率が９０重量％以上と高く、不純物である塩素
及び亜塩素酸イオンの含有量が５重量％以下と低く、運
転操作が簡単で、高圧ガスや有害化合物を原料とせず、
その上、得られる二酸化塩素水のｐＨが弱酸性〜中性付
近にあるような二酸化塩素水を連続して製造する事が出
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でもある。本
発明は低濃度の二酸化塩素水の製造にも好適であるばか
りでなく、種々の用途に応じた広範囲の濃度の二酸化塩
素水の製造にもタイムリーに対応可能である。また、本
発明の製造装置は予備混合反応装置および静的混合反応
装置を備えているので、亜塩素酸塩の二酸化塩素への転
換率が高く、高純度、弱酸性〜中性付近のｐＨの二酸化
塩素水を経済性と安全性高く、簡単な操作で、各種濃度
の二酸化塩素水を製造する事が出来る装置である。According to the production method of the present invention, the chemical reaction rate is at room temperature by injecting the chemical solution passed through the premixing reactor into a static mixing reactor having a static mixing effect connected immediately after the premixing reactor. However, it is fast, and the conversion efficiency of chlorite to chlorine dioxide is as high as 90% by weight or more, and the content of impurities such as chlorine and chlorite ions is as low as 5% by weight or less. Without using gas or harmful compounds as raw materials,
In addition, it is possible to continuously produce chlorine dioxide water in which the pH of the obtained chlorine dioxide water is weakly acidic to about neutral. And it is a method 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 the production of low-concentration chlorine dioxide water, but also can timely cope with the production of a wide range of concentration of chlorine dioxide water according to various uses. Further, since the production apparatus of the present invention is provided with a premixing reaction apparatus and a static mixing reaction apparatus, the conversion rate of chlorite to chlorine dioxide is high, and high purity, weak acidity to pH around neutrality are obtained. This is an equipment that can produce chlorine dioxide water of various concentrations by simple operation with high economic efficiency and safety.
【 図１】本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.
１：オイルレスベビ−コンプレッサ− ２：空気三方弁 ３：圧力調節弁 ４：亜塩素酸塩水溶液タンク ５：次亜塩素酸塩水溶液タンク ６：酸水溶液タンク ７：流量調節弁 ８：流量計 ９：逆止弁 １０：静的混合反応装置（スタテイックミキサ−） １１：二酸化塩素水レシ−バ−タンク １２：希釈水（清水）入口 １３：ストップ弁 １４：予備混合反応装置 １５：亜硫酸ソ−ダ溶液ガス洗瓶 １６：タンクレベル計 1: oilless baby compressor 2: air three-way valve 3: pressure control valve 4: chlorite aqueous solution tank 5: hypochlorite aqueous solution tank 6: acid aqueous solution tank 7: flow control valve 8: flow meter 9: reverse Stop valve 10: Static mixing reactor (static mixer) 11: Chlorine dioxide water receiver tank 12: Dilution water (clear water) inlet 13: Stop valve 14: Premix reactor 15: Sodium sulfite solution Gas Wash Bottle 16: Tank Level Meter
Claims (6)
的混合反応装置を用いることを特徴とする二酸化塩素水
製造装置。1. An apparatus for producing chlorine dioxide water, wherein a premixing reactor and a static mixing reactor are used as a reactor.
加えた空気圧によりタンクより薬液を予備混合反応装置
へ送り出す圧送装置を備えた請求項１記載の二酸化塩素
水製造装置。2. The chlorine dioxide water producing apparatus according to claim 1, further comprising a pressure feeding device for feeding the chemical solution from the tank to the premixing reaction device by air pressure applied to the surface of the chemical solution in the tank.
び塩酸を原料とする二酸化塩素水の製造方法であって、
予備混合反応装置中に所望量の亜塩素酸塩水溶液、次亜
塩素酸塩水溶液及び塩酸を注入し、清水流量計を通り静
的混合反応装置までの間で分岐させた清水の一部を該予
備混合反応器の最上部より該予備混合反応装置中へ導入
し、予備混合反応装置底部から流出した混合反応希釈液
を、静的混合反応装置直下から清水主流中に注入し、該
静的混合反応装置中へ導入して、反応と希釈を行わせる
ことを特徴とする二酸化塩素水の製造方法。3. A method for producing chlorine dioxide water from a chlorite aqueous solution, a hypochlorite aqueous solution and hydrochloric acid as raw materials,
A desired amount of chlorite aqueous solution, hypochlorite aqueous solution, and hydrochloric acid were injected into the premixing reactor, and a portion of fresh water branched to a static mixing reactor through a freshwater flow meter was removed. The mixed reaction diluent introduced from the top of the premix reactor into the premix reactor, and the mixed reaction diluent flowing out from the bottom of the premix reactor is injected into the mainstream of fresh water from immediately below the static mixing reactor, and the static mixing is performed. A method for producing chlorine dioxide water, wherein the chlorine dioxide water is introduced into a reactor to cause a reaction and dilution.
び塩酸をタンク内の薬液面に加えた空気圧により、タン
クから予備混合反応装置に供給する請求項３記載の二酸
化塩素水の製造方法。4. The process for producing chlorine dioxide water according to claim 3, wherein the aqueous solution of chlorite, aqueous solution of hypochlorite and hydrochloric acid are supplied to the premixing reactor from the tank by air pressure applied to the surface of the chemical in the tank. Method.
置に導入する流量の１／１０００〜１／２の流量である
請求項３記載の二酸化塩素水の製造方法。5. The method for producing chlorine dioxide water according to claim 3, wherein the flow rate of the branched fresh water is 1/1000 to 1/2 of the flow rate introduced into the static mixing reactor.
０．０１ｍ／秒〜０．５ｍ／秒であり、得られる二酸化
塩素水中の二酸化塩素濃度が０．５ｐｐｍ（ｍｇ／リッ
トル）〜３０００ｐｐｍ（ｍｇ／リットル）であること
を特徴とする請求項３〜請求項５のいずれか１項記載の
二酸化塩素水の製造方法。6. The flow rate of fresh water supplied to the static mixing reactor is 0.01 m / sec to 0.5 m / sec, and the concentration of chlorine dioxide in the obtained chlorine dioxide water is 0.5 ppm (mg / liter). The method for producing chlorine dioxide water according to any one of claims 3 to 5, wherein the concentration is 3000 ppm (mg / liter).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11040824A JP2000239003A (en) | 1999-02-19 | 1999-02-19 | Method and apparatus for producing chlorine dioxide water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11040824A JP2000239003A (en) | 1999-02-19 | 1999-02-19 | Method and apparatus for producing chlorine dioxide water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000239003A true JP2000239003A (en) | 2000-09-05 |
Family
ID=12591423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11040824A Withdrawn JP2000239003A (en) | 1999-02-19 | 1999-02-19 | Method and apparatus for producing chlorine dioxide water |
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| Country | Link |
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| JP (1) | JP2000239003A (en) |
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| JP2006044973A (en) * | 2004-08-03 | 2006-02-16 | Business Plan Kk | Chlorine dioxide aqueous solution manufacturing method |
| WO2009001777A1 (en) * | 2007-06-26 | 2008-12-31 | Taiko Pharmaceutical Co., Ltd. | Method for producing chlorine dioxide and alkali composition for chlorine dioxide production which is used in the method |
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| WO2009001777A1 (en) * | 2007-06-26 | 2008-12-31 | Taiko Pharmaceutical Co., Ltd. | Method for producing chlorine dioxide and alkali composition for chlorine dioxide production which is used in the method |
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