JP2006007190A - Method for generating chlorine dioxide solution - Google Patents
Method for generating chlorine dioxide solution Download PDFInfo
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- JP2006007190A JP2006007190A JP2004213669A JP2004213669A JP2006007190A JP 2006007190 A JP2006007190 A JP 2006007190A JP 2004213669 A JP2004213669 A JP 2004213669A JP 2004213669 A JP2004213669 A JP 2004213669A JP 2006007190 A JP2006007190 A JP 2006007190A
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- chlorine dioxide
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- acid
- dioxide solution
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 41
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 29
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000001384 succinic acid Substances 0.000 claims abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004332 deodorization Methods 0.000 claims abstract description 4
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 abstract 3
- 230000001954 sterilising effect Effects 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- -1 pulp Substances 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- 230000009182 swimming Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
本発明は、消毒・消臭用途において有用な二酸化塩素溶液について機械的な装置を必要とせず、短時間かつ安全に任意の濃度の溶液を生成する事を可能にする生成方法ならびに生成剤に関するものである。 The present invention relates to a production method and a production agent capable of producing a solution of any concentration in a short time and safely without requiring a mechanical device for a chlorine dioxide solution useful for disinfection and deodorization applications. It is.
二酸化塩素溶液は紙、綿、パルプ、及びその他繊維材料中における自然色素の酸化による漂白剤として、また、殺菌剤、殺ウイルス剤、殺藻剤として上下水道の殺菌、スイミングプールの殺菌・濁度の改善、観賞用池水における殺藻処理など広汎な用途で利用されてきた。しかし、このように有用な二酸化塩素は実用的な側面において問題があった。
Chlorine dioxide solution is a bleaching agent by oxidation of natural pigments in paper, cotton, pulp, and other textile materials, as well as disinfecting water and sewage as a disinfectant, viricide, and algicide, disinfecting and turbidity of swimming pools It has been used for a wide range of purposes, such as improving the quality of water and algae treatment in ornamental pond water. However, such useful chlorine dioxide has a problem in practical aspects.
それは、二酸化塩素はその物性において爆発性、毒性、光・熱に対する分解性を有するためガス状で運搬出来ない点である。また安定性の増す二酸化塩素溶液についても本来の物性による不可避的な問題として濃度の維持が難しく、ガス状の二酸化塩素と同様、運搬による使用には難点があった。 That is, chlorine dioxide cannot be transported in the form of gas because it has explosive properties, toxicity, and decomposability to light and heat. In addition, the chlorine dioxide solution with increased stability is difficult to maintain as an unavoidable problem due to the original physical properties, and there is a difficulty in using it by transportation like gaseous chlorine dioxide.
その結果、現場で容易に生成出来る二酸化塩素溶液生成装置が求められ、「特許文献１」や「特許文献２」他多くの知見が示されている。 As a result, a chlorine dioxide solution generating device that can be easily generated on site is required, and many other findings such as “Patent Document 1” and “Patent Document 2” are shown.
二酸化塩素溶液を現場で日常的な作業に支障をきたさない３０分以内に任意の濃度を生成するためには、従来は取扱いの上で危険な塩素や塩酸、硫酸といった強酸を用いる必要があり、その結果、前記のように安全性を保つため次亜塩素酸や亜塩素酸など二酸化塩素溶液の生成に必要な液剤を処理水系に分注する装置が利用されてきた。 In order to produce an arbitrary concentration within 30 minutes that does not interfere with daily work at the site, it is necessary to use a strong acid such as chlorine, hydrochloric acid or sulfuric acid, which is dangerous in handling. As a result, in order to maintain safety as described above, an apparatus for dispensing a liquid agent necessary for producing a chlorine dioxide solution such as hypochlorous acid or chlorous acid into a treated water system has been used.
しかし、この方法では設備導入にかかる経済的な負担が多大であり、また、薬剤による設備への悪影響が問題であった。 However, this method has a great economic burden on the introduction of the equipment, and the adverse effect of the medicine on the equipment has been a problem.
一方、まったく化学的な素養のない一般の使用を前提として、二酸化塩素溶液を提供する場合、二酸化塩素発生剤と比較的安全性の高い有機酸、代表的にはクエン酸などを用いて両液を混合する事により二酸化塩素溶液を供給する方法が取られている。 On the other hand, in the case of providing a chlorine dioxide solution on the premise of general use without any chemical knowledge, both solutions using a chlorine dioxide generator and a relatively safe organic acid, typically citric acid, are used. A method of supplying a chlorine dioxide solution by mixing the two is used.
しかしこのような方法では３０分以内で実用的な濃度を生成する事は事実上不可能であり。およそ１２時間〜２４時間かかる事が常であった。 However, with such a method, it is practically impossible to produce a practical concentration within 30 minutes. It usually took about 12-24 hours.
つまり、従来は短時間で実用的な二酸化塩素溶液を得るには極めて危険な薬剤を用いるか、大規模な機械装置を必要とし、安全な薬剤を用いると到底実用的な作業時間内で二酸化塩素溶液を得る事は出来なかった。 In other words, conventionally, a very dangerous chemical is used to obtain a practical chlorine dioxide solution in a short time, or a large-scale mechanical device is required. If a safe chemical is used, chlorine dioxide can be used within a practical working time. The solution could not be obtained.
例えば、「特許文献３」「特許文献４」のように亜塩素酸と酸を反応させる一般的な方法の理解や広いｐＨにおける有効性、さらにはゲルなどに吸着させる事による応用的な使用法などを示す情報はあっても、前記の諸問題を根本的に解決する知見は存在しない。従って、本発明はこの二律背反的な事象に整合性をもたらし、安全な薬剤を用いて短時間の作業性を実現する事を目的とする。 For example, as in “Patent Document 3” and “Patent Document 4”, an understanding of a general method of reacting chlorous acid with an acid, the effectiveness in a wide pH range, and an applied usage method by adsorbing to a gel or the like However, there is no knowledge to fundamentally solve the above problems. Accordingly, it is an object of the present invention to bring consistency to this contradictory event and to realize a short workability using a safe drug.
前記課題の解決にあたり、本発明者は鋭意研究を重ねた結果、二酸化塩素発生剤にコハク酸を含有する活性剤を用いる事により、目的を達成出来る事を知見し、本発明を完成した。 As a result of intensive studies, the present inventor has found that the object can be achieved by using an activator containing succinic acid as a chlorine dioxide generator, and has completed the present invention.
本発明の請求項２は産業的な実用性の観点から２０℃〜４５℃の水温、０．５ｔ〜８００ｔ程度の水量を所与の外的条件とした上で、コハク酸の有効な含有率を算出している。
具体的には、公衆浴場など４２℃前後の水温に設定されている場合を想定しており、当然に水温が高いほど反応が速く短時間に二酸化塩素の濃度が高くなる。Claim 2 of the present invention is an effective content of succinic acid with a water temperature of 20 ° C. to 45 ° C. and a water amount of about 0.5 t to 800 t being given external conditions from the viewpoint of industrial practicality. Is calculated.
Specifically, it is assumed that the water temperature is set to around 42 ° C., such as a public bath, and naturally the higher the water temperature, the faster the reaction and the higher the concentration of chlorine dioxide in a short time.
一方プールなどでは、水温の設定がおよそ３０℃〜３５℃に設定されている。また、およそ水の水温が２０℃前後である事を鑑み、本発明では実用的な水温として２０℃以上を採用した。 On the other hand, in a pool or the like, the water temperature is set to about 30 ° C to 35 ° C. In view of the fact that the water temperature is about 20 ° C., a practical water temperature of 20 ° C. or higher is adopted in the present invention.
一般論として、処理対象の水温が高ければ高いほど、反応に要する時間は短くなり、少量の薬剤でもって、必要な濃度を得る事が可能になる。しかし、既に述べたように実際の産業的な利用価値は２０℃〜４５℃の範囲に収束しており、その範囲を著しく逸脱する条件下での仮定は実用的に無価値であるため本発明ではその仮定を排除した。 In general, the higher the water temperature to be treated, the shorter the time required for the reaction, and the necessary concentration can be obtained with a small amount of chemicals. However, as described above, the actual industrial utility value has converged in the range of 20 ° C. to 45 ° C., and assumptions under conditions that deviate significantly from the range are practically worthless. So I removed that assumption.
また、主剤の処理水量に対する含有量を著しく増大させる事によって、二酸化塩素濃度を得る事も考えられるが、未反応の亜塩素酸イオンが多量に残るがごとき状況は安全性、経済性の両面から好ましくないため本発明においてはその仮定を排除した。 In addition, it is conceivable to obtain a chlorine dioxide concentration by significantly increasing the content of the main agent with respect to the amount of treated water, but a large amount of unreacted chlorite ions remain, but the situation is both safe and economical. Since it is not preferable, the assumption is excluded in the present invention.
一方、本発明はその精神において、コハク酸が他の活性剤に対して著しく二酸化塩素を生成する上で有効である事を示す知見であって、他の活性剤の候補となる、クエン酸や乳酸などの混合を排除する物ではない。 On the other hand, the present invention is a knowledge showing that succinic acid is remarkably effective in producing chlorine dioxide with respect to other active agents in its spirit, and is a candidate for other active agents such as citric acid and It is not something that excludes mixing of lactic acid.
この発明による二酸化塩素溶液の生成にはコハク酸を固相で用いる事がより望ましく、高い濃度を短時間で得る事が可能になる。 For the production of the chlorine dioxide solution according to the present invention, it is more desirable to use succinic acid in the solid phase, and a high concentration can be obtained in a short time.
固相のコハク酸は必要ならば香料、安定剤、賦形剤等を添加して、円柱状などに調剤する事も可能であるが、二酸化塩素の生成時間に影響を与えるためその点に留意して調剤する事が望ましい。 If necessary, succinic acid in the solid phase can be added to the columnar shape by adding fragrances, stabilizers, excipients, etc., but note that this affects the production time of chlorine dioxide. It is desirable to dispense.
より短時間での濃度の生成を求めるのであれば、コハク酸は微粉末状にする事が最も望ましい。 If it is desired to produce a concentration in a shorter time, it is most desirable to make succinic acid into a fine powder form.
以上のようにコハク酸を用いる事で安全に任意の濃度の二酸化塩素溶液を短時間で生成する事が可能となる。本発明の結果、従来の二律背反の課題は完全に解消され工業的に極めて有効である。 As described above, by using succinic acid, a chlorine dioxide solution having an arbitrary concentration can be safely produced in a short time. As a result of the present invention, the conventional trade-off problem is completely solved and industrially extremely effective.
発明の実施の形態において、述べたように、本発明による二酸化塩素溶液の生成方法を採用する事で、様々な局面において最適な濃度の二酸化塩素溶液を生成する事が可能になり、従来のように長時間待つ必要も、大規模な機械装置も不必要となり、容易に二酸化塩素の優れた特性を享受する事が可能になる。 In the embodiments of the invention, as described above, it is possible to produce a chlorine dioxide solution having an optimum concentration in various aspects by adopting the method for producing a chlorine dioxide solution according to the present invention. Therefore, it is not necessary to wait for a long time and a large-scale mechanical device is not required, and it is possible to easily enjoy the excellent characteristics of chlorine dioxide.
次に具体的実施例に基づいて、本発明による二酸化塩素溶液を使用した消毒処理を詳細に説明する。 Next, based on specific examples, the disinfection treatment using the chlorine dioxide solution according to the present invention will be described in detail.
水量１ｔ水温４２℃の循環式浴槽において、亜塩素酸ナトリウム水溶液（２５％）６０ｇとコハク酸９ｇを同時に同じ箇所から循環式浴槽内に加える。その結果、約２０分後浴槽における二酸化塩素濃度は１．４９ｐｐｍとなり確実な消毒処理が行えた事が認められた。 In a circulating bath having an amount of water of 1 t and a water temperature of 42 ° C., 60 g of an aqueous sodium chlorite solution (25%) and 9 g of succinic acid are simultaneously added into the circulating bath from the same location. As a result, after about 20 minutes, the chlorine dioxide concentration in the bathtub was 1.49 ppm, and it was confirmed that reliable disinfection treatment could be performed.
水量２００ｔ水温３３℃のスイミング用プールにおいて、亜塩素酸ナトリウム水溶液（２５％）１０Ｌとコハク酸１．８ｋｇクエン酸１．２ｋｇを同時に同じ箇所から加えスイミングプール内の水を循環させる。その結果、約２０分後プールにおける二酸化塩素濃度は１．２ｐｐｍに達し、確実な消毒処理が行えた事が認められた。 In a swimming pool with a water volume of 200 t and a water temperature of 33 ° C., 10 L of a sodium chlorite aqueous solution (25%) and 1.8 kg of succinic acid and 1.2 kg of citric acid are added simultaneously from the same location to circulate the water in the swimming pool. As a result, after about 20 minutes, the chlorine dioxide concentration in the pool reached 1.2 ppm, and it was confirmed that reliable disinfection treatment could be performed.
５００Ｌの小規模な池の藻を除去するために、１０Ｌの容器に亜塩素酸ナトリウム水溶液（２５％）６００ｇとコハク酸９０ｇクエン酸９０ｇを注ぎ１５分静置した所、２５３０ｐｐｍ．の二酸化塩素溶液を得る事が出来、その溶液を池に注ぐ事で殺藻出来る事が確認された。 In order to remove 500 L of small pond algae, a 10 L container was poured with 600 g of sodium chlorite aqueous solution (25%) and 90 g of succinic acid 90 g of citric acid, and allowed to stand for 15 minutes. It was confirmed that a chlorine dioxide solution can be obtained, and that the algae can be killed by pouring the solution into a pond.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007259810A (en) * | 2006-03-29 | 2007-10-11 | Japan Carlit Co Ltd:The | Sodium chlorite injection equipment |
| US8121257B2 (en) | 2008-12-11 | 2012-02-21 | Canon Kabushiki Kaisha | X-ray image capturing device and a method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007259810A (en) * | 2006-03-29 | 2007-10-11 | Japan Carlit Co Ltd:The | Sodium chlorite injection equipment |
| US8121257B2 (en) | 2008-12-11 | 2012-02-21 | Canon Kabushiki Kaisha | X-ray image capturing device and a method thereof |
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