JP2013199390A - Method for preserving sodium hypochlorite - Google Patents
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Abstract
Description
本発明は、殺菌剤などとして広く利用されている次亜塩素酸ナトリウムの保存方法に関し、特に次亜塩素酸ナトリウムの有効塩素濃度の低下を抑制した保存方法に関する。 The present invention relates to a method for preserving sodium hypochlorite that is widely used as a disinfectant and the like, and more particularly, to a method for preserving a reduction in the effective chlorine concentration of sodium hypochlorite.
次亜塩素酸ナトリウムは、工業用、民生用などの各種用水の殺菌剤として液体（溶液）の態様で用いられている。この次亜塩素酸ナトリウム溶液においては、次亜塩素酸などが殺菌性能を発揮するので、これら殺菌性能を発揮する成分に含まれている塩素を有効塩素として、その濃度を殺菌性の指標としている。 Sodium hypochlorite is used in the form of a liquid (solution) as a disinfectant for various industrial and consumer waters. In this sodium hypochlorite solution, hypochlorous acid and the like exhibit sterilizing performance, so chlorine contained in these sterilizing performance components is regarded as effective chlorine, and its concentration is used as an index of sterilizing properties. .
しかしながら、市販の次亜塩素酸ナトリウム溶液は不安定で、保存中に徐々に次亜塩素酸が自己分解して有効塩素濃度が低下していく。この自己分解を抑制するためにｐＨを高く維持することを目的として、水酸化ナトリウムが添加されているが、それでも例えば有効塩素濃度１３重量％の有効塩素濃度を含む次亜塩素酸ナトリウム溶液の場合、２０℃で保存すると、２ケ月で１．５〜２．０重量％程度、３０℃では５．０〜６．０重量％も有効塩素濃度が低下し、殺菌効果の低下が著しい、という問題点がある。また、この自己分解した次亜塩素酸は亜塩素酸を経て塩素酸になるが、この塩素酸は毒性が強く、外部環境への排出が問題となる。これらが次亜塩素酸ナトリウムの利用にとって大きな障害となっている。特に、通常、工業用、水道用として市販されている次亜塩素酸ナトリウムには保存のために水酸化ナトリウムが添加されているが、この水酸化ナトリウムを含む次亜塩素酸ナトリウム溶液の自己分解を抑制できるのが望ましい。 However, commercially available sodium hypochlorite solutions are unstable, and hypochlorous acid gradually self-decomposes during storage and the effective chlorine concentration decreases. Sodium hydroxide is added for the purpose of maintaining a high pH in order to suppress this autolysis, but in the case of a sodium hypochlorite solution containing an effective chlorine concentration of, for example, 13% by weight, When stored at 20 ° C., the effective chlorine concentration is reduced by about 1.5 to 2.0% by weight in 2 months, and 5.0 to 6.0% by weight at 30 ° C., and the bactericidal effect is significantly reduced. There is a point. In addition, this self-decomposed hypochlorous acid becomes chloric acid via chlorous acid, but this chloric acid is highly toxic and the release to the external environment becomes a problem. These are major obstacles to the use of sodium hypochlorite. In particular, sodium hypochlorite, which is usually marketed for industrial use and water supply use, has been added with sodium hydroxide for storage, but self-decomposition of sodium hypochlorite solution containing this sodium hydroxide. It is desirable to be able to suppress this.
そこで、次亜塩素酸ナトリウムに代わる長期保存可能な殺菌剤として、固形塩素剤が提案されている。この固形塩素剤としては、ジクロロイソシアヌル酸およびそのナトリウム塩、トリクロロイソシアヌル酸、次亜塩素酸カルシウム等がある。しかしながら、これらは固定化のための薬剤が高価であることや、粉末であるため取り扱いが困難である、という問題がある。 Therefore, a solid chlorine agent has been proposed as a disinfectant that can be stored for a long time instead of sodium hypochlorite. Examples of the solid chlorine agent include dichloroisocyanuric acid and its sodium salt, trichloroisocyanuric acid, calcium hypochlorite and the like. However, these have the problem that the chemical | medical agent for fixation | immobilization is expensive, and since it is powder, handling is difficult.
また、スルファミン酸やアンモニアを添加した安定化塩素を用いることも考えられるが、これらの塩素剤は、安定化効果は高いものの、塩素の固定化効果が大きすぎるために殺菌力が小さく、多量に添加する必要がある、という問題点がある。 It is also possible to use stabilized chlorine to which sulfamic acid or ammonia has been added, but these chlorinating agents have a high stabilizing effect, but the effect of fixing the chlorine is too great, so the bactericidal power is small and a large amount There is a problem that it is necessary to add.
このように殺菌剤としての次亜塩素酸ナトリウムの有用性は依然として高いにもかかわらず、簡単かつ安価に次亜塩素酸ナトリウムを長期間安定して保存する方法はなかった。 Thus, although the usefulness of sodium hypochlorite as a disinfectant is still high, there has been no simple and inexpensive method for stably storing sodium hypochlorite for a long period of time.
本発明は、かかる課題を解決して、簡単かつ安価な方法で次亜塩素酸ナトリウムを長期間安定して保存することの可能な次亜塩素酸ナトリウム溶液の保存方法を提供することを目的とする。 An object of the present invention is to solve this problem and provide a method for storing a sodium hypochlorite solution capable of stably storing sodium hypochlorite for a long period of time by a simple and inexpensive method. To do.
上記課題を解決するために、本発明は、次亜塩素酸ナトリウム溶液に、リン酸塩又はホスホン酸塩を添加することを特徴とする次亜塩素酸ナトリウム溶液の保存方法を提供する（発明１）。 In order to solve the above problems, the present invention provides a method for preserving a sodium hypochlorite solution, characterized by adding a phosphate or phosphonate to a sodium hypochlorite solution (Invention 1). ).
かかる発明（発明１）によれば、次亜塩素酸ナトリウム有効塩素濃度の低下を大幅に抑制することができる。このような効果が得られる理由については必ずしも明らかではないが、次亜塩素酸ナトリウム溶液中には金属類などの不純物が含まれており、次亜塩素酸の自己分解にはこの不純物が影響していると考えられる。そこで、この不純物がリン酸又はホスホン酸とキレート化合物などの化合物を形成することにより、次亜塩素酸の分解に寄与する不純物が大幅に減少するためであると考えられる。 According to this invention (invention 1), it is possible to greatly suppress a decrease in the effective chlorine concentration of sodium hypochlorite. The reason why such an effect is obtained is not necessarily clear, but the sodium hypochlorite solution contains impurities such as metals, and this impurity affects the self-decomposition of hypochlorous acid. It is thought that. Therefore, it is considered that the impurities contributing to the decomposition of hypochlorous acid are significantly reduced by forming compounds such as chelate compounds with phosphoric acid or phosphonic acid.
上記発明（発明１）においては、前記リン酸塩又はホスホン酸塩が、正リン酸、トリポリリン酸、ポリメタリン酸、亜リン酸の塩から選ばれた１種又は２種以上であるのが好ましい（発明２）。 In the said invention (invention 1), it is preferable that the said phosphate or phosphonate is 1 type, or 2 or more types chosen from the salt of orthophosphoric acid, tripolyphosphoric acid, polymetaphosphoric acid, and phosphorous acid ( Invention 2).
かかる発明（発明２）によれば、これらのリン酸塩又はホスホン酸塩を次亜塩素酸ナトリウム溶液に添加することで、次亜塩素酸ナトリウム溶液の有効塩素濃度の低下を効果的に抑制することができる。 According to this invention (Invention 2), by adding these phosphates or phosphonates to the sodium hypochlorite solution, the effective chlorine concentration of the sodium hypochlorite solution is effectively suppressed. be able to.
上記発明（発明１，２）においては、前記次亜塩素酸ナトリウム溶液の有効塩素濃度が１〜３０重量％であるのが好ましい（発明３）。 In the said invention (invention 1 and 2), it is preferable that the effective chlorine concentration of the said sodium hypochlorite solution is 1 to 30 weight% (invention 3).
かかる発明（発明３）によれば、上記有効塩素濃度の次亜塩素酸ナトリウム溶液にリン酸塩又はホスホン酸塩を添加することにより、次亜塩素酸ナトリウム溶液の有効塩素濃度の低下により顕著な効果を得ることができる。 According to this invention (Invention 3), by adding a phosphate or phosphonate to the sodium hypochlorite solution having the above effective chlorine concentration, the reduction in the effective chlorine concentration of the sodium hypochlorite solution is more remarkable. An effect can be obtained.
上記発明（発明１〜３）においては、前記リン酸塩又はホスホン酸塩の添加量が、前記次亜塩素酸ナトリウム溶液に対して０．１〜５重量％（リン酸又はホスホン酸換算）であるのが好ましい（発明４）。 In the said invention (invention 1-3), the addition amount of the said phosphate or phosphonate is 0.1 to 5 weight% (phosphoric acid or phosphonic acid conversion) with respect to the said sodium hypochlorite solution. It is preferable (Invention 4).
かかる発明（発明４）によれば、次亜塩素酸ナトリウム溶液に上記濃度でリン酸塩又はホスホン酸塩を添加することにより、次亜塩素酸ナトリウム溶液の有効塩素濃度の低下を効果的に抑制することができる。 According to this invention (invention 4), by adding phosphate or phosphonate at the above concentration to the sodium hypochlorite solution, it is possible to effectively suppress the decrease in the effective chlorine concentration of the sodium hypochlorite solution. can do.
本発明の次亜塩素酸ナトリウム溶液の保存方法によれば、次亜塩素酸ナトリウム溶液に、リン酸塩又はホスホン酸塩を添加することにより、次亜塩素酸ナトリウム有効塩素濃度の低下を大幅に抑制することができる。 According to the method for preserving a sodium hypochlorite solution of the present invention, by adding a phosphate or phosphonate to a sodium hypochlorite solution, a significant decrease in the effective chlorine concentration of sodium hypochlorite is greatly reduced. Can be suppressed.
本実施形態の次亜塩素酸ナトリウム溶液の保存方法は、次亜塩素酸ナトリウム溶液に、リン酸塩又はホスホン酸塩を添加するものである。 The storage method of the sodium hypochlorite solution of this embodiment is to add a phosphate or phosphonate to the sodium hypochlorite solution.
上記次亜塩素酸ナトリウム溶液としては特に制限はなく、有効塩素を１〜３０重量％含有するものを用いることができる。特に殺菌能力の点で有効塩素濃度８重量％以上が好ましく、特に有効塩素濃度１２重量％以上の高濃度のものが好ましい。この次亜塩素酸ナトリウムとしては、低食塩品と通常品があるが、食塩は薬剤性能に影響を及ぼさないため、どちらでも構わない。 There is no restriction | limiting in particular as said sodium hypochlorite solution, What contains 1-30 weight% of effective chlorine can be used. In particular, an effective chlorine concentration of 8% by weight or more is preferable from the viewpoint of sterilizing ability, and a high concentration having an effective chlorine concentration of 12% by weight or more is particularly preferable. As this sodium hypochlorite, there are a low-salt product and a normal product, but salt may be used because it does not affect the drug performance.
上述したような次亜塩素酸ナトリウム溶液に添加するリン酸塩としては、正リン酸、トリポリリン酸、ポリメタリン酸、亜リン酸の塩から選ばれた１種又は２種以上を用いることができる。具体的には、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、トリポリリン酸ナトリウム、ポリメタリン酸ナトリウムなどのリン酸ナトリウム塩を単独で、もしくは２種以上を組み合わせて用いることができる。また、リン酸カリウム塩等の他のリン酸塩もリン酸ナトリウム塩と同様に用いることができる。また、ホスホン酸ナトリウムなどのホスホン酸塩も用いることができる。これらの中では、安定でかつ効果が高く安全性に優れていることから正リン酸、リン酸ナトリウム塩（リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム）が好ましい。 As a phosphate added to the sodium hypochlorite solution as described above, one or more selected from orthophosphoric acid, tripolyphosphoric acid, polymetaphosphoric acid, and a salt of phosphorous acid can be used. Specifically, sodium phosphate salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium tripolyphosphate and sodium polymetaphosphate can be used alone or in combination of two or more. Further, other phosphates such as potassium phosphate can be used in the same manner as sodium phosphate. Further, phosphonates such as sodium phosphonate can also be used. Among these, orthophosphoric acid and sodium phosphate (monosodium phosphate, disodium phosphate, trisodium phosphate) are preferable because they are stable, effective and excellent in safety.
これらのリン酸塩又はホスホン酸塩の添加量は、特に制限はないが、リン酸又はホスホン酸換算で１〜５０ｇ／Ｌ（０．１〜５重量％）であるのが好ましい。リン酸塩又はホスホン酸塩の添加量が１ｇ／Ｌ以下では、次亜塩素酸ナトリウム溶液の有効塩素濃度の低下を抑制する効果が十分でない一方、５０ｇ／Ｌを超えると、低温での保存中にリン酸三ナトリウムなどのナトリウム塩の結晶が析出する虞があるため好ましくない。 The addition amount of these phosphates or phosphonates is not particularly limited, but is preferably 1 to 50 g / L (0.1 to 5% by weight) in terms of phosphoric acid or phosphonic acid. When the amount of phosphate or phosphonate added is 1 g / L or less, the effect of suppressing the decrease in effective chlorine concentration of the sodium hypochlorite solution is not sufficient. On the other hand, when it exceeds 50 g / L, it is being stored at a low temperature. In this case, crystals of sodium salts such as trisodium phosphate may be precipitated, which is not preferable.
このような本実施形態の次亜塩素酸ナトリウム溶液の保存方法においては、次亜塩素酸ナトリウム溶液は、ｐＨが９〜１３の範囲内にあるのが好ましく、特に１０〜１２の範囲内にあるのが好ましい。次亜塩素酸ナトリウム溶液のｐＨが９未満では、次亜塩素酸の自己分解速度の抑制が困難となるばかりか殺菌性能も低下する一方、ｐＨが１３を超えると、リン酸塩又はホスホン酸塩の添加量によっては、リン酸三ナトリウムなどのナトリウム塩の結晶が析出する虞があるため好ましくない。したがって、所望のｐＨとなるように必要に応じてＮａＯＨを添加してもよい。また、場合によっては塩酸（ＨＣｌ）によってｐＨを調整してもよい。 In such a storage method of the sodium hypochlorite solution of the present embodiment, the sodium hypochlorite solution preferably has a pH in the range of 9 to 13, particularly in the range of 10 to 12. Is preferred. When the pH of the sodium hypochlorite solution is less than 9, it becomes difficult to suppress the rate of self-decomposition of hypochlorous acid, and the bactericidal performance is lowered. On the other hand, when the pH exceeds 13, phosphate or phosphonate Depending on the amount added, it is not preferable because crystals of sodium salts such as trisodium phosphate may be precipitated. Therefore, you may add NaOH as needed so that it may become desired pH. In some cases, the pH may be adjusted with hydrochloric acid (HCl).
上述したような本実施形態の次亜塩素酸ナトリウム溶液の保存方法によれば、例えば、有効塩素濃度１３重量％の次亜塩素酸ナトリウム溶液に０．１〜５重量％（リン酸又はホスホン酸換算）でリン酸塩又はホスホン酸塩を添加して、２５℃で保存した場合、有効塩素濃度の低下を３０日経過後で０．５重量％以下程度に、６０日経過後でも１重量％以下程度に抑制することができる。これに対し、配合しない場合では有効塩素濃度の低下は３０日経過後で３〜５重量％程度、６０日経過後で５〜７重量％程度であることから、その抑制効果は極めて大きいといえる。 According to the storage method of the sodium hypochlorite solution of this embodiment as described above, for example, 0.1 to 5% by weight (phosphoric acid or phosphonic acid is added to the sodium hypochlorite solution having an effective chlorine concentration of 13% by weight. When the phosphate or phosphonate is added at a conversion rate and stored at 25 ° C., the decrease in effective chlorine concentration is about 0.5% by weight or less after 30 days, and about 1% by weight or less after 60 days. Can be suppressed. On the other hand, when not blended, the effective chlorine concentration is about 3 to 5% by weight after 30 days, and about 5 to 7% by weight after 60 days.
以下の具体的実施例により本発明をさらに詳細に説明する。
〔比較例１〕
The following specific examples further illustrate the present invention.
[Comparative Example 1]
市販の工業用次亜塩素酸ナトリウム溶液１８Ｌを用意した。この次亜塩素酸ナトリウム溶液の有効塩素濃度は１３．９重量％で、遊離水酸化ナトリウムは０．２７重量％であった。 A commercially available industrial sodium hypochlorite solution 18L was prepared. The effective chlorine concentration of this sodium hypochlorite solution was 13.9% by weight, and free sodium hydroxide was 0.27% by weight.
そして、この次亜塩素酸ナトリウム溶液１Ｌをポリエチレン製容器に入れ、密栓して２５℃で暗所に保管し、３０日後及び６０日後の有効塩素濃度の変化を測定した結果を表１に示す。
〔実施例１〜４〕
Then, 1 L of this sodium hypochlorite solution was put in a polyethylene container, sealed and stored in a dark place at 25 ° C., and the results of measuring the change in effective chlorine concentration after 30 days and 60 days are shown in Table 1.
[Examples 1 to 4]
比較例１で用いた次亜塩素酸ナトリウム溶液１Ｌにリン酸二ナトリウムをリン酸換算で０．１重量％、０．５重量％、２．０重量％、４．０重量％それぞれ添加したものをポリエチレン製容器に入れ、密栓して２５℃で暗所に保管し、有効塩素濃度の変化を測定した結果を表１に合わせて示す。 What added 0.1 weight%, 0.5 weight%, 2.0 weight%, and 4.0 weight% of phosphoric acid disodium phosphate to 1 L of sodium hypochlorite solutions used in Comparative Example 1, respectively. Is put in a polyethylene container, sealed and stored in a dark place at 25 ° C., and the results of measuring the change in effective chlorine concentration are shown in Table 1.
表１から明らかな通り、比較例１では６０日間保管後の有効塩素濃度が５重量％以上低下したのに対し、実施例１〜４では１重量％以下の低下で維持でき、特に４．０重量％の添加では有効塩素濃度の低下がほとんどなかった。これらのことから実施例１〜４の次亜塩素酸ナトリウムの保存方法が有効塩素濃度の保持性に優れていることが確認された。
〔実施例５〜７〕
As is clear from Table 1, the effective chlorine concentration after 60 days storage decreased by 5% by weight or more in Comparative Example 1, whereas in Examples 1 to 4, it could be maintained at a decrease of 1% by weight or less, particularly 4.0. With the addition of wt%, there was almost no decrease in the effective chlorine concentration. From these facts, it was confirmed that the method for preserving sodium hypochlorite of Examples 1 to 4 was excellent in retention of effective chlorine concentration.
[Examples 5 to 7]
比較例１で用いた次亜塩素酸ナトリウム溶液１Ｌにホスホン酸ナトリウム、トリポリリン酸ナトリウム及びヘキサメタリン酸ナトリウムをリン酸換算又はホスホン酸換算でそれぞれ０．５重量％添加したものをポリエチレン製容器に入れ、密栓して２５℃で暗所に保管し、有効塩素濃度の変化を測定した結果を表２に示す。 A solution obtained by adding 0.5% by weight of sodium phosphonate, sodium tripolyphosphate and sodium hexametaphosphate to each of 1 L of sodium hypochlorite solution used in Comparative Example 1 in terms of phosphoric acid or phosphonic acid was placed in a polyethylene container. Table 2 shows the results of measuring the change in effective chlorine concentration after sealing and storing in a dark place at 25 ° C.
表２から明らかな通り、比較例１では６０日間保管後の有効塩素濃度が５重量％以上低下したのに対し、実施例５〜７では１．２重量％以下の低下で維持でき、リン酸二ナトリウム以外でも有効塩素濃度の保持性に優れていることが確認された。 As is clear from Table 2, in Comparative Example 1, the effective chlorine concentration after storage for 60 days was reduced by 5% by weight or more, whereas in Examples 5-7, it could be maintained at a decrease of 1.2% by weight or less, and phosphoric acid. It was confirmed that excluding disodium, the retention of effective chlorine concentration is excellent.
本発明の次亜塩素酸ナトリウムの保存方法は、工業用、民生用などの各種用水に用いる次亜塩素酸ナトリウム溶液の保存方法として好適に使用できる。 The method for preserving sodium hypochlorite according to the present invention can be suitably used as a method for preserving a sodium hypochlorite solution used in various industrial and consumer waters.
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| JP2012067306A JP2013199390A (en) | 2012-03-23 | 2012-03-23 | Method for preserving sodium hypochlorite |
| PCT/JP2013/055071 WO2013140962A1 (en) | 2012-03-23 | 2013-02-27 | Method for storing sodium hypochlorite |
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Cited By (3)
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| JP2016108552A (en) * | 2014-12-05 | 2016-06-20 | 株式会社Adeka | Liquid detergent composition and cleaning method using the same |
| JP2021053546A (en) * | 2019-09-27 | 2021-04-08 | 合同会社Ｆｍｃ | Manufacturing equipment and manufacturing method for carbonic acid-containing hypochlorous acid water |
| JP2021091829A (en) * | 2019-12-12 | 2021-06-17 | クリーンケミカル株式会社 | Sodium hypochlorite preparation |
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| JP2021091829A (en) * | 2019-12-12 | 2021-06-17 | クリーンケミカル株式会社 | Sodium hypochlorite preparation |
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