JP2013094766A - Ship ballast water treatment agent and ship ballast water treatment method using the same - Google Patents
Ship ballast water treatment agent and ship ballast water treatment method using the same Download PDFInfo
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Abstract
【課題】 船舶バラスト水に含まれる細菌類およびプランクトンなどの微小水生生物の殺滅性に優れているとともに、安定性と防食性を有する船舶バラスト水の処理剤を提供する。
【解決手段】 船舶バラスト水の処理剤は、次亜塩素酸塩溶液に、ホスホン酸塩又はリン酸塩と、イソシアヌル酸又はスルファミン酸とを配合したものである。この船舶バラスト水処理剤のｐＨは１１以下であるのが好ましい。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a treatment agent for ship ballast water that is excellent in killing micro-aquatic organisms such as bacteria and plankton contained in ship ballast water, and has stability and anticorrosion properties.
A ship ballast water treatment agent is a hypochlorite solution containing phosphonate or phosphate and isocyanuric acid or sulfamic acid. It is preferable that pH of this ship ballast water treatment agent is 11 or less.
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Description
本発明は、船舶のバラストタンクに積み込まれる船舶バラスト水に含まれる細菌類およびプランクトンなどの微小水生生物の殺滅を行う船舶バラスト水の処理剤及びこれを用いた船舶バラスト水の処理方法に関し、特に安定性と防食性に優れた船舶バラスト水の処理剤及びこれを用いた船舶バラスト水の処理方法に関する。 The present invention relates to a treatment agent for ship ballast water that kills microaquatic organisms such as bacteria and plankton contained in ship ballast water loaded in the ballast tank of the ship, and a treatment method for ship ballast water using the same. In particular, the present invention relates to a ship ballast water treatment agent having excellent stability and anticorrosion properties and a ship ballast water treatment method using the same.
一般に船舶、特に貨物船は、積載貨物などの重量を含めて設計されているため、空荷または積荷が少ない状態の船舶は、プロペラ没水深度の確保、空荷時における安全航行の確保等の必要性から、出港前に港において海水を取水して船舶のバランスを取るが、このバラストとして用いられる水のことを船舶バラスト水とよぶ。この船舶バラスト水は、無積載で出港するとき、その出港地で港の海水などをバラストタンクに積み込む一方、逆に港内で積荷をするときには、船舶バラスト水の排水を行う。 In general, since ships, especially cargo ships, are designed to include the weight of cargo, etc., ships that are unloaded or lightly loaded must be able to ensure proper submersion depth and safe navigation during unloaded conditions. From the necessity, seawater is taken in the port before leaving the port to balance the ship. The water used as this ballast is called ship ballast water. When the ship ballast water leaves the port without loading, the seawater of the port is loaded into the ballast tank at the port of departure, while the ship ballast water is drained when loading in the port.
ところで、環境の異なる荷積み港と荷下し港との間を往復する船舶によって船舶バラスト水の注排水が行われると、荷積み港と荷下し港における船舶バラスト水に含まれる微生物の差異により沿岸生態系に悪影響を及ぼすことが懸念されている。そこで、船舶の船舶バラスト水管理に関する国際会議において２００４年２月に船舶の船舶バラスト水及び沈殿物の規制及び管理のための国際条約が採択され、船舶バラスト水の処理が義務付けられることとなった。 By the way, when the ship ballast water is poured and discharged by a ship that goes back and forth between the loading port and the unloading port in different environments, the difference in microorganisms contained in the ship ballast water at the loading port and the unloading port. There are concerns that it will adversely affect coastal ecosystems. Therefore, an international convention for the regulation and management of ship ballast water and sediment of ships was adopted in February 2004 at the international conference on ship ballast water management of ships, and the treatment of ship ballast water became obligatory. .
船舶バラスト水の処理基準として国際海事機構（ＩＭＯ）が定める基準は、船舶から排出される船舶バラスト水に含まれる５０μｍ以上の生物（主に動物プランクトン）の数が１ｍ３中に１０個未満、１０μｍ以上５０μｍ未満の生物（主に植物プランクトン）の数が１ｍｌ中に１０個未満、コレラ菌の数が１００ｍｌ中に１ｃｆｕ未満、大腸菌の数が１００ｍｌ中に２５０ｃｆｕ未満、腸球菌の数が１００ｍｌ中に１００ｃｆｕ未満となっている。 The standard set by the International Maritime Organization (IMO) as a standard for the treatment of ship ballast water is that the number of organisms (mainly zooplankton) of 50 μm or more contained in the ship ballast water discharged from the ship is less than 10 in 1 m 3 , The number of organisms (mainly phytoplankton) of 10 μm or more and less than 50 μm is less than 10 in 1 ml, the number of Vibrio cholerae is less than 1 cfu in 100 ml, the number of E. coli is less than 250 cfu in 100 ml, and the number of enterococci in 100 ml Less than 100 cfu.
このような船舶バラスト水の処理基準を満たすために、バラストタンクへ注水する海水中の微生物等を殺菌する船舶バラスト水の処理剤が種々提案されている。例えば、特許文献１には、船舶バラスト水に次亜塩素酸ナトリウムや次亜塩素酸カルシウムなどの塩素系の殺菌剤を添加して、滞留時間を確保することにより微生物等を殺菌する船舶バラスト水の処理方法が開示されている。また、特許文献２及び３には、船舶バラスト水に次亜塩素酸ナトリウムを添加して微生物等を殺菌する船舶バラスト水の処理装置が開示されている。さらに、塩素酸塩、過酸化水素及び硫酸から酸化物としての二酸化塩素を生成させて殺菌剤とする技術、過酸化水素と酢酸とから過酢酸を生成させ、余剰の過酸化水素と過酢酸とにより殺菌する技術が知られている。 In order to satisfy such ship ballast water treatment standards, various ship ballast water treatment agents have been proposed for sterilizing microorganisms in seawater poured into a ballast tank. For example, Patent Document 1 discloses a ship ballast water that sterilizes microorganisms and the like by adding a chlorine-based disinfectant such as sodium hypochlorite or calcium hypochlorite to ship ballast water to ensure a residence time. The processing method is disclosed. Patent Documents 2 and 3 disclose a ship ballast water treatment apparatus that sterilizes microorganisms by adding sodium hypochlorite to ship ballast water. Furthermore, a technology for producing chlorine dioxide as an oxide from chlorate, hydrogen peroxide and sulfuric acid to make a disinfectant, generating peracetic acid from hydrogen peroxide and acetic acid, and surplus hydrogen peroxide and peracetic acid The technique of sterilizing by is known.
しかしながら、特許文献１〜３で使用されている次亜塩素酸ナトリウムは、安価で液体であるので使用法も簡単であるが、高温では不安定で自己分解してしまうため、冷却装置を設けて３０℃以下に保持する必要があり、管理が面倒であるという問題点がある。一方、特許文献１で使用されている次亜塩素酸カルシウムは、海水に溶解すると硫酸カルシウムが析出し、スケールとなるため、淡水化のための装置を設けるか、スケールの除去が必要となる、という問題点がある。 However, sodium hypochlorite used in Patent Documents 1 to 3 is inexpensive and liquid, so its usage is simple, but it is unstable and self-decomposes at high temperatures, so a cooling device is provided. There is a problem that it is necessary to keep the temperature at 30 ° C. or lower, and management is troublesome. On the other hand, when calcium hypochlorite used in Patent Document 1 is dissolved in seawater, calcium sulfate precipitates and becomes a scale. Therefore, it is necessary to provide a device for desalination or to remove the scale. There is a problem.
また、塩素酸塩、過酸化水素及び硫酸から酸化物としての二酸化塩素を生成させて殺菌剤とする技術、過酸化水素と酢酸とから過酢酸を生成させ、余剰の過酸化水素と過酢酸とにより殺菌する技術では、これらの殺菌成分は非常に不安定であり、使用の直前に船上などで合成する必要があるという問題点がある。 In addition, a technology that produces chlorine dioxide as an oxide from chlorate, hydrogen peroxide and sulfuric acid to make a disinfectant, generates peracetic acid from hydrogen peroxide and acetic acid, and produces excess hydrogen peroxide and peracetic acid. In the technique of sterilizing by the above, these sterilizing components are very unstable, and there is a problem that it is necessary to synthesize them on the ship or the like immediately before use.
さらに、これらの殺菌剤はいずれも酸化剤（酸化性）であるので、十分なプランクトンの殺滅効果を得られるだけの量を添加すると、船舶バラスト水の配管やバラストタンクが腐食することがある。このような腐食の問題は、建造されて間もない船舶の場合には十分な塗装が施されているので問題とならないが、塗装から数年を経過したものでは、塗装の劣化や亀裂が生じ、極めて腐食しやすい状態となっている。このため、既存の船舶においては、これらの殺菌剤による腐食が大きな問題となっている。特にバラストタンクは船舶の外周側に設置されることが多いため、腐食が進むと浸水等の問題が生じかねないため、バラストタンクの腐食は船舶の寿命に大きく影響する。 Furthermore, since all of these disinfectants are oxidizing agents (oxidizing), adding an amount sufficient to obtain a sufficient plankton killing effect may corrode ship ballast water piping and ballast tanks. . Such corrosion problems do not pose a problem for ships that have just been built because they have been sufficiently painted, but in the case of several years after painting, paint deterioration and cracks occur. It is in an extremely corrosive state. For this reason, corrosion by these disinfectants is a major problem in existing ships. In particular, since the ballast tank is often installed on the outer peripheral side of the ship, the corrosion of the ballast tank greatly affects the life of the ship because corrosion may cause problems such as flooding.
このように従来は、優れた殺菌性能を発揮するとともに防食性と安定性とに優れた船舶バラスト水の処理剤はなかった。 Thus, conventionally, there has been no ship ballast water treatment agent that exhibits excellent sterilization performance and is excellent in anticorrosion and stability.
本発明は、かかる課題を解決して、船舶バラスト水に含まれる細菌類およびプランクトンなどの微小水生生物の殺滅性に優れているとともに、安定性と防食性を有する船舶バラスト水の処理剤を提供することを目的とする。また、本発明はこのような船舶バラスト水の処理剤を用いた船舶バラスト水の処理方法を提供することを目的とする。 The present invention solves this problem and provides a treatment agent for ship ballast water that is excellent in killing micro-aquatic organisms such as bacteria and plankton contained in ship ballast water, and that has stability and anticorrosive properties. The purpose is to provide. Another object of the present invention is to provide a ship ballast water treatment method using such a ship ballast water treatment agent.
上記課題を解決するために、第一に本発明は、次亜塩素酸塩溶液に、ホスホン酸塩又はリン酸塩と、イソシアヌル酸又はスルファミン酸とを配合したことを特徴とする船舶バラスト水処理剤を提供する（発明１）。 In order to solve the above-mentioned problem, first, the present invention is a ship ballast water treatment characterized in that a hypochlorite solution is blended with a phosphonate or phosphate and isocyanuric acid or sulfamic acid. An agent is provided (Invention 1).
かかる発明（発明１）によれば、次亜塩素酸により船舶バラスト水の細菌類およびプランクトンなどの微小水生生物の殺滅を行う一方、ホスホン酸塩又はリン酸塩によりバラストタンクの腐食を抑制することができる。このとき、十分な量のホスホン酸塩又はリン酸塩を溶解するには、ｐＨをあまり高くすることができない一方、ｐＨが低いと次亜塩素酸の自己分解が促進して有効塩素濃度が低下する。しかしながら、イソシアヌル酸又はスルファミン酸を配合することにより、次亜塩素酸の自己分解を抑制することができる。これにより、船舶バラスト水に含まれる細菌類およびプランクトンなどの微小水生生物の殺滅性を発揮しつつ、安定性及び防食性に優れた船舶バラスト水の処理剤とすることができる。 According to this invention (Invention 1), micro-aquatic organisms such as marine ballast water and plankton are killed by hypochlorous acid, while corrosion of the ballast tank is suppressed by phosphonate or phosphate. be able to. At this time, in order to dissolve a sufficient amount of phosphonate or phosphate, it is not possible to raise the pH so much, but when the pH is low, the autochlorination of hypochlorous acid is promoted and the effective chlorine concentration is lowered. To do. However, by adding isocyanuric acid or sulfamic acid, autolysis of hypochlorous acid can be suppressed. Thereby, it can be set as the processing agent of ship ballast water excellent in stability and anticorrosion property, exhibiting the killing property of microaquatic organisms, such as bacteria and plankton contained in ship ballast water.
上記発明（発明１）においては、前記船舶バラスト水処理剤のｐＨが１１以下であるのが好ましい（発明２）。 In the said invention (invention 1), it is preferable that pH of the said ship ballast water treatment agent is 11 or less (invention 2).
かかる発明（発明２）によれば、防食性の上で十分な量のホスホン酸塩又はリン酸塩を次亜塩素酸塩溶液に溶解することができる。 According to this invention (invention 2), a sufficient amount of phosphonate or phosphate can be dissolved in the hypochlorite solution in terms of corrosion resistance.
また、第二に本発明は、次亜塩素酸塩溶液に、ホスホン酸塩又はリン酸塩と、イソシアヌル酸又はスルファミン酸とを配合した処理剤を船舶バラスト水に添加することを特徴とする船舶バラスト水の処理方法を提供する（発明３）。 In addition, secondly, the present invention is a ship characterized by adding a treatment agent containing phosphonate or phosphate and isocyanuric acid or sulfamic acid to a hypochlorite solution to ship ballast water. A method for treating ballast water is provided (Invention 3).
かかる発明（発明３）によれば、次亜塩素酸により船舶バラスト水の細菌類およびプランクトンなどの微小水生生物の殺滅を行う一方、ホスホン酸塩又はリン酸塩によりバラストタンクの腐食を抑制することができる。このとき、十分な量のホスホン酸塩又はリン酸塩を溶解するには、ｐＨをあまり高くすることができない一方、ｐＨが低いと次亜塩素酸の自己分解が促進して有効塩素濃度が低下する。しかしながら、イソシアヌル酸又はスルファミン酸を配合することにより、次亜塩素酸の自己分解を抑制することができる。これにより、船舶バラスト水に含まれる細菌類およびプランクトンなどの微小水生生物の殺滅性を発揮しつつ、有効塩素濃度を長期間維持するとともに防食効果を有する船舶バラスト水の処理方法とすることができる。 According to this invention (Invention 3), micro-aquatic organisms such as marine ballast water bacteria and plankton are killed by hypochlorous acid, while corrosion of the ballast tank is suppressed by phosphonate or phosphate. be able to. At this time, in order to dissolve a sufficient amount of phosphonate or phosphate, it is not possible to raise the pH so much, but when the pH is low, the autochlorination of hypochlorous acid is promoted and the effective chlorine concentration is lowered. To do. However, by adding isocyanuric acid or sulfamic acid, autolysis of hypochlorous acid can be suppressed. Accordingly, a method for treating ship ballast water that maintains the effective chlorine concentration for a long period of time and has an anticorrosive effect while demonstrating the killing of microaquatic organisms such as bacteria and plankton contained in ship ballast water. it can.
本発明の船舶バラスト水処理剤によれば、次亜塩素酸により船舶バラスト水の細菌類およびプランクトンなどの微小水生生物の殺滅を行う一方、ホスホン酸塩又はリン酸塩によりバラストタンクの腐食を抑制することができる。このとき、十分な量のホスホン酸塩又はリン酸塩を溶解するには、ｐＨをあまり高くすることができない。その一方でｐＨが低いと次亜塩素酸の自己分解が促進されることにより経時安定性が低下し有効塩素濃度が低下する。しかしながら、イソシアヌル酸又はスルファミン酸を配合することにより、次亜塩素酸の自己分解を抑制することができる。 According to the ship ballast water treatment agent of the present invention, hypochlorous acid kills ship aquatic organisms such as bacteria and plankton in ballast water, while phosphonate or phosphate corrodes the ballast tank. Can be suppressed. At this time, the pH cannot be made too high to dissolve a sufficient amount of phosphonate or phosphate. On the other hand, when pH is low, autolysis of hypochlorous acid is promoted, so that the temporal stability is lowered and the effective chlorine concentration is lowered. However, by adding isocyanuric acid or sulfamic acid, autolysis of hypochlorous acid can be suppressed.
本実施形態の船舶バラスト水の処理剤は、次亜塩素酸塩溶液に、ホスホン酸塩又はリン酸塩と、イソシアヌル酸又はスルファミン酸とを配合したものである。 The processing agent for ship ballast water of this embodiment mixes a phosphonate or phosphate and isocyanuric acid or sulfamic acid in a hypochlorite solution.
上記次亜塩素酸塩としては、次亜塩素酸ナトリウム、次亜塩素酸カルシウムなどを用いることができる。 As said hypochlorite, sodium hypochlorite, calcium hypochlorite, etc. can be used.
ホスホン酸塩としては、ホスホン酸ナトリウムなどを用いることができ、リン酸塩としては、リン酸ナトリウムなどの正リン酸塩、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などの重合リン酸塩等を用いることができる。 As the phosphonate, sodium phosphonate or the like can be used. As the phosphate, a normal phosphate such as sodium phosphate, a polymerized phosphate such as sodium tripolyphosphate or sodium hexametaphosphate, or the like can be used. it can.
イソシアヌル酸は、Ｃ３Ｈ３Ｎ３Ｏ３の分子式で表されるシアヌル酸の同位体であり、イソシアヌル酸に限らず、塩素化物などを用いることもできる。 Isocyanuric acid is an isotope of cyanuric acid represented by the molecular formula of C 3 H 3 N 3 O 3 , and is not limited to isocyanuric acid, and chlorinated products can also be used.
さらに、スルファミン酸としては、スルファミン酸に限らず、アルカリ金属スルファミン酸なども用いることができる。 Furthermore, as sulfamic acid, not only sulfamic acid but also alkali metal sulfamic acid can be used.
また、本実施形態においては、犠牲電極として金属亜鉛を添加することができる。金属亜鉛の形態としては特に制限はなく、亜鉛の板状体、粒状体、粉状体などを用いることができ、防食のためには、一定量以上の亜鉛が溶解する必要があることから、表面積の大きい粒状体が少ない添加量で済む。一方、実用的には、亜鉛の板状体用いるのが簡単である。なお、本明細書中において金属亜鉛とは、純亜鉛に限らず、亜鉛を５０％以上、特に７０％以上含有する亜鉛合金も含む。 In this embodiment, metallic zinc can be added as a sacrificial electrode. The form of metallic zinc is not particularly limited, and zinc plates, granules, powders, etc. can be used, and for corrosion protection, a certain amount or more of zinc needs to be dissolved. A small amount of granule having a large surface area is sufficient. On the other hand, it is practical to use a zinc plate. In the present specification, metallic zinc is not limited to pure zinc but also includes a zinc alloy containing 50% or more, particularly 70% or more of zinc.
上述したような各種成分からなる本実施形態の船舶バラスト水の処理剤において、次亜塩素酸塩溶液は、有効塩素濃度４重量％以上、特に８重量％以上であるのが好ましい。有効塩素濃度４重量％未満では、船舶バラスト水に対して十分な殺菌性を発揮するための添加量が多くなりすぎる。また、有効塩素濃度の上限は安定性の面で１５重量％以下程度である。 In the treatment agent for ship ballast water of the present embodiment composed of various components as described above, the hypochlorite solution preferably has an effective chlorine concentration of 4% by weight or more, particularly 8% by weight or more. If the effective chlorine concentration is less than 4% by weight, the amount added for exhibiting sufficient bactericidal properties against ship ballast water is too large. The upper limit of the effective chlorine concentration is about 15% by weight or less in terms of stability.
また、ホスホン酸塩又はリン酸塩の配合量は、ホスホン酸（ＰＯ３）又はリン酸（ＰＯ４）が有効塩素量との重量比で０．０５以上となるように配合するのが好ましい。ホスホン酸（ＰＯ３）又はリン酸（ＰＯ４）が有効塩素量との重量比で０．０５未満では、次亜塩素酸塩溶液の酸化性に対して十分な防食性を発揮できなくなる。また、ホスホン酸塩又はリン酸塩の配合量の上限については、特に制限はないが、次亜塩素酸塩溶液への溶解性からホスホン酸（ＰＯ３）又はリン酸（ＰＯ４）が塩素との重量比で１．００以下であるのが好ましい。 The amount of phosphonate or phosphate salt, phosphonic acid (PO 3) or phosphate (PO 4) is preferably blended such that 0.05 or more at a weight ratio of the effective amount of chlorine. When phosphonic acid (PO 3 ) or phosphoric acid (PO 4 ) is less than 0.05 by weight ratio to the amount of effective chlorine, it becomes impossible to exhibit sufficient anticorrosive properties against the oxidizability of the hypochlorite solution. Further, the upper limit of the amount of phosphonate or phosphate is not particularly limited, but phosphonic acid (PO 3 ) or phosphoric acid (PO 4 ) is chlorine and is soluble in hypochlorite solution. The weight ratio is preferably 1.00 or less.
船舶バラスト水中における防食に必要なホスホン酸又はリン酸の量は、犠牲電極として金属亜鉛がない場合には、３〜１００ｍｇ／Ｌ、好ましくは５〜５０ｍｇ／Ｌであり、金属亜鉛がある場合には、１〜５０ｍｇ／Ｌ、好ましくは２〜１０ｍｇ／Ｌである。これらを考慮すると、具体的には、有効塩素濃度１３重量％の次亜塩素酸塩溶液の場合には、ホスホン酸塩又はリン酸塩を０．４〜６．５重量％配合すればよい。 The amount of phosphonic acid or phosphoric acid necessary for anticorrosion in ship ballast water is 3 to 100 mg / L, preferably 5 to 50 mg / L when there is no metallic zinc as a sacrificial electrode, and when there is metallic zinc. Is 1 to 50 mg / L, preferably 2 to 10 mg / L. In consideration of these, specifically, in the case of a hypochlorite solution having an effective chlorine concentration of 13% by weight, 0.4 to 6.5% by weight of phosphonate or phosphate may be blended.
さらに、イソシアヌル酸又はスルファミン酸の配合量は、有効塩素量に対してイソシアヌル酸の場合１〜１００モル％、スルファミン酸の場合２〜１００モル％である。イソシアヌル酸又はスルファミン酸の配合量が下限値未満では、次亜塩素酸の自己分解の抑制効果が十分でない一方、上限値を超えると次亜塩素酸塩溶液への溶解が困難となる。具体的には、有効塩素濃度１３重量％の次亜塩素酸塩溶液ではイソシアヌル酸の場合には０．２〜２６重量％程度、スルファミン酸の場合には０．３〜１８．５重量％程度配合すればよい。 Furthermore, the compounding quantity of isocyanuric acid or sulfamic acid is 1-100 mol% in the case of isocyanuric acid, and 2-100 mol% in the case of sulfamic acid with respect to the amount of effective chlorine. When the blending amount of isocyanuric acid or sulfamic acid is less than the lower limit value, the effect of suppressing the self-decomposition of hypochlorous acid is not sufficient. On the other hand, when the upper limit value is exceeded, dissolution in a hypochlorite solution becomes difficult. Specifically, in a hypochlorite solution having an effective chlorine concentration of 13% by weight, about 0.2 to 26% by weight in the case of isocyanuric acid, and about 0.3 to 18.5% by weight in the case of sulfamic acid. What is necessary is just to mix | blend.
また、金属亜鉛を添加する場合、亜鉛溶出量が電流値として５〜５０ｍＡ／ｍ２となる量を設置すればよい。電流値５ｍＡ／ｍ２以下では防食剤の低減効果が十分でない一方、５０ｍＡ／ｍ２を超えると亜鉛が無駄になるため好ましくない。 Moreover, when adding metal zinc, what is necessary is just to install the quantity from which zinc elution amount will be 5-50 mA / m < 2 > as an electric current value. If the current value is 5 mA / m 2 or less, the effect of reducing the anticorrosive is not sufficient, but if it exceeds 50 mA / m 2 , zinc is wasted, which is not preferable.
このような次亜塩素酸塩溶液をベースとした船舶バラスト水の処理剤は、ｐＨは１１以下であるのが好ましい。また、下限についてはｐＨ８以上、特に９以上であるのが好ましい。これは以下のような理由による。 The treating agent for ship ballast water based on such a hypochlorite solution preferably has a pH of 11 or less. Moreover, about a minimum, it is preferable that it is pH8 or more, especially 9 or more. This is due to the following reasons.
すなわち、ｐＨが１１を超えると、次亜塩素酸塩溶液に十分な防食性を発揮する量のホスホン酸塩又はリン酸塩を溶解するのが困難となる一方、ｐＨが１１以下では、有効塩素濃度が８重量％では、次亜塩素酸の自己分解速度が大きくなるが、イソシアヌル酸又はスルファミン酸を配合することにより、次亜塩素酸の自己分解速度を小さく抑えることが可能となる。なお、ｐＨ８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。 That is, when the pH exceeds 11, it becomes difficult to dissolve an amount of phosphonate or phosphate that exhibits sufficient corrosion resistance in the hypochlorite solution. When the concentration is 8% by weight, the self-decomposition rate of hypochlorous acid increases, but by adding isocyanuric acid or sulfamic acid, the self-decomposition rate of hypochlorous acid can be kept small. In addition, if it is less than pH 8, it will become difficult to suppress the self-decomposition rate of hypochlorous acid, and also sterilization performance will fall.
上述したような本実施形態の船舶バラスト水の処理剤の船舶バラスト水への添加量は、次亜塩素酸塩が２〜５０ｍｇ／Ｌ程度（有効塩素濃度換算）とすればよい。なお、処理剤の添加量は、船舶バラスト水中の有機物（ＤＯＣ、ＰＯＣなど）の量やアンモニアの濃度によって適宜調整すればよい。 The amount of the vessel ballast water treatment agent of this embodiment as described above added to the vessel ballast water may be about 2 to 50 mg / L of hypochlorite (in terms of effective chlorine concentration). In addition, what is necessary is just to adjust the addition amount of a processing agent suitably with the quantity of organic substance (DOC, POC, etc.) in ship ballast water, and the density | concentration of ammonia.
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]
有効塩素濃度１３重量％、ｐＨ１１．５の次亜塩素酸ナトリウム溶液１Ｌにリン酸としてリン酸１ナトリウム４５ｇを溶解しところ、有効塩素濃度１２．６重量％でｐＨは６．３となり、十分な殺菌性と防食性とを有するものであった。この溶液を室温（２６℃）で１０分間ゆるやかに攪拌したところ、有効塩素濃度は９．６％へと低下し、その後も有効塩素濃度が急激に低下し、殺菌性が大幅に低下した。
〔比較例２〕
Dissolving 45 g of monosodium phosphate as phosphoric acid in 1 L of sodium hypochlorite solution having an effective chlorine concentration of 13% by weight and pH 11.5 results in a pH of 6.3 with an effective chlorine concentration of 12.6% by weight. It had bactericidal and anticorrosive properties. When this solution was gently stirred at room temperature (26 ° C.) for 10 minutes, the effective chlorine concentration decreased to 9.6%, and thereafter, the effective chlorine concentration rapidly decreased and the bactericidal property significantly decreased.
[Comparative Example 2]
有効塩素濃度１３重量％、ｐＨ１１．５の次亜塩素酸ナトリウム溶液１Ｌにリン酸としてリン酸１ナトリウム４５ｇを溶解したところ、有効塩素濃度１２．６重量％でｐＨは６．３となった。この溶液に顆粒のＮａＯＨを徐々に添加したところｐＨが９．５を超えたところで、無色透明なリン酸１ナトリウムの析出物が確認され、防食性が大幅に低下することが確認された。
〔比較例３〕
When 45 g of monosodium phosphate as phosphoric acid was dissolved in 1 L of a sodium hypochlorite solution having an effective chlorine concentration of 13 wt% and a pH of 11.5, the pH became 6.3 at an effective chlorine concentration of 12.6 wt%. When granular NaOH was gradually added to this solution, when the pH exceeded 9.5, a colorless transparent monosodium phosphate precipitate was confirmed, confirming that the anticorrosion properties were greatly reduced.
[Comparative Example 3]
比較例２においてｐＨが９．０の時点でＮａＯＨの添加を止め、この溶液を３０℃で保存し、有効塩素濃度を経時的に測定したところ、１日当たり３．５重量％の有効塩素濃度の低下が観測され、殺菌性が大幅に低下した。
〔実施例１〕
In Comparative Example 2, the addition of NaOH was stopped when the pH was 9.0, the solution was stored at 30 ° C., and the effective chlorine concentration was measured over time. As a result, the effective chlorine concentration was 3.5 wt% per day. A decrease was observed and the bactericidal properties were greatly reduced.
[Example 1]
有効塩素濃度１３重量％、ｐＨ１１．５の次亜塩素酸ナトリウム溶液１Ｌにリン酸としてリン酸１ナトリウム４５ｇを溶解しところ、有効塩素濃度１２．６重量％でｐＨは６．３となり、十分な殺菌性と防食性とを有するものであった。この溶液にイソシアヌル酸５００ｍｇ／Ｌを添加し、さらに顆粒のＮａＯＨを徐々に添加し、ｐＨが９．０の時点でＮａＯＨの添加を止めた。この溶液を３０℃で保存し、有効塩素濃度を経時的に測定したところ、１日当たりの有効塩素濃度の低下は１．２重量％に抑制され、殺菌性を長期間維持できることが確認された。
〔実施例２〕
Dissolving 45 g of monosodium phosphate as phosphoric acid in 1 L of sodium hypochlorite solution having an effective chlorine concentration of 13% by weight and pH 11.5 results in a pH of 6.3 with an effective chlorine concentration of 12.6% by weight. It had bactericidal and anticorrosive properties. To this solution, 500 mg / L of isocyanuric acid was added, and granular NaOH was gradually added. When the pH was 9.0, the addition of NaOH was stopped. When this solution was stored at 30 ° C. and the effective chlorine concentration was measured over time, the decrease in effective chlorine concentration per day was suppressed to 1.2% by weight, and it was confirmed that bactericidal properties could be maintained for a long time.
[Example 2]
実施例１において、イソシアヌル酸５００ｍｇ／Ｌの代わりにスルファミン酸１０００ｍｇ／Ｌを添加した以外は同様にして、有効塩素濃度を経時的に測定したところ、１日当たりの有効塩素濃度の低下は１．４重量％に抑制され、殺菌性を長期間維持できることが確認された。 In Example 1, the effective chlorine concentration was measured over time in the same manner except that 1000 mg / L of sulfamic acid was added instead of 500 mg / L of isocyanuric acid. As a result, the decrease in effective chlorine concentration per day was 1.4. It was confirmed that the sterilization property can be maintained for a long period of time by being suppressed by weight percent.
これら実施例１、２及び比較例１〜３から明らかなとおり、次亜塩素酸ナトリウムにリン酸塩とイソシアヌル酸又はスルファミン酸を添加することにより、殺菌性と防食性と有効塩素濃度の安定性とを兼ね備えることがわかった。 As is clear from these Examples 1 and 2 and Comparative Examples 1 to 3, by adding phosphate and isocyanuric acid or sulfamic acid to sodium hypochlorite, bactericidal properties, anticorrosive properties, and stability of effective chlorine concentration It turns out that it combines.
本発明の船舶のバラストの水処理剤は、各種船舶、特に大型の船舶の船舶バラスト水の処理に好適に使用できる。 The water treatment agent for ship ballast of the present invention can be suitably used for the treatment of ship ballast water of various ships, particularly large ships.
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| DE102013111150A1 (en) * | 2013-10-09 | 2015-04-09 | Witty-Chemie Gmbh & Co. Kg | Aqueous suspension for dosing in an aqueous system, in particular in swimming pool water and method for dosing an aqueous suspension in an aqueous system |
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