JP2018030132A - Method for treating service water - Google Patents
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- JP2018030132A JP2018030132A JP2017220654A JP2017220654A JP2018030132A JP 2018030132 A JP2018030132 A JP 2018030132A JP 2017220654 A JP2017220654 A JP 2017220654A JP 2017220654 A JP2017220654 A JP 2017220654A JP 2018030132 A JP2018030132 A JP 2018030132A
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- 238000000034 method Methods 0.000 title claims description 13
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- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
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- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
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- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- YTIXGBHAPNMOKU-UHFFFAOYSA-N 2-nitropropane-1,3-diol Chemical compound OCC(CO)[N+]([O-])=O YTIXGBHAPNMOKU-UHFFFAOYSA-N 0.000 description 1
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- CZLSHVQVNDDHDQ-UHFFFAOYSA-N pyrene-1,3,6,8-tetrasulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC(S(O)(=O)=O)=C(C=C3)C2=C2C3=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 CZLSHVQVNDDHDQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、水処理剤、特に、カルボン酸およびカルボン酸塩からなる群から選ばれた少なくとも一つの単量体単位を有する水溶性重合体を含む水処理剤に関する。 The present invention relates to a water treatment agent, particularly a water treatment agent comprising a water-soluble polymer having at least one monomer unit selected from the group consisting of a carboxylic acid and a carboxylate.
ボイラへの給水や冷却塔の循環冷却水などの用水として用いられる工業用水や水道水は、水質を原因とする各種の障害、例えばスケール生成、腐食およびスライム生成などを抑制するために、所要の薬剤を添加することが多い。この場合、用水は、薬剤による効果を発揮させたり、当該効果を維持したりするために、流通経路の要所において、継続的な薬剤濃度の管理が求められる。 Industrial water and tap water used as water for boiler supply water and circulating cooling water for cooling towers, etc. are required to suppress various obstacles caused by water quality, such as scale formation, corrosion and slime formation. Drugs are often added. In this case, the irrigation water is required to continuously manage the concentration of the drug at key points in the distribution channel in order to exert the effect of the drug or maintain the effect.
用水に添加した薬剤の濃度管理は、添加された薬剤そのものの濃度を測定するのが理想的であるが、薬剤の種類によっては簡便かつ迅速な濃度測定が困難な場合がある。また、数種類の薬剤が併用されることもあり、その場合は個々の薬剤濃度を正確に測定するのに困難を伴う。そこで、用水に対して薬剤とともにトレーサー物質であるリチウムの水溶性塩を添加し、用水中のリチウム濃度を測定することで薬剤の濃度管理をする方法が提案されている（例えば、特許文献１。）。 The concentration control of the drug added to the water is ideally to measure the concentration of the added drug itself, but depending on the type of drug, simple and rapid concentration measurement may be difficult. In addition, several types of drugs may be used in combination, and in that case, it is difficult to accurately measure the concentration of each drug. Then, the method of managing the chemical | medical agent density | concentration by adding the water-soluble salt of lithium which is a tracer substance with a chemical | medical agent with respect to water and measuring the lithium density | concentration in water is proposed (for example, patent document 1). ).
しかし、用水中のリチウム濃度の測定は、原子吸光法などの特殊な測定方法による必要があることから、当該方法を実施するための測定装置を備えた分析室へサンプリングした用水を移送する必要がある。このため、リチウム濃度の測定による方法では、流通している用水の薬剤濃度をその場で簡便にかつ迅速に測定するのが困難である。 However, since the measurement of the lithium concentration in the service water needs to be performed by a special measurement method such as atomic absorption, it is necessary to transfer the sampled water to an analysis room equipped with a measurement device for carrying out the method. is there. For this reason, it is difficult for the method using the measurement of the lithium concentration to easily and quickly measure the chemical concentration of the circulated water.
一方、リチウムの水溶性塩に替えて、スルホン化ピレン系化合物をトレーサー物質として用いる薬剤濃度の測定方法が提案されている（例えば、特許文献２。）。スルホン化ピレン系化合物は、蛍光物質であることから蛍光光度計を用いた濃度測定が可能であるため、用水に添加する薬剤中に同化合物を併せて添加しておくと、用水の流通系に蛍光光度計を設置することで用水の薬剤濃度のその場測定を実現可能である。 On the other hand, a method for measuring a drug concentration using a sulfonated pyrene compound as a tracer substance instead of a water-soluble salt of lithium has been proposed (for example, Patent Document 2). Since the sulfonated pyrene compound is a fluorescent substance, its concentration can be measured using a fluorimeter. Therefore, if the same compound is added to the agent to be added to the service water, In-situ measurement of the chemical concentration of water can be realized by installing a fluorometer.
ところが、スルホン化ピレン系化合物は、日光の照射下において蛍光能が劣化しやすい。この傾向は、用水に添加する薬剤中にスケール抑制剤として一般的なカルボン酸やカルボン酸塩を単量体単位として有する水溶性重合体と、スルホン化ピレン系化合物とが共存する場合に加速され、より顕著になる。したがって、建物の屋外や屋上などの日光に晒される環境に設置して使用されるのが一般的な小型の冷却塔設備等において、上述の水溶性重合体を含む薬剤の用水中の濃度をスルホン化ピレン系化合物を用いて測定しようとすると、スルホン化ピレン系化合物の貯蔵部や用水への供給経路を高度に遮光しない限り、薬剤の測定結果は信頼性を欠くものになる可能性がある。 However, the sulfonated pyrene compound tends to deteriorate its fluorescence ability under sunlight. This tendency is accelerated when a water-soluble polymer having a carboxylic acid or carboxylate as a monomer unit as a scale unit coexists with a sulfonated pyrene compound in the chemical added to the water. , Become more prominent. Therefore, in small cooling towers and the like that are generally installed and used in an environment exposed to sunlight, such as outdoors or on the roof of a building, the concentration of the above-mentioned drug containing the water-soluble polymer in the sewage water is reduced. If an attempt is made to measure using a fluorinated pyrene compound, the measurement result of the drug may be unreliable unless the storage route of the sulfonated pyrene compound and the supply route to the irrigation water are highly shielded.
本発明は、カルボン酸やカルボン酸塩を単量体単位として有する水溶性重合体とスルホン化ピレン系化合物とを含む水処理剤について、日光の照射環境下でのスルホン化ピレン系化合物の劣化を抑制しようとするものである。 The present invention relates to a water treatment agent containing a water-soluble polymer having a carboxylic acid or a carboxylate as a monomer unit and a sulfonated pyrene compound, and the deterioration of the sulfonated pyrene compound in a sunlight irradiation environment. It is something to be suppressed.
本発明は水処理剤に関するものであり、この水処理剤は、カルボン酸およびカルボン酸塩からなる群から選ばれた少なくとも一つの単量体単位を有する水溶性重合体と、スルホン化ピレン系化合物とを含み、ｐＨが２以下に調整されている。 The present invention relates to a water treatment agent, which comprises a water-soluble polymer having at least one monomer unit selected from the group consisting of a carboxylic acid and a carboxylate salt, and a sulfonated pyrene compound. And the pH is adjusted to 2 or less.
ここで用いられるスルホン化ピレン系化合物は、例えば、ピレンテトラスルホン酸およびピレンテトラスルホン酸塩からなる群から選ばれた少なくとも一つである。 The sulfonated pyrene compound used here is, for example, at least one selected from the group consisting of pyrenetetrasulfonic acid and pyrenetetrasulfonate.
本発明の水処理剤は、ホスホン酸およびホスホン酸塩からなる群から選ばれた少なくとも一つのホスホン酸系化合物をさらに含んでいてもよい。 The water treatment agent of the present invention may further contain at least one phosphonic acid compound selected from the group consisting of phosphonic acid and phosphonate.
また、本発明の水処理剤は、アゾ−ル系化合物をさらに含んでいてもよい。アゾ−ル系化合物として好ましいものは、例えば、１，２，３−ベンゾトリアゾールである。 The water treatment agent of the present invention may further contain an azole compound. A preferable example of the azole compound is 1,2,3-benzotriazole.
本発明の水処理剤は、カルボン酸およびカルボン酸塩からなる群から選ばれた少なくとも一つの単量体単位を有する水溶性重合体と、スルホン化ピレン系化合物とを含むものでありながら、ｐＨが２以下に調整されているため、日光の照射環境においてもスルホン化ピレン系化合物が劣化しにくい。 The water treatment agent of the present invention contains a water-soluble polymer having at least one monomer unit selected from the group consisting of a carboxylic acid and a carboxylate salt, and a sulfonated pyrene compound. Is adjusted to 2 or less, the sulfonated pyrene-based compound is hardly deteriorated even in an irradiation environment of sunlight.
本発明の水処理剤は、ボイラへの給水や冷却塔の循環冷却水などの用水として用いられる工業用水や水道水またはこれらを脱気処理、軟水化処理若しくはろ過処理等した処理水に対して添加されるものであり、水溶性重合体とスルホン化ピレン系化合物とを含む。 The water treatment agent of the present invention is used for industrial water and tap water used as water for boiler feed water and circulating cooling water for cooling towers, or for treated water that has been degassed, softened or filtered, etc. It is added and contains a water-soluble polymer and a sulfonated pyrene compound.
ここで用いられる水溶性重合体は、カルボン酸およびカルボン酸塩からなる群から選ばれた少なくとも一つの単量体単位を有するものである。このような水溶性重合体は、所要の目的のためのもの、例えばスケール抑制剤として用いられるものであれば特に限定されるものではなく、各種のものを用いることができる。 The water-soluble polymer used here has at least one monomer unit selected from the group consisting of carboxylic acid and carboxylate. Such a water-soluble polymer is not particularly limited as long as it is used for a required purpose, for example, as a scale inhibitor, and various types can be used.
水溶性重合体の例としては、スケール抑制剤として利用可能な次のＡ群〜Ｄ群に分類される化合物を挙げることができる。
〔Ａ〕カルボン酸系ホモポリマー
◎ポリアクリル酸およびその塩
◎ポリメタクリル酸およびその塩
◎ポリマレイン酸およびその塩
〔Ｂ〕カルボン酸系コポリマー
◎アクリル酸／２−アクリルアミド−２−メチルプロパンスルホン酸二元共重合体
◎アクリル酸／マレイン酸二元共重合体
◎マレイン酸／メチルビニルエーテル二元共重合体
◎アクリル酸／ヒドロキシプロピルアクリル酸塩二元共重合体
◎スルホン化スチレン／無水マレイン酸二元共重合体
〔Ｃ〕カルボン酸系ターポリマー
◎マレイン酸／アクリル酸アルキルエステル／ビニルアセテート三元共重合体
◎アクリル酸／スルホン酸／スチレンスルホン酸ナトリウム三元共重合体
◎アクリル酸／スルホン酸／置換アクリルアミド三元共重合体
〔Ｄ〕ホスホノカルボン酸系ポリマー
◎四ナトリウムホスホノエタン−１，２−ジカルボン酸塩
◎六ナトリウムホスホノブタン−１，２，３，４−テトラカルボン酸塩
As an example of a water-soluble polymer, the compound classified into the following A group-D group which can be utilized as a scale inhibitor can be mentioned.
[A] Carboxylic acid homopolymer ◎ Polyacrylic acid and its salt ◎ Polymethacrylic acid and its salt ◎ Polymaleic acid and its salt [B] Carboxylic acid copolymer ◎ Acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid Copolymer ◎ Acrylic acid / maleic acid binary copolymer ◎ Maleic acid / methyl vinyl ether binary copolymer ◎ Acrylic acid / hydroxypropyl acrylate binary copolymer ◎ Sulfonated styrene / maleic anhydride binary Copolymer [C] Carboxylic acid terpolymer ◎ Maleic acid / acrylic acid alkyl ester / vinyl acetate terpolymer ◎ Acrylic acid / sulfonic acid / sodium styrenesulfonate terpolymer ◎ Acrylic acid / sulfonic acid / Substituted acrylamide terpolymer [D] phosphonocarboxylic acid polymer ◎ tetrasodium phosphono-1,2-dicarboxylate ◎ hexasodium phosphono butane-1,2,3,4-tetracarboxylic acid salt
例示した水溶性重合体は、それぞれ単独で用いられてもよいし、任意の二種類以上を含む混合物（例えば、四ナトリウムホスホノエタン−１，２−ジカルボン酸塩と六ナトリウムホスホノブタン−１，２，３，４−テトラカルボン酸塩との混合物）として用いられてもよい。後者の場合、二種類以上の水溶性重合体は、同じ群の中から選択されたものでもよいし、異なる群から選択されたものでもよい。 The exemplified water-soluble polymers may be used singly or as a mixture containing two or more kinds (for example, tetrasodium phosphonoethane-1,2-dicarboxylate and hexasodium phosphonobutane-1). , 2,3,4-tetracarboxylate). In the latter case, the two or more types of water-soluble polymers may be selected from the same group or may be selected from different groups.
スルホン化ピレン系化合物は、蛍光物質であり、本発明の水処理剤を添加した用水に含まれる、当該水処理剤に由来の水溶性重合体や後記する他の効能成分の濃度を蛍光光度法により間接的に測定するためのトレーサー物質である。スルホン化ピレン系化合物としては、水溶性重合体および他の効能成分に対して不活性であり、水処理剤に含まれるこれらの成分のトレーサー物質として機能し得るものであれば各種のものを用いることができ、例えば、ピレンスルホン酸またはその塩を用いるのが好ましい。ピレンスルホン酸塩は、通常、ナトリウム塩などのアルカリ金属塩である。ピレンスルホン酸とその塩とは適宜併用することもできる。 The sulfonated pyrene compound is a fluorescent substance, and the concentration of the water-soluble polymer derived from the water treatment agent and other active ingredients described later is contained in the water to which the water treatment agent of the present invention is added. It is a tracer substance for measuring indirectly. As the sulfonated pyrene compound, various compounds are used as long as they are inactive with respect to the water-soluble polymer and other active ingredients and can function as tracer substances for these components contained in the water treatment agent. For example, it is preferable to use pyrenesulfonic acid or a salt thereof. Pyrenesulfonate is usually an alkali metal salt such as a sodium salt. Pyrenesulfonic acid and its salt can be used in combination as appropriate.
ピレンスルホン酸またはその塩は、それぞれスルホ基またはスルホン酸塩基の置換数が化学的に許容されるものであれば種類が特に限定されるものではないが、通常はスルホ基またはスルホン酸塩基が四つ置換したもの、すなわち、ピレンテトラスルホン酸またはその塩が好ましく、特に、１，３，６，８−ピレンテトラスルホン酸またはその塩（例えば、四ナトリウム塩）が好ましい。ピレンテトラスルホン酸とその塩とは適宜併用することもできる。 The type of pyrenesulfonic acid or a salt thereof is not particularly limited as long as the number of substitutions of the sulfo group or sulfonate group is chemically acceptable, but usually the sulfo group or sulfonate group has four groups. One, ie, pyrenetetrasulfonic acid or a salt thereof is preferable, and 1,3,6,8-pyrenetetrasulfonic acid or a salt thereof (for example, a tetrasodium salt) is particularly preferable. Pyrenetetrasulfonic acid and its salt can be used in combination as appropriate.
本発明の水処理剤は、その使用目的に応じて、水溶性重合体およびスルホン化ピレン系化合物以外の効能成分を含んでいてもよい。例えば、水溶性重合体以外のスケール抑制剤、防食剤および殺菌剤などから選択した一種または二種以上の効能成分を含んでいてもよい。 The water treatment agent of the present invention may contain efficacy components other than the water-soluble polymer and the sulfonated pyrene compound depending on the purpose of use. For example, one or more active ingredients selected from scale inhibitors, anticorrosives, bactericides, and the like other than water-soluble polymers may be included.
水溶性重合体以外のスケール抑制剤としては、例えば、ホスホン酸およびその塩（通常はアルカリ金属塩）並びに２−ホスホノブタン−１，２，４−トリカルボン酸等が挙げられる。このうち、水溶性重合体によるスケール抑制効果を高めることができることから、ホスホン酸およびその塩を用いるのが好ましい。 Examples of the scale inhibitor other than the water-soluble polymer include phosphonic acid and its salt (usually alkali metal salt), 2-phosphonobutane-1,2,4-tricarboxylic acid, and the like. Among these, it is preferable to use phosphonic acid and its salt since the scale inhibiting effect by the water-soluble polymer can be enhanced.
防食剤は、水処理剤を添加する用水が流通する、銅や鋼鉄などの金属製の配管およびその他の水系の腐食を抑制するためのものであり、例えば、ピロール、ジアゾール、トリアゾール、テトラゾール、ベンゾアゾール、ベンゾジアゾールおよびベンゾトリアゾールなどのアゾール系化合物、リン化合物、亜鉛化合物並びにリグニン等が挙げられる。このうち、紫外線吸収能を有し、日光の照射環境下でのスルホン化ピレン系化合物の劣化を抑制可能なアゾール系化合物、特に、１，２，３−ベンゾトリアゾールを用いるのが好ましい。 The anticorrosive agent is for suppressing corrosion of metal pipes such as copper and steel and other aqueous systems through which water for adding a water treatment agent circulates. For example, pyrrole, diazole, triazole, tetrazole, benzoate. Examples thereof include azole compounds such as azole, benzodiazole and benzotriazole, phosphorus compounds, zinc compounds and lignin. Among these, it is preferable to use an azole compound, particularly 1,2,3-benzotriazole, which has an ultraviolet absorbing ability and can suppress deterioration of the sulfonated pyrene compound in the sunlight irradiation environment.
殺菌剤は、用水において雑菌が繁殖したりスライムが生成したりするのを抑制等するためのものである。殺菌剤としては、例えば、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オンおよび２−ブロモ−２−ニトロプロパン−１，３−ジオールを挙げることができる。これらの殺菌剤は、二種以上のものを併用することもできる。 A disinfectant is for suppressing the propagation of various bacteria or the formation of slime in the water. Examples of bactericides include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol. Can be mentioned. These fungicides can be used in combination of two or more.
さらに、本発明の水処理剤は、各種の添加剤、例えば、硝酸マグネシウムや塩化マグネシウム等の安定剤、界面活性剤および溶剤等を含んでいてもよい。 Furthermore, the water treatment agent of the present invention may contain various additives, for example, stabilizers such as magnesium nitrate and magnesium chloride, surfactants and solvents.
本発明の水処理剤は、水溶性重合体およびスルホン化ピレン系化合物並びに他の効能成分を混合することで得られる液状のもの、または、所要の成分を水またはアルコール類等の水溶性有機溶剤に溶解した溶液として提供されるが、ｐＨが２以下に調整されている。このｐＨ調整により、水処理剤に含まれるスルホン化ピレン系化合物は、日光の照射環境下においても劣化が抑制され、蛍光能を比較的安定に維持し得る。 The water treatment agent of the present invention is a liquid obtained by mixing a water-soluble polymer, a sulfonated pyrene compound and other active ingredients, or a water-soluble organic solvent such as water or alcohols as a required component. PH is adjusted to 2 or less. By this pH adjustment, deterioration of the sulfonated pyrene compound contained in the water treatment agent can be suppressed even under the sunlight irradiation environment, and the fluorescence ability can be maintained relatively stably.
水処理剤のｐＨは、通常、塩酸、硫酸または硝酸などの鉱酸水溶液を添加することで調整することができる。 The pH of the water treatment agent can usually be adjusted by adding an aqueous mineral acid such as hydrochloric acid, sulfuric acid or nitric acid.
本発明の水処理剤において、水溶性重合体の濃度は、通常、１〜２５重量％になるよう設定するのが好ましく、７〜２０重量％になるよう設定するのがより好ましい。また、スルホン化ピレン系化合物の含有量は特に限定されるものではないが、通常は１００〜１，０００ｍｇ／ｋｇになるよう設定するのが好ましい。 In the water treatment agent of the present invention, the concentration of the water-soluble polymer is usually preferably set to 1 to 25% by weight, and more preferably 7 to 20% by weight. Further, the content of the sulfonated pyrene compound is not particularly limited, but it is usually preferable to set the content to be 100 to 1,000 mg / kg.
本発明の水処理剤の組成として好ましいものの例は表１の通りである。 Examples of preferable compositions for the water treatment agent of the present invention are shown in Table 1.
本発明の水処理剤は、ボイラの給水や冷却塔の循環冷却水などの用水に添加すると、水溶性重合体がスケール抑制剤等として機能し、また、その他の効能成分を含む場合は当該効能成分が所要の機能を発揮する。用水に添加された水処理剤の濃度は、水処理剤に含まれるトレーサー物質であるスルホン化ピレン系化合物による蛍光強度を蛍光光度計で測定し、その結果に基づいて算出することができる。ここで、本発明の水処理剤は、日光の照射環境下で貯蔵したり用水に供給されたりするような場合であっても、ｐＨが２以下に調整されていることからスルホン化ピレン系化合物が劣化しにくく、効能成分の濃度測定結果の信頼性を高めることができる。 When the water treatment agent of the present invention is added to service water such as boiler feed water or circulating cooling water in a cooling tower, the water-soluble polymer functions as a scale inhibitor or the like, and when it contains other efficacy components, Ingredients perform their required functions. The concentration of the water treatment agent added to the water can be calculated based on the result of measuring the fluorescence intensity of the sulfonated pyrene compound, which is a tracer substance contained in the water treatment agent, with a fluorometer. Here, the water treatment agent of the present invention is a sulfonated pyrene-based compound because the pH is adjusted to 2 or less even when it is stored in a sunlight irradiation environment or supplied to water. Is less likely to deteriorate, and the reliability of the concentration measurement result of the active ingredient can be improved.
実験例
純水にポリマレイン酸（ＢＷＡ社の商品名「ベルクリン２００ＬＡ」）を加えて溶解し、通常の水処理剤よりもポリマレイン酸の濃度を高めた水溶液（ポリマレイン酸濃度：２０重量％）を調製した。この水溶液に対し、含有量が約１００ｍｇ／ｋｇになるよう１，３，６，８−ピレンテトラスルホン酸四ナトリウム塩（関東化学株式会社販売のＡＣＲＯＳ社製品）を添加し、ｐＨが１．３の試験用水処理剤（１）を調製した。そして、製造直後のこの試験用水処理剤（１）について、分光蛍光光度計（日立ハイテック株式会社の型番「Ｆ−２７００」）を用いて３８５ｎｍの蛍光波長の蛍光強度（以下、「基準蛍光強度」という。）を測定した。
Experimental Example Polymaleic acid (BWA's trade name “Berculin 200LA”) was added to pure water and dissolved to prepare an aqueous solution (polymaleic acid concentration: 20% by weight) with a higher concentration of polymaleic acid than a normal water treatment agent. did. To this aqueous solution, 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (ACROS product sold by Kanto Chemical Co., Inc.) was added so that the content was about 100 mg / kg, and the pH was 1.3. The test water treatment agent (1) was prepared. And about this test water treatment agent (1) immediately after manufacture, the fluorescence intensity (henceforth "reference fluorescence intensity") of the fluorescence wavelength of 385 nm using a spectrofluorometer (model number "F-2700" of Hitachi High-Tech Co., Ltd.) Measured).
試験用水処理剤（１）を透明のガラス瓶に入れて晴天時の屋外に放置することで直射日光に曝露させ、曝露開始から１時間後に１００ｍｇの試料を採取した。この試料を約１，０００倍に希釈して３８５ｎｍの蛍光波長の蛍光強度を測定し、基準蛍光強度に対する蛍光強度の残存率（測定した蛍光強度／基準蛍光強度×１００：単位％）を求めた。 The test water treatment agent (1) was placed in a transparent glass bottle and allowed to stand outdoors in fine weather to be exposed to direct sunlight. A sample of 100 mg was collected 1 hour after the start of exposure. This sample was diluted about 1,000 times, and the fluorescence intensity at a fluorescence wavelength of 385 nm was measured, and the residual ratio of the fluorescence intensity with respect to the reference fluorescence intensity (measured fluorescence intensity / reference fluorescence intensity × 100: unit%) was determined. .
試験用水処理剤（１）に水酸化ナトリウム水溶液を添加することでｐＨを３．２に調整した試験用水処理剤（２）、ｐＨを３．７に調整した試験用水処理剤（３）およびｐＨを６．４に調整した試験用水処理剤（４）を調製し、これらの試験用水処理剤についても試験用水処理剤（１）と同様にして曝露開始から１時間後の蛍光強度の基準蛍光光度に対する残存率を求めた。結果を図１に示す。 Test water treatment agent (2) adjusted to pH 3.2 by adding aqueous sodium hydroxide solution to test water treatment agent (1), test water treatment agent (3) adjusted to pH 3.7 and pH The test water treatment agent (4) adjusted to 6.4 was prepared, and these test water treatment agents were also used in the same manner as in the test water treatment agent (1), and the fluorescence intensity reference fluorescence intensity after 1 hour from the start of exposure. The residual rate with respect to was determined. The results are shown in FIG.
実施例１
純水５０．６重量％、ポリマレイン酸（ＢＷＡ社の商品名「ベルクリン２００ＬＡ」）１５．０重量％、２−ホスホノブタン−１，２，４−トリカルボン酸（ＢＷＡ社の商品名「ベルクリン６５０」）５．０重量％、１，２，３−ベンゾトリアゾール（ＢＷＡ社の商品名「ベルクリン５１０」）０．５重量％、５−クロロ−２−メチル−４−イソチアゾリン−３−オン１０．０〜１５．０重量％と２−メチル−４−イソチアゾリン−３−オン３．０〜５．０重量％との混合物（Ｒｏｈｍ ＆ Ｈａａｓ社の商品名「ＫＡＴＨＯＮ」）１５．０重量％、２−ブロモ−２−ニトロプロパン−１，３−ジオール（ＡｃｃｕＳｔａｎｄａｒｄ社製）７．５重量％、硝酸マグネシウム２．６重量％および塩化マグネシウム０．６重量％を含む水溶液を調製した。この水溶液に対して１，３，６，８−ピレンテトラスルホン酸四ナトリウム塩（関東化学株式会社販売のＡＣＲＯＳ社製品）を含有量が９９．４ｍｇ／ｋｇになるよう添加し、また、７０重量％硫酸の添加によりｐＨを０．７に調整し、水処理剤を得た。そして、製造直後の水処理剤の基準蛍光強度を測定した。
Example 1
Pure water 50.6% by weight, polymaleic acid (BWA trade name “Berculin 200LA”) 15.0% by weight, 2-phosphonobutane-1,2,4-tricarboxylic acid (BWA trade name “Berculin 650”) 5.0% by weight, 0.5% by weight of 1,2,3-benzotriazole (BWA trade name “Berculin 510”), 5-chloro-2-methyl-4-isothiazolin-3-one 10.0- 15.0% by weight and 2-methyl-4-isothiazolin-3-one 3.0-5.0% by weight (Rohm & Haas trade name “KATHON”) 15.0% by weight, 2-bromo An aqueous solution containing 7.5% by weight of 2-nitropropane-1,3-diol (manufactured by AccuStandard), 2.6% by weight of magnesium nitrate and 0.6% by weight of magnesium chloride was prepared. It was. To this aqueous solution, 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (ACROS product sold by Kanto Chemical Co., Inc.) was added to a content of 99.4 mg / kg, and 70 wt. The pH was adjusted to 0.7 by adding% sulfuric acid to obtain a water treatment agent. And the reference | standard fluorescence intensity of the water treatment agent immediately after manufacture was measured.
水処理剤を透明のガラス瓶に入れて晴天時の屋外に放置することで直射日光に曝露させ、曝露開始から１時間後に１００ｍｇの試料を採取した。この試料を約１，０００倍に希釈して３８５ｎｍの蛍光波長の蛍光強度を測定し、基準蛍光強度に対する蛍光強度の残存率を求めたところ、８７．４％であった。 The water treatment agent was placed in a transparent glass bottle and allowed to stand outdoors in fine weather to be exposed to direct sunlight, and a sample of 100 mg was collected 1 hour after the start of exposure. When this sample was diluted about 1,000 times, the fluorescence intensity at a fluorescence wavelength of 385 nm was measured, and the residual ratio of the fluorescence intensity with respect to the reference fluorescence intensity was determined to be 87.4%.
実施例２
実施例１で調製した水処理剤に水酸化ナトリウム水溶液を添加することでｐＨを２．０に調整した水処理剤を製造し、製造直後のこの水処理剤の基準蛍光強度を測定した。そして、この水処理剤を透明のガラス瓶に入れて晴天時の屋外に放置することで直射日光に曝露させ、実施例１と同様に操作して曝露開始から１時間後の蛍光強度の残存率を求めたところ、８５．７％であった。
Example 2
A water treatment agent adjusted to pH 2.0 by adding an aqueous sodium hydroxide solution to the water treatment agent prepared in Example 1 was produced, and the reference fluorescence intensity of this water treatment agent immediately after production was measured. Then, this water treatment agent is placed in a transparent glass bottle and left outdoors in fine weather to be exposed to direct sunlight, and the residual rate of fluorescence intensity after 1 hour from the start of exposure by operating in the same manner as in Example 1. When calculated, it was 85.7%.
比較例
水酸化ナトリウム水溶液の添加により水処理剤のｐＨを２．６に調整した点を除いて実施例２と同様に操作したところ、直射日光への曝露開始から１時間後の蛍光強度の残存率は７８．８％であった。
Comparative Example The same procedure as in Example 2 was performed except that the pH of the water treatment agent was adjusted to 2.6 by adding an aqueous sodium hydroxide solution. As a result, the fluorescence intensity remained 1 hour after the start of exposure to direct sunlight. The rate was 78.8%.
評価
実施例１，２の水処理剤は、ｐＨが２以下であることから、日光の照射環境下でのスルホン化ピレン系化合物の残存率（曝露開始から１時間後の蛍光強度の残存率）が８５％以上に確保されている。ボイラへの給水や冷却塔の循環冷却水などの用水へ水処理剤を供給するための供給装置は、通常、薬液タンクの液面計や薬注ホース等、部分的に透明または半透明の材料を使用されることがあり、これらの部位を完全に遮光するのは困難な場合があるが、このような場合であっても、実施例１、２の水処理剤は、スルホン化ピレン系化合物の劣化が抑えられる。したがって、実施例１、２の水処理剤を用いれば、消費された水処理剤を供給装置に補充する間隔（通常、夏場で２〜７日程度。）において、用水に添加した水処理剤の濃度管理を安定に実施することができる。
Since the water treatment agents of Evaluation Examples 1 and 2 have a pH of 2 or less, the residual rate of the sulfonated pyrene compound in the sunlight irradiation environment (the residual rate of the fluorescence intensity 1 hour after the start of exposure) Is secured to 85% or more. Supply devices for supplying water treatment agents to water supply such as boiler feed water and cooling cooling water for cooling towers are usually partially transparent or translucent materials such as liquid level gauges and chemical injection hoses for chemical tanks. In some cases, it is difficult to completely shield light from these sites. Even in such a case, the water treatment agents of Examples 1 and 2 are sulfonated pyrene compounds. Degradation can be suppressed. Therefore, if the water treatment agent of Example 1, 2 is used, in the space | interval (usually about 2-7 days in the summer) of the water treatment agent consumed, it is the water treatment agent added to water. Concentration management can be carried out stably.
本発明は用水の処理方法に関するものであり、この処理方法では、カルボン酸およびカルボン酸塩からなる群から選ばれた少なくとも一つの単量体単位を有する水溶性重合体とスルホン化ピレン系化合物とを含み、かつ、ｐＨが２以下に調整されている水処理剤を用水に対して添加する。 The present invention relates to method of treating water, in this processing method, a water-soluble polymer having at least one monomer unit selected from the group consisting of carboxylic acid and carboxylic acid salt and vinegar sulfonated pyrene A water treatment agent containing a compound and having a pH adjusted to 2 or less is added to the water .
水処理剤に含まれるスルホン化ピレン系化合物は、例えば、ピレンテトラスルホン酸およびピレンテトラスルホン酸塩からなる群から選ばれた少なくとも一つである。 The sulfonated pyrene compound contained in the water treatment agent is, for example, at least one selected from the group consisting of pyrene tetrasulfonic acid and pyrene tetrasulfonate.
水処理剤は、ホスホン酸およびホスホン酸塩からなる群から選ばれた少なくとも一つのホスホン酸系化合物をさらに含んでいてもよい。 The water treatment agent may further contain at least one phosphonic acid compound selected from the group consisting of phosphonic acid and phosphonate.
また、水処理剤は、アゾ−ル系化合物をさらに含んでいてもよい。アゾ−ル系化合物として好ましいものは、例えば、１，２，３−ベンゾトリアゾールである。
本発明に係る用水の処理方法の一形態では、日光の照射環境下において水処理剤を用水に対して添加する。
Further , the water treatment agent may further contain an azole compound. A preferable example of the azole compound is 1,2,3-benzotriazole.
In one form of the water treatment method according to the present invention, a water treatment agent is added to the water under sunlight irradiation environment.
Claims (5)
用水の処理方法。 A water treatment agent comprising a water-soluble polymer having at least one monomer unit selected from the group consisting of a carboxylic acid and a carboxylate and a sulfonated pyrene compound and having a pH adjusted to 2 or less Is added to the water,
Water treatment method.
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