WO2016135916A1

WO2016135916A1 - Water treatment agent composition, method for producing water treatment agent composition, and water treatment method

Info

Publication number: WO2016135916A1
Application number: PCT/JP2015/055569
Authority: WO
Inventors: 雅人都司; 染谷　新太郎; 吉川　浩; 千晴大森
Original assignee: オルガノ株式会社
Priority date: 2015-02-26
Filing date: 2015-02-26
Publication date: 2016-09-01
Also published as: KR102031472B1; CN107249332B; KR20170118174A; CN107249332A

Abstract

Provided is a water treatment agent composition which is a one-part preparation comprising a hypobromite salt that acts as an inorganic slime control agent and an anti-corrosive agent, and in which the inorganic slime control agent is prevented from the significant deterioration in slime control performance thereof (i.e., the significant deterioration in oxidizing power thereof). A water treatment agent composition comprising a bromine-containing oxidizing agent or a reaction product of a bromine compound with a chlorine-containing oxidizing agent, a sulfamic acid compound, and at least one anti-corrosive agent selected from a polymer containing a monomer unit represented by formula (1), a polymer containing a monomer unit represented by formula (2), a binary copolymer containing a monomer unit represented by formula (1) and a monomer unit represented by formula (3), a ternary copolymer containing a monomer unit represented by formula (1), a monomer unit represented by formula (3) and a monomer unit represented by formula (4), a phosphino carboxylic acid copolymer represented by formula (5), a bis(poly-2-carboxylethyl)phosphinic acid represented by formula (6), a 2-phosphonobutane-1,2,4-tricarboxylic acid represented by formula (7) and salts thereof, and an azole compound, wherein the components are compounded at pH 13 or higher.

Description

Water treatment agent composition, method for producing water treatment agent composition, and water treatment method

The present invention relates to a water treatment agent composition for controlling water-based organism adhesion, a method for producing the water treatment agent composition, and a water treatment method using the water treatment agent composition.

As an antibacterial agent for controlling the adhesion of organisms in industrial water systems such as cooling water systems and papermaking processes, an inorganic slime control agent is used that has more oxidizing power than organic slime control agents, that is, has a higher immediate effect. The number of cases being increased. As inorganic slime control agent, hypochlorite such as sodium hypochlorite is mainly used, but hypobromite such as sodium hypobromite is used to enhance the effect. Sometimes.

Sodium hypobromite, which has higher slime control performance than sodium hypochlorite, is unstable, and industrially, for example, bromide salts such as sodium bromide and hypochlorite salts such as sodium hypochlorite Are used immediately before use to produce sodium hypobromite in the system and a method of providing stabilized hypobromite.

When these inorganic slime control agents and metal anticorrosives are used in combination, a plurality of chemical tanks and liquid feed pumps are required, which requires a lot of management. In addition, it is necessary to supply the inorganic slime control agent and the metal anticorrosive agent to the water system at an appropriate ratio. For example, when the inorganic slime control agent is added excessively compared to the metal anticorrosive agent, the oxidation power of the metal There was a possibility that the anticorrosive agent was decomposed and the aqueous metal was corroded.

For this reason, it is desirable that an inorganic slime control agent having a high oxidizing power and a metal anticorrosive are always supplied to the water system at a constant ratio, and it is possible to combine the inorganic slime control agent and the metal anticorrosive into one agent. Most desirable.

For example, Patent Document 1 presents a monolithic slime prevention composition comprising a chlorine-based oxidizing agent such as sodium hypochlorite, a sulfamic acid compound, and an anionic polymer, and having a pH of 12 or higher. is doing. However, in the slime prevention composition of Patent Document 1, since the chlorine-based oxidizing agent and sulfamic acid are reacted and stabilized as bound chlorine, the composition has increased stability, but the oxidizing power of the slime control agent is increased. That is, there is a problem that the slime control performance is significantly lowered.

For example, Patent Document 2 contains a chlorinated oxidant such as sodium hypochlorite, an azole compound, and sulfamic acid or a salt thereof, and is a one-part sterilizing algicidal composition having a pH of 13 or more. Presenting things. However, in the bactericidal algicidal composition of Patent Document 2, since the chlorine-based oxidizing agent is reacted with sulfamic acid and stabilized as bound chlorine, the composition has increased stability, but the oxidizing power of the slime control agent is increased. That is, there is a problem that the slime control performance is significantly lowered.

In this way, when trying to combine inorganic slime control agent and metal anticorrosive agent, oxidative decomposition of metal anticorrosive agent and degradation of performance of slime control agent (decrease in oxidizing power) occur. It was extremely difficult. Therefore, the inorganic slime control agent suppresses a significant decrease in the slime control performance (a significant decrease in oxidizing power), and the inorganic slime control agent, particularly a hypobromite having a higher slime control performance than hypochlorite. Therefore, there is a need for a technique for combining the anticorrosive agent.

International Publication No. 2003/096810 Pamphlet Japanese Patent No. 3832399

The object of the present invention is to suppress a significant decrease in the slime control performance of the inorganic slime control agent (a significant decrease in oxidizing power) and to combine hypobromite, which is an inorganic slime control agent, and an anticorrosive agent. It is in providing the water treatment agent composition, the manufacturing method of the water treatment agent composition, and the water treatment method using the water treatment agent composition.

The present invention provides a brominated oxidant or a reaction product of a bromine compound and a chlorinated oxidant;
A sulfamic acid compound;
A polymer containing a monomer unit of formula (1), a polymer containing a monomer unit of formula (2), a monomer unit of formula (1) and a monomer unit of formula (3) A binary copolymer, a ternary copolymer comprising a monomer unit of formula (1), a monomer unit of formula (3), and a monomer unit of formula (4), a phosphine of formula (5) A phynocarboxylic acid copolymer, bis (poly-2-carboxylethyl) phosphinic acid of formula (6), 2-phosphonobutane-1,2,4-tricarboxylic acid of formula (7) and salts thereof, and azole compounds Is a water treatment composition containing at least one anticorrosive agent at a pH of 13 or more.

(1)
(In Formula (1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic ammonium group.)

(2)
(In Formula (2), R ² and R ³ each independently represent a hydrogen atom or a methyl group, and X ² and X ³ each independently represent a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic ammonium group. Represents a group.)

(3)
(In the formula (3), R ⁴ represents a hydrogen atom or a methyl group, and X ⁴ is an alkylsulfonic acid group having 1 to 10 carbon atoms or a salt thereof, or an arylsulfonic acid group having 6 to 10 carbon atoms or a salt thereof. In the case of a salt, it is a monovalent or divalent metal salt, ammonium salt or organic ammonium salt.)

(4)
(In Formula (4), R ⁵ represents a hydrogen atom or a methyl group, and X ⁵ and X ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which has 1 to 10 carbon atoms. The alkyl group of

(5)
(In Formula (5), Y represents a hydrogen atom or an alkali metal atom, Z represents —CONHC (CH ₃ ) ₂ CH ₂ SO ₃ Na, and h, l, m, and n are each 0 or positive. (It is an integer, and h + 1 + m + n is an integer of 1 to 100.)

(6)
(In Formula (6), Y represents a hydrogen atom or an alkali metal atom, m and n are each 0 or a positive integer, and m + n is an integer of 1 to 100.)

(7)
(In Formula (7), Y ¹ and Y ² each independently represent a hydrogen atom or an alkali metal atom.)

In the water treatment composition, it is preferable that bromine, the sulfamic acid compound, and the anticorrosive agent are blended at a pH of 13 or more as the bromine-based oxidizing agent.

Moreover, in the water treatment agent composition, it is preferable that the bromic acid concentration in the water treatment agent composition is less than 5 mg / kg.

The present invention is also a method for producing the water treatment agent composition, comprising a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere and reacting the mixture. It is a manufacturing method of a composition.

Further, the present invention is a water treatment method for treating water using the water treatment agent composition.

In the present invention, a hypobromite that is an inorganic slime control agent, a sulfamic acid compound, and the above specific anticorrosive agent are blended at a pH of 13 or more, thereby significantly reducing the slime control performance of the inorganic slime control agent ( (Remarkable reduction in oxidizing power) can be suppressed, and hypobromite, which is an inorganic slime control agent, and the above-mentioned specific anticorrosive can be combined into one agent.

Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

<Water treatment agent composition>
As a result of intensive studies by the present inventors, a stabilized composition of hypobromite formed from “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” And a polymer containing a monomer unit of the following formula (1), a polymer containing a monomer unit of the following formula (2), a monomer unit of the following formula (1) and the formula (3) A binary copolymer comprising a monomer unit, a ternary copolymer comprising a monomer unit of the following formula (1), a monomer unit of the formula (3) and a monomer unit of the formula (4) A phosphinocarboxylic acid copolymer of the following formula (5), bis (poly-2-carboxylethyl) phosphinic acid of the following formula (6), 2-phosphonobutane-1,2,4- of the following formula (7) At least one specific anticorrosive of a tricarboxylic acid and a salt thereof and an azole compound ”is blended at a pH of 13 or more. And in, we found the hypobromite is highly oxidative inorganic slime control agent, that it is possible to one agent of the above-mentioned specific anticorrosive. Among the above-mentioned “specific anticorrosives”, “a polymer containing a monomer unit of the following formula (1), a polymer containing a monomer unit of the following formula (2), and a monomer of the following formula (1)” A binary copolymer comprising a unit and a monomer unit of the formula (3), a monomer unit of the following formula (1), a monomer unit of the formula (3) and a monomer unit of the formula (4) A phosphinocarboxylic acid copolymer of the following formula (5), bis (poly-2-carboxylethyl) phosphinic acid of the following formula (6), 2-phosphonobutane of the following formula (7) “-1,2,4-tricarboxylic acid and its salts” usually function as a metal anticorrosive for iron-based metals, and azole compounds usually function as an anticorrosive for copper-based metals such as copper and copper alloys. To do.

The water treatment agent composition according to the present embodiment stabilizes hypobromite formed from “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound”. A composition containing the above-mentioned “specific anticorrosive agent”, but comprising a stabilized composition of hypobromite containing “a reaction product of a bromine-based oxidant and a sulfamic acid compound”, and the above “specific anticorrosive agent” Agent ", or a composition for stabilizing hypobromite containing" a reaction product of a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound ", and the above-mentioned" specific anticorrosive agent " May be included.

The organic ammonium salt in the formulas (1) to (3) is preferably, for example, an alkylammonium group having 1 to 4 carbon atoms or a hydroxyalkyl group or a (hydroxy) alkylammonium group.

Examples of the monovalent or divalent metal salt in the formulas (1) to (3) include sodium salt, potassium salt, calcium salt, magnesium salt and the like.

As the alkyl group when X ⁴ in the formula (3) is an alkylsulfonic acid group or a salt thereof, an alkyl group having 1 to 8 carbon atoms is preferable. When X ⁴ is an aryl sulfonic acid group or a salt thereof, the aryl group is preferably an aryl group having 6 to 10 carbon atoms or an arylalkyl group.

The alkyl group in formula (4) is preferably an alkyl group having 1 to 8 carbon atoms.

The weight ratio of the monomer unit in the binary copolymer containing the monomer unit of the formula (1) and the monomer unit of the formula (3) is preferably 1 to 99:99 to 1. .

The weight ratio of the monomer unit in the ternary copolymer containing the monomer unit of the formula (1), the monomer unit of the formula (3) and the monomer unit of the formula (4) is 1 to It is preferably 98: 1 to 98: 1 to 98.

The weight average molecular weight of the polymer containing the monomer units of the formulas (1) to (3) is preferably in the range of 500 to 100,000. When the weight average molecular weight is less than 500 or exceeds 100,000, the anticorrosion performance may be deteriorated.

The weight average molecular weight of the phosphinocarboxylic acid copolymer of the formula (5) is preferably in the range of 500 to 100,000. When the weight average molecular weight is less than 500 or exceeds 100,000, the anticorrosion performance may be deteriorated. The weight average molecular weight of the bis (poly-2-carboxylethyl) phosphinic acid of the formula (6) is preferably in the range of 500 to 100,000. When the weight average molecular weight is less than 500 or exceeds 100,000, the anticorrosion performance may be deteriorated.

As an alkali metal atom in Formula (5), (6), (7), a sodium atom and a potassium atom are preferable and a sodium atom is more preferable. 2-phosphonobutane-1,2,4-tricarboxylic acid in which Y ¹ and Y ^{2 in} formula (7) are hydrogen atoms is the following compound.

The azole compound usually works as an anticorrosive for copper-based metals such as copper and copper alloys. Examples of the azole compound include 1,2,3-benzotriazole, tolyltriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, imidazole, 2-mercaptobenzimidazole, and 2-mercapto. Examples thereof include benzothiazole, and one kind may be used alone, or two or more kinds may be used in combination. Among these, benzotriazole and tolyltriazole are preferable from the viewpoint of production cost and the like.

The ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidizing agent” or “reaction product of bromine compound and chlorine-based oxidizing agent” is preferably 1 or more. When the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” is less than 1, the amount of bromic acid produced in the reaction system increases. There is a case.

The effective bromine concentration contained in the composition is preferably in the range of 1% by weight to 20% by weight with respect to the total amount of the composition. When the effective bromine concentration is less than 1% by weight with respect to the total amount of the composition, the control of biofouling may be inferior, and when it exceeds 25% by weight, the amount of bromic acid produced in the reaction system increases. There is.

Bromine constituting the stabilizing composition of hypobromite needs to be supplied as active bromine by some means, bromine (liquid bromine) may be used as a bromine-based oxidizing agent, or a bromine compound and hypochlorous acid may be used. Active bromine generated by reacting with chlorate may be used, or active bromine via bromine chloride, bromate or the like may be used as a bromine-based oxidizing agent. Of these, the most preferred is the use of liquid bromine.

Examples of bromine-based oxidizing agents include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromite.

Among these, the composition containing "bromine and sulfamic acid compound" or "reaction product of bromine and sulfamic acid compound" using bromine is a composition containing "hypochlorous acid, bromine compound and sulfamic acid" Compared with a composition containing “bromine chloride and sulfamic acid” and the like, effective bromine is more stable, and by-product of bromic acid can be suppressed, which is more preferable.

That is, it is preferable that the water treatment agent composition according to the present embodiment contains bromine, a sulfamic acid compound, and the anticorrosive as a bromine-based oxidizing agent at a pH of 13 or more.

Examples of bromine compounds include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Of these, sodium bromide is preferable from the viewpoint of production cost and the like.

Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof. Etc. Among these, examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite. Metal salts, alkali metal chlorites such as sodium chlorite and potassium chlorite, alkaline earth metal chlorites such as barium chlorite, and other metal chlorites such as nickel chlorite , Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth metal chlorates such as calcium chlorate and barium chlorate. These chlorine-based oxidants may be used alone or in combination of two or more. As the chlorine-based oxidant, sodium hypochlorite is preferably used from the viewpoint of handleability.

The sulfamic acid compound is a compound represented by the following general formula (8).
R ₂ NSO ₃ H (8)
(In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

Examples of the sulfamic acid compound that is considered to act as a stabilizer for the inorganic slime control agent that constitutes the stabilized composition of hypobromite include, for example, sulfamic acid (amide) in which both two R groups are hydrogen atoms. Sulfuric acid), and one of the two R groups such as N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N-isopropylsulfamic acid, N-butylsulfamic acid is a hydrogen atom, Sulphamic acid compounds in which the other is an alkyl group having 1 to 8 carbon atoms, N, N-dimethylsulfamic acid, N, N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N Both R groups such as -methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid etc. are carbon A sulfamic acid compound in which one of two R groups such as a sulfamic acid compound having 1 to 8 alkyl groups and N-phenylsulfamic acid is a hydrogen atom and the other is an aryl group having 6 to 10 carbon atoms, or these And the like. Examples of the sulfamate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned. The sulfamic acid compounds and salts thereof may be used alone or in combination of two or more. As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load.

The water treatment agent composition according to the present embodiment may further contain an alkali. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures, sodium hydroxide and potassium hydroxide may be used in combination. Further, the alkali is not solid and may be used as an aqueous solution.

When the hypobromite stabilizing composition and the anticorrosive agent are combined into one agent, pH control is very important. Before and after mixing the hypobromite stabilizing composition and the anticorrosive agent, the pH is 13 or more. It is desirable that The pH of the composition is 13 or more, more preferably 13.2 or more, and further preferably 13.5 or more. If the pH of the composition is less than 13.0, the stability of the hypobromite stabilizing composition changes and it becomes difficult to make a one-component solution. When the anticorrosive agent is an azole compound, if the pH of the composition is less than 13.2, the stability of the hypobromite stabilization composition changes and decomposes the azole compound, making it difficult to make a one-component solution. There is a case. This is an event that is significantly different from the one-componentization of N-monochlorosulfuramic acid and azole compound formed from sodium hypochlorite and sulfamic acid, as shown in Patent Document 2.

The content of bromate ions in the water treatment agent composition according to this embodiment is preferably 10 mg / kg or less, and more preferably 5 mg / kg or less. If the bromate ion content exceeds 10 mg / kg, the compatibility with the anticorrosive agent may gradually deteriorate. When the anticorrosive is an azole compound, decomposition of the azole compound may be promoted when the bromate ion content exceeds 10 mg / kg.

<Method for producing water treatment agent composition>
The water treatment agent composition according to the present embodiment, for example, after mixing a bromine-based oxidizing agent and a sulfamic acid compound, or after mixing a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound, It is obtained by mixing with the anticorrosive agent, and may further be mixed with alkali.

Water treatment composition containing bromine, sulfamic acid compound and anticorrosive, or method for producing water treatment composition containing reaction product of bromine and sulfamic acid compound and anticorrosive It is preferable to include a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound in an inert gas atmosphere to cause a reaction, and then a step of mixing the reaction product with the anticorrosive. By adding and reacting under an inert gas atmosphere, the bromate ion concentration in the composition is lowered.

Although the inert gas to be used is not limited, at least one of nitrogen and argon is preferable from the viewpoint of production and the like, and nitrogen is particularly preferable from the viewpoint of manufacturing cost and the like.

The oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.

The addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less based on the total amount of the composition. If the bromine addition rate exceeds 25% by weight relative to the total amount of the composition, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the sterilizing power may be inferior.

The reaction temperature at the time of bromine addition is preferably controlled in the range of 0 ° C. to 25 ° C., but more preferably in the range of 0 ° C. to 15 ° C. from the viewpoint of production cost. When the reaction temperature at the time of bromine addition exceeds 25 degreeC, the production amount of the bromic acid in a reaction system may increase, and when it is less than 0 degreeC, it may freeze.

By the method for producing a water treating agent composition according to the present embodiment, the sulfamic acid-sodium hypobromite sodium salt composition does not substantially contain bromate ions and can be handled safely. By the method for producing a water treatment agent composition according to this embodiment, a one-component water treatment agent composition that is substantially free of bromate ions, is excellent in bactericidal performance, and is excellent in storage stability is obtained.

<Water treatment method using water treatment agent composition>
The water treatment agent composition according to the present embodiment can be used in water treatment methods such as water treatment in industrial water systems such as cooling water, and pipe cleaning with advanced biofouling.

The effective bromine concentration in the aqueous system to which the water treating agent composition according to this embodiment is added is preferably 0.01 to 100 mg / L. If it is less than 0.01 mg / L, a sufficient slime suppression effect may not be obtained. If it is more than 100 mg / L, corrosion of piping or the like may be caused.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Examples and Comparative Examples were formulated by adding the blending compositions (% by weight) shown in Tables 1 to 8 in the order (added in order from the top of the table). Formulation was performed in a PTFE (polytetrafluoroethylene) container by cooling to room temperature or lower and adding each drug while stirring with a stirrer.

In Tables 1 to 5, “PAA” is an acrylic acid homopolymer (weight average molecular weight of about 4,500), and “AABI” is acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid. The original copolymer (weight average molecular weight of about 4,500), “PMAA” is maleic acid homopolymer (weight average molecular weight of about 1,000), “AATER” is acrylic acid, 2-acrylamido-2-methyl An acrylic acid terpolymer of propanesulfonic acid and alkyl acrylamide (weight average molecular weight of about 4,500). “PCABI” is a phosphinocarboxylic acid copolymer of formula (5) (average value of h + 1 + m + n is about 16), and “BCAP” is bis (poly-2-carboxylethyl) phosphinic acid (m + n) of formula (6) (PBTC) is 2-phosphonobutane-1,2,4-tricarboxylic acid, and “HEDP” is 1-hydroxyethylidene-1,1-diphosphonic acid.

In Tables 1 to 8, stabilized hypobromite A, a, B, and C are as follows.

[Stabilized hypobromite A]
Add 1436 g of water and 361 g of sodium hydroxide to a 2 L 4-nose flask sealed by continuous injection while controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel is maintained at 1%. Then, 300 g of sulfamic acid was added and mixed, and while maintaining cooling so that the temperature of the reaction solution was 0 to 15 ° C., 473 g of liquid bromine was added, and 230 g of 48% potassium hydroxide solution was further added. The target stabilized hypobromite A having 10.7% sulfamic acid, 16.9% bromine, and an equivalent ratio of sulfamic acid to an equivalent of bromine of 1.04 by weight ratio to the total amount of the composition was obtained. . The pH of the resulting solution was 14.0 as measured by the glass electrode method. The bromine content of the resulting solution was 16.9% as measured by a redox titration method using sodium thiosulfate after bromine was converted to iodine with potassium iodide, and the theoretical content (16.9% ) Of 100.0%. The oxygen concentration in the reaction vessel during the bromine reaction was measured using “Oxygen Monitor JKO-02 LJDII” manufactured by Zico Corporation.

The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: IOL-30, manufactured by Toa DKK Corporation Electrode calibration: Neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto Chemical Co., boric acid manufactured by the same company Salt temperature (9.18) Standard solution (type 2) was measured by two-point calibration Measurement temperature: 25 ° C
Measurement value: Immerse the electrode in the measurement solution and use the value after stabilization as the measurement value.

[Stabilized hypobromite a]
The target stabilized hypobromite a was obtained by the same composition ratio and production method as those of the stabilized hypobromite A except that the reaction was performed in the atmosphere without flowing nitrogen gas. The pH of the stabilized hypobromite a was 14, and the bromine content was 16.9%.

[Stabilized hypobromite B]
A composition prepared according to the following procedure based on the contents described in JP-T-11-506139. Stabilized hypobromite B had a pH of 14, and a bromine content of 9.2%.
(1) 50.0 grams of 12% sodium hypochlorite solution was added to 60.0 grams of 40 wt% sodium bromide pure aqueous solution and stirred.
(2) A stabilizing solution composed of 20.6 grams of pure water, 9.6 grams of sulfamic acid, and 6.6 grams of sodium hydroxide was prepared.
(3) The stabilized solution of (2) was added to the solution of (1) while stirring to obtain the target stabilized hypobromite B.

[Stabilized hypobromite C]
A composition containing bromine chloride, sulfamic acid, and sodium hydroxide. The pH of the stabilized hypobromite C was 14, and the bromine content was 15.5%.

In Examples and Comparative Examples, the effective bromine concentration was determined by measuring the effective chlorine (DPD (diethyl-p-phenylenediamine) method) using a multi-item water quality analyzer DR / 4000 manufactured by HACH after diluting the sample 20,000 times. ), And after that, it was calculated by converting the molecular weight of chlorine and bromine into the effective bromine concentration. Moreover, about each water treatment agent composition, the effective bromine density | concentration after preserve | saving for 5 days or 14 days under light-shielding at 25 degreeC was measured, and the residual rate with respect to the effective bromine density | concentration immediately after formulation was computed.

Free halogen concentration and total halogen concentration were measured by effective chlorine measurement method (DPD (diethyl-p-phenylenediamine) method) using HACH multi-item water quality analyzer DR / 4000 after diluting the sample 20,000 times. did. The free bromine concentration and the total bromine concentration were calculated from the molecular weights of chlorine and bromine after obtaining values as the free chlorine concentration and the total chlorine concentration.

The residual ratio of the azole compound is shown as a residual ratio with respect to the initial concentration of the azole compound after each composition was stored at 50 ° C. under shading for 5 days. The azole compound was measured using a liquid chromatograph (8020 series) manufactured by Tosoh Corporation under the following conditions.
Column: TSKGEL ODS-80TS (manufactured by Tosoh)
Eluent: acetonitrile 20% solution Eluent flow rate: 1.0 mL / min
Detector: Multi-wavelength detector Measurement wavelength: 275 nm

For the compositions in Tables 2, 3, 4, 7, and 8, the bromate ion concentration was determined according to the analysis method of “JWWA K 120 (2008) sodium hypochlorite for water supply 5.4.5 bromic acid”. Measurement was performed by a post column-ion chromatography method.

When the free halogen concentration (free bromine concentration or free chlorine concentration) was 70% or more of the total halogen concentration (total bromine concentration or total chlorine concentration), it was judged to have high oxidizing power, that is, slime control performance.

Further, for the compositions in Tables 2 and 3, the presence or absence of precipitates was visually confirmed, and the turbidity was measured by an absorptiometry using a multi-item water quality analyzer DR / 4000 manufactured by HACH.

In the compositions of the examples, the inorganic slime control agent hypobromite, the sulfamic acid compound, and the specific anticorrosive agent are blended at a pH of 13 or more, so that the slime control performance of the inorganic slime control agent is improved. Suppressing significant decrease (remarkable decrease in oxidizing power), and without forming white precipitates, hypobromite, an inorganic slime control agent, and anticorrosive can be combined into one agent. It was. From the results shown in Table 1, it became clear that the effective bromine residual ratio increases at pH 13.0 or higher. The effective bromine concentration immediately after formulation of Example 1-1 was 6.8% by weight, of which free bromine was 6.7% by weight, and the ratio of free bromine in the total effective bromine was 98%. It was also found that a single formulation could be obtained with a high oxidizing power. In particular, the compositions of Examples 1 to 4 and 10 to 12 containing stabilized hypobromite A formed from “bromine” and “sulfamic acid compound” include “hypochlorous acid and bromine compound and Compared to the compositions containing “sulfamic acid” (stabilized hypobromite B) and the compositions of Examples 5-9, 13-15 containing “bromine chloride and sulfamic acid” (stabilized hypobromite C) The stability of effective bromine was high, and the byproduct of bromic acid could be suppressed. From the comparison of Examples 1 to 3, 5 to 7, 9 to 11, 13, and 14 with Examples 4, 8, 12, and 15, the composition containing the anticorrosive agents 1 to 3, 5, and 6 The turbidity of the water treatment composition was particularly low, and it was possible to prepare a water treatment composition with high quality. The case where the stabilized hypobromite A (Example 1-1) prepared under a nitrogen atmosphere is used is compared with the case where the stabilized hypobromite a (Example 16) prepared under air is used. (See Table 4), it can be seen that by using the stabilized hypobromite A prepared in a nitrogen atmosphere, the by-product of bromic acid can be suppressed. From the results in Table 5, the stability of effective bromine was high even when an azole compound was added.

From the results shown in Table 6, it was revealed that the residual ratio of the azole compound was high at pH 13.2 or higher. In particular, the compositions of Examples 20, 23 to 26 containing stabilized hypobromite A formed from “bromine” and “sulfamic acid compound” are described in “Hypochlorous acid, bromine compound and sulfamic acid”. In comparison to the composition of Examples 21, 22, 27, 28 comprising “brominated chloride and sulfamic acid” (stabilized hypobromite C). The residual ratio of the compound was high, and the bromate ion concentration was low.

Although the cause of the difference in the stability of the azole compound has not been clearly grasped regarding this difference, bromate ions are not detected from the stabilized hypobromite A, while the stabilized hypobromite B, C From this, bromate ions were detected, and it is assumed that the azole compound was decomposed by bromate ions.

Since Comparative Example 7 (corresponding to Patent Document 2) is a bonded chlorine in which hypochlorous acid and sulfamic acid are firmly bonded, the azole compound is hardly decomposed and the azole residual ratio is high, but the ratio of free halogen Was as low as 9.1%, and the slime control performance was low. When using stabilized hypobromite A (Example 20-1) prepared under a nitrogen atmosphere and when using stabilized hypobromite a (Example 20-4) prepared under air (See Table 8), it can be seen that by using stabilized hypobromite A prepared in a nitrogen atmosphere, the by-product of bromic acid can be further suppressed, and the residual ratio of the azole compound is slightly high. .

Claims

A brominated oxidant or a reaction product of a bromine compound and a chlorinated oxidant;
A sulfamic acid compound;
A polymer containing a monomer unit of formula (1), a polymer containing a monomer unit of formula (2), a monomer unit of formula (1) and a monomer unit of formula (3) A binary copolymer, a ternary copolymer comprising a monomer unit of formula (1), a monomer unit of formula (3), and a monomer unit of formula (4), a phosphine of formula (5) A phynocarboxylic acid copolymer, bis (poly-2-carboxylethyl) phosphinic acid of formula (6), 2-phosphonobutane-1,2,4-tricarboxylic acid of formula (7) and salts thereof, and azole compounds At least one anticorrosive of
Is formulated at a pH of 13 or more.

(1)
(In Formula (1), R 1 represents a hydrogen atom or a methyl group, and X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic ammonium group.)

(2)
(In Formula (2), R 2 and R 3 each independently represent a hydrogen atom or a methyl group, and X 2 and X 3 each independently represent a hydrogen atom, a monovalent or divalent metal atom, an ammonium group, or an organic ammonium group. Represents a group.)

(3)
(In the formula (3), R 4 represents a hydrogen atom or a methyl group, and X 4 is an alkylsulfonic acid group having 1 to 10 carbon atoms or a salt thereof, or an arylsulfonic acid group having 6 to 10 carbon atoms or a salt thereof. In the case of a salt, it is a monovalent or divalent metal salt, ammonium salt or organic ammonium salt.)

(4)
(In Formula (4), R 5 represents a hydrogen atom or a methyl group, and X 5 and X 6 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which has 1 to 10 carbon atoms. The alkyl group of

(5)
(In Formula (5), Y represents a hydrogen atom or an alkali metal atom, Z represents —CONHC (CH 3 ) 2 CH 2 SO 3 Na, and h, l, m, and n are each 0 or positive. (It is an integer, and h + 1 + m + n is an integer of 1 to 100.)

(6)
(In Formula (6), Y represents a hydrogen atom or an alkali metal atom, m and n are each 0 or a positive integer, and m + n is an integer of 1 to 100.)

(7)
(In Formula (7), Y 1 and Y 2 each independently represent a hydrogen atom or an alkali metal atom.)
The water treatment agent composition according to claim 1,
A water treatment agent composition, wherein bromine, the sulfamic acid compound, and the anticorrosive agent are blended at a pH of 13 or more as the bromine-based oxidizing agent.
The water treatment composition according to claim 2,
The water treatment agent composition, wherein the bromate concentration in the water treatment agent composition is less than 5 mg / kg.
It is a manufacturing method of the water treatment agent composition according to claim 2 or 3,
A method for producing a water treating agent composition comprising a step of reacting a mixed liquid containing water, an alkali and a sulfamic acid compound by adding bromine under an inert gas atmosphere.
A water treatment method comprising treating water with the water treatment agent composition according to any one of claims 1 to 3.