JP2015044764A - Water treatment agent composition, method for producing water treatment agent composition, and water treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water treatment agent composition in which an inorganic-type slime control agent of hypobromite, and at least one of metal corrosion preventing agent and scale dispersing agent are formed into a one-pack type agent, that suppresses the conspicuous reduction in slime control performance (the conspicuous reduction in oxidizing power) of the inorganic-type slime control agent.SOLUTION: Provided is a water treatment agent composition in which a bromine-type oxidizing agent or a reaction product between bromine compound and chlorine-type oxidizing agent, a sulfamic acid compound, and a polymer comprising a monomer unit represented by the following formula are blended under a pH of 13 or more.

Description

  The present invention relates to a water treatment agent composition for controlling water-based biological 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 are used in combination with metal anticorrosives and scale dispersants, a plurality of chemical tanks and liquid feed pumps are required, and there is a problem that it takes time and effort for management. In addition, it is necessary to supply the inorganic slime control agent and the metal anticorrosive agent and the scale dispersant to the water system at an appropriate ratio. For example, the inorganic slime control agent is added excessively compared to the metal anticorrosive agent and the scale dispersant. In such a case, the metal anticorrosive and the scale dispersant are decomposed by the oxidizing power, and the water-based metal may be corroded or scale may be generated.

  For this reason, it is desirable that the inorganic slime control agent and the metal anticorrosive agent and the scale dispersant are always supplied to the aqueous system at a constant ratio, and the inorganic slime control agent and the metal anticorrosive agent and the scale dispersant are combined as one agent. Is 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. 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.

  In this way, when trying to combine an inorganic slime control agent with a metal anti-corrosion agent and a scale dispersant, the metal anti-corrosion agent and the scale dispersant are oxidatively decomposed and the performance of the slime control agent is reduced (decrease in oxidizing power). Because of this, it was extremely difficult to make a single agent. 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. In addition, there is a need for a technique for combining at least one of a metal anticorrosive and a scale dispersant.

International Publication No. 2003/096810 Pamphlet

  An object of the present invention is to suppress a significant decrease in the slime control performance (a significant decrease in oxidizing power) of an inorganic slime control agent, and a hypobromite that is an inorganic slime control agent, a metal anticorrosive, and a scale dispersant. An object of the present invention is to provide a water treatment composition comprising at least one of them, a method for producing the water treatment composition, and a water treatment method using the water treatment composition.

（１）
（式（１）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）

（２）
（式（２）中、Ｒ^２とＲ^３はそれぞれ独立に水素原子またはメチル基を表し、Ｘ^２とＸ^３はそれぞれ独立に水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。） In the present invention, a bromine-based oxidant or a reaction product of a bromine compound and a chlorine-based oxidant, a sulfamic acid compound, and a polymer containing a monomer unit of the formula (1) or the formula (2) have a pH of 13 It is the water treatment agent composition mix | blended above.

(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.)

（１）
（式（１）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）

（３）
（式（３）中、Ｒ^４は水素原子またはメチル基を表し、Ｘ^４はアルキルスルホン酸基もしくはその塩、または、アリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。） The present invention also provides a brominated oxidant, or a reaction product of a bromine compound and a chlorinated oxidant, a sulfamic acid compound, a monomer unit of the formula (1), and a monomer unit of the formula (3). Is a water treatment agent composition that is blended 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.)

(3)
(In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, X ⁴ represents an alkyl sulfonic acid group or a salt thereof, or an aryl sulfonic acid group or a salt thereof. Metal salts, ammonium salts or organic ammonium salts of

（１）
（式（１）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）

（３）
（式（３）中、Ｒ^４は水素原子またはメチル基を表し、Ｘ^４はアルキルスルホン酸基もしくはその塩、または、アリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。）

（４）
（式（４）中、Ｒ^５は水素原子またはメチル基を表し、Ｘ^５とＸ^６はそれぞれ独立に水素原子またはアルキル基を表すが、少なくとも一方がアルキル基である。） The present invention also provides a brominated oxidant, or a reaction product of a bromine compound and a chlorinated oxidant, a sulfamic acid compound, a monomer unit of the formula (1), and a monomer unit of the formula (3). A ternary copolymer containing a monomer unit of the formula (4) is a water treatment agent composition blended 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.)

(3)
(In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, X ⁴ represents an alkyl sulfonic acid group or a salt thereof, or an aryl sulfonic acid group or a salt thereof. Metal salts, ammonium salts or organic ammonium salts of

(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, but at least one of them is an alkyl group.)

  Moreover, in the water treatment agent composition, it is preferable that bromine, the sulfamic acid compound, and the polymer 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.

  Moreover, this invention is a water treatment method which processes water using the said water treatment agent composition.

  In the present invention, by mixing the sulfamic acid compound and the specific polymer at a pH of 13 or more, the inorganic slime control agent can be prevented from significantly reducing the slime control performance (remarkably reducing the oxidizing power) of the inorganic slime control agent. Can be combined with at least one of the metal anticorrosive and the scale dispersant.

  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 binary copolymer containing a monomer unit of the following formula (1) or (2), a monomer unit of the following formula (1) and a monomer unit of the formula (3) A polymer or a specific polymer comprising a terpolymer comprising a monomer unit of formula (1), a monomer unit of formula (3) and a monomer unit of formula (4) " It has been found that by blending at a pH of 13 or more, hypobromite, which is an inorganic slime control agent, and at least one of a metal anticorrosive and a scale dispersant can be combined. The “specific polymer” functions as a metal anticorrosive and a scale dispersant.

  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 polymer", but containing a "hypobromite stabilization composition containing a reaction product of a bromine-based oxidant and a sulfamic acid compound" ”, Or a“ hypobromite stabilizing composition 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“ specific polymer ” May be included.

（１）
（式（１）中、Ｒ^１は水素原子またはメチル基を表し、Ｘ^１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）

（２）
（式（２）中、Ｒ^２とＲ^３はそれぞれ独立に水素原子またはメチル基を表し、Ｘ^２とＸ^３はそれぞれ独立に水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）

（３）
（式（３）中、Ｒ^４は水素原子またはメチル基を表し、Ｘ^４はアルキルスルホン酸基もしくはその塩、または、アリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。）

（４）
（式（４）中、Ｒ^５は水素原子またはメチル基を表し、Ｘ^５とＸ^６はそれぞれ独立に水素原子またはアルキル基を表すが、少なくとも一方がアルキル基である。）

(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 Formula (3), R ⁴ represents a hydrogen atom or a methyl group, X ⁴ represents an alkyl sulfonic acid group or a salt thereof, or an aryl sulfonic acid group or a salt thereof. Metal salts, ammonium salts or organic ammonium salts of

(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, but at least one of them is an alkyl group.)

  In addition, as an organic ammonium salt in Formula (1)-(3), the alkylammonium group or (hydroxy) alkylammonium group which has a C1-C4 alkyl group or a hydroxyalkyl group is preferable, for example.

  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 Formula (3) is an alkylsulfonic acid group or a salt thereof, an alkyl group having 1 to 8 carbon atoms is preferable. The aryl group when X ⁴ is an arylsulfonic acid group or a salt thereof is preferably an aryl group having 6 to 10 carbon atoms or an arylalkyl group.

  As an alkyl group in Formula (4), a C1-C8 alkyl group is preferable.

  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: 99-1. .

  The weight ratio of the monomer unit in the ternary copolymer including 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 preferable that it is 98: 1-98: 1-98.

  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. If the weight average molecular weight is less than 500 or exceeds 100,000, the dispersion performance such as scale may be lowered.

  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, and bromate.

  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.

  Examples of bromine compounds include sodium bromide, potassium bromide, lithium 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 (1).
R ₂ NSO ₃ H (1)
(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), in addition, one of two R groups such as N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N-isopropylsulfamic acid, N-butylsulfamic acid is a hydrogen atom, A sulfamic acid compound 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. A sulfamic acid compound in which one of two R groups such as a sulfamic acid compound having an alkyl group of 8 to 8 and N-phenylsulfamic acid is a hydrogen atom and the other is an aryl group having 6 to 10 carbon atoms, or these Examples include salts. 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 this 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 combining a stabilizing composition of hypobromite with a metal anticorrosive or a scale dispersant, pH control is very important, and the stabilizing composition of hypobromite and the above polymer are mixed. It is desirable that the pH is 13 or more before and after. 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.

  The bromate ion content 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 polymer may gradually deteriorate.

<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 above polymer, and may further be mixed with alkali.

  Water treatment agent composition containing bromine, sulfamic acid compound and polymer, or method for producing water treatment composition containing reaction product of bromine and sulfamic acid compound and polymer 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 polymer. By adding and reacting under an inert gas atmosphere, the bromate ion concentration in the composition is lowered.

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

  The oxygen concentration in the reactor upon 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 during the addition of bromine 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 and the like. 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 treatment agent composition according to the present embodiment, the sulfamic acid-hypobromite sodium salt composition mainly contains no 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, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

  About the Example and the comparative example, the formulation (weight%) shown to Tables 1-4 and addition were carried out in order (it added in order from the table top), and formulation was performed. 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 4, “PAA” is acrylic acid homopolymer (weight average molecular weight 4,500), and “AABI” is acrylic acid-based binary of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid. Copolymer (weight average molecular weight 4,500), “PMAA” is maleic acid homopolymer (weight average molecular weight 1,000), “AATER” is acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid And an acrylic acrylate terpolymer of alkylacrylamide (weight average molecular weight 4,500).

  Moreover, in Tables 1-4, composition A, a, B, C is as follows.

[Composition 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 further 230 g of 48% potassium hydroxide solution was added, The target composition A was obtained, in which the sulfamic acid was 10.7% by weight relative to the total amount of the composition, 16.9% bromine, and the equivalent ratio of sulfamic acid to the equivalent of bromine was 1.04. 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%. In addition, 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 type 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.

[Composition a]
The target composition a was obtained with the same composition ratio and production method as the composition A except that the reaction was performed in the air without flowing nitrogen gas. The pH of the composition was 14, and the bromine content was 16.9%.

[Composition B]
It is a composition prepared by the following procedure based on the contents described in JP-T-11-506139. The pH of the composition was 14, and the bromine content was 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 composition B.

[Composition C]
A composition containing bromine chloride, sulfamic acid, and sodium hydroxide. The pH of the composition 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) by diluting the sample 20,000 times and using a multi-item water quality analyzer DR / 4000 manufactured by HACH. ), 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.

  Moreover, about the composition of Examples 1-1, 2-10, bromate ion concentration was analyzed by the analysis method of "JWWA K 120 (2008) sodium hypochlorite 5.4.5 bromic acid for water supply", It measured by the post column-ion chromatograph method.

  In the compositions of the examples, by mixing the sulfamic acid compound and the specific polymer at a pH of 13 or more, the inorganic slime control agent suppresses a significant decrease in slime control performance (a significant decrease in oxidizing power), and an inorganic system. Hypobromite, which is a slime control agent, and at least one of a metal anticorrosive and a scale dispersant could be combined into one agent. From the results shown in Table 1, it became clear that the effective bromine residual ratio increases at pH 13.0 or higher. In addition, although the effective bromine density | concentration immediately after formulation of Example 1-1 was 6.8 weight%, of these, free bromine is 6.7 weight%, The ratio of the free bromine in the whole effective bromine is 98. It was also found that a single formulation could be obtained with a high oxidizing power. Further, in particular, the composition of Example 1 containing a stabilizing composition of hypobromite formed from “bromine” and “sulfamic acid compound” contains “hypochlorous acid, bromine compound and sulfamic acid”. Compared with the composition of Examples 5-9 containing the composition containing and "bromine chloride and sulfamic acid", stability of effective bromine was high and it was able to suppress the byproduct of bromic acid. When the composition A prepared in a nitrogen atmosphere (Example 1-1) was used and the composition a prepared in the atmosphere (Example 10) was compared (see Table 3), nitrogen It can be seen that by using Composition A prepared in an atmosphere, by-product of bromic acid can be suppressed. Moreover, even if it mix | blended the azole compound from the result of Table 4, the stability of effective bromine was high.

Claims (7)

A brominated oxidant or a reaction product of a bromine compound and a chlorinated oxidant;
A sulfamic acid compound;
A polymer comprising monomer units of formula (1) or formula (2);
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.) A brominated oxidant or a reaction product of a bromine compound and a chlorinated oxidant;
A sulfamic acid compound;
A binary copolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3);
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.)

(3)
(In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, X ⁴ represents an alkyl sulfonic acid group or a salt thereof, or an aryl sulfonic acid group or a salt thereof. Metal salts, ammonium salts or organic ammonium salts of A brominated oxidant or a reaction product of a bromine compound and a chlorinated oxidant;
A sulfamic acid compound;
A terpolymer comprising a monomer unit of formula (1), a monomer unit of formula (3) and a monomer unit of formula (4);
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.)

(3)
(In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, X ⁴ represents an alkyl sulfonic acid group or a salt thereof, or an aryl sulfonic acid group or a salt thereof. Metal salts, ammonium salts or organic ammonium salts of

(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, but at least one of them is an alkyl group.) The water treatment agent composition according to any one of claims 1 to 3,
A water treatment agent composition, wherein bromine, the sulfamic acid compound, and the polymer are blended at a pH of 13 or more as the bromine-based oxidizing agent. The water treatment agent composition according to claim 4,
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 4 or 5,
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.   The water treatment method characterized by processing water using the water treatment agent composition of any one of Claims 1-5.