CN107249332B - Water treatment agent composition, method for producing water treatment agent composition, and water treatment method - Google Patents
Water treatment agent composition, method for producing water treatment agent composition, and water treatment method Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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Abstract
Provided is a water treatment agent composition which suppresses a significant decrease in sludge control performance (a significant decrease in oxidizing power) of an inorganic sludge control agent and which comprises a hypobromite, which is an inorganic sludge control agent, and an anticorrosive agent as a single agent. A water treatment agent composition prepared by compounding at least 1 corrosion inhibitor selected from a bromine-based oxidizing agent, a reaction product of a bromine compound and a chlorine-based oxidizing agent, a sulfamic acid compound, a polymer comprising a monomer unit of formula (1), a polymer comprising a monomer unit of formula (2), a binary copolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3), a ternary copolymer comprising a monomer unit of formula (1), a monomer unit of formula (3), and a monomer unit of formula (4), a phosphinocarboxylic acid copolymer of formula (5), a bis (poly-2-carboxyethyl) phosphinic acid of formula (6), a 2-phosphonobutane-1, 2, 4-tricarboxylic acid of formula (7) and a salt thereof, and an azole compound at a pH of 13 or higher.
Description
Technical Field
The present invention relates to a water treatment agent composition for controlling biological adhesion or the like in a water system, a method for producing the water treatment agent composition, and a water treatment method using the water treatment agent composition.
Background
As a bactericide for controlling the adhesion of organisms and the like in an industrial water system such as a cooling water system, a paper making process and the like, an inorganic sludge control agent having an oxidizing power, that is, having a high immediate effect, is used more frequently than an organic sludge control agent. Hypochlorite such as sodium hypochlorite is mainly used as the inorganic sludge control agent, and hypobromite such as sodium hypobromite is sometimes used to further improve the effect.
Sodium hypobromite, which has higher sludge control properties than sodium hypobromite, is unstable and is used industrially, for example, in the following ways: a method in which a bromide salt such as sodium bromide and a hypochlorite salt such as sodium hypochlorite are mixed immediately before use to produce sodium hypobromite in the system; a method of stabilizing hypobromite is provided.
When these inorganic sludge control agents and metal anticorrosive agents are used in combination, a plurality of liquid chemical tanks and liquid feeding pumps are required, and there is a problem that much time is required for management. In addition, the inorganic sludge control agent and the metal anticorrosive agent must be supplied to the water system at an appropriate ratio, and for example, if the inorganic sludge control agent is added in excess of the metal anticorrosive agent, the metal anticorrosive agent is decomposed by its oxidizing power, and there is a fear that the metal in the water system is corroded.
Therefore, it is desirable that the inorganic sludge control agent having a high oxidizing power and the metal anticorrosive agent are always supplied to the water system at a constant ratio, and it is most desirable that the inorganic sludge control agent and the metal anticorrosive agent are combined into one.
For example, patent document 1 discloses a one-pack sludge-preventing composition containing a chlorine-based oxidizing agent such as sodium hypochlorite, a sulfamic acid compound and an anionic polymer, and having a pH of 12 or more. However, in the composition for preventing sludge of patent document 1, since the chlorine-based oxidizing agent is reacted with sulfamic acid to stabilize the composition in the form of bound chlorine, the composition has a problem that the oxidizing power of the sludge control agent, that is, the sludge control performance is significantly lowered although the stability of the composition is increased.
For example, patent document 2 discloses a formulated bactericidal/algicidal composition containing a chlorine-based oxidizing agent such as sodium hypochlorite, an azole-based compound, and sulfamic acid or its salt, and having a pH of 13 or more. However, in the bactericidal/algicidal composition of patent document 2, since the chlorine-based oxidizing agent is reacted with sulfamic acid to stabilize the composition in the form of bound chlorine, the composition has a problem that the oxidizing power of the sludge control agent, that is, the sludge control performance, is significantly reduced although the stability of the composition is increased.
Thus, when the inorganic sludge control agent and the metal anticorrosive agent are to be formed into one, oxidative decomposition of the metal anticorrosive agent, a decrease in performance of the sludge control agent (a decrease in oxidizing power), and the like are caused, and therefore, it is extremely difficult to form one. Therefore, the following techniques are sought: the inorganic sludge controlling agent, particularly hypobromite having a sludge controlling performance higher than that of hypochlorite, is formulated with an anticorrosive agent while suppressing a significant decrease in the sludge controlling performance (a significant decrease in oxidizing power) of the inorganic sludge controlling agent.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2003/096810 pamphlet
Patent document 2: japanese patent No. 3832399
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide: a water treatment agent composition obtained by adding a hypobromite, which is an inorganic sludge control agent, and an anticorrosive agent in one agent while suppressing a significant decrease in sludge control performance (a significant decrease in oxidizing power) of the inorganic sludge control agent; a process for producing the water treatment agent composition; and a water treatment method using the water treatment agent composition.
Means for solving the problems
The invention relates to a water treatment agent composition, which is prepared by reacting bromine-series oxidant or reactant of bromine compound and chlorine-series oxidant with
Sulfamic acid compounds, and
at least 1 anticorrosive agent selected from the group consisting of a polymer comprising a monomer unit of formula (1), a polymer comprising a monomer unit of formula (2), a bipolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3), a terpolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3) and a monomer unit of formula (4), a phosphinocarboxylic acid copolymer of formula (5), a bis (poly-2-carboxyethyl) phosphinic acid of formula (6), a 2-phosphonobutane-1, 2, 4-tricarboxylic acid of formula (7) and salts thereof, and an azole compound
Compounded at a pH of 13 or above.
(in the formula (1), R1Represents a hydrogen atom or a methyl group, X1Represents a hydrogen atom, a 1-or 2-valent metal atom, an ammonium group or an organic ammonium group. )
(in the formula (2), R2And R3Each independently represents a hydrogen atom or a methyl group, X2And X3Each independently represents a hydrogen atom, a 1-or 2-valent metal atom, an ammonium group or an organic ammonium group. )
(in the formula (3), R4Represents a hydrogen atom or a methyl group, X4The salt is a C1-10 alkylsulfonic acid group or a salt thereof, or a C6-10 arylsulfonic acid group or a salt thereof, and in the case of the salt, the salt is a 1-or 2-valent metal salt, ammonium salt or organic ammonium salt. )
(in the formula (4), R5Represents a hydrogen atom or a methyl group, X5And X6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least one is an alkyl group having 1 to 10 carbon atoms. )
(formula (II)(5) Wherein Y represents a hydrogen atom or an alkali metal atom, and Z represents-CONHC (CH)3)2CH2SO3Na, h, l, m and n are respectively 0 or positive integers, and h + l + m + n is an integer of 1-100. )
(in the 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.)
(in the formula (7), Y1And Y2Each independently represents a hydrogen atom or an alkali metal atom. )
In addition, in the water treatment agent composition, it is preferable that bromine as the bromine-based oxidizing agent, the sulfamic acid compound, and the anticorrosive agent are blended at a pH of 13 or more.
In addition, in the water treatment agent composition, the concentration g of the bromic acid in the water treatment agent composition is preferably less than 5 mg/k.
The present invention also provides a method for producing a water treatment agent composition, comprising the steps of: bromine is added to a mixed solution containing water, a base and a sulfamic acid compound in an inert gas atmosphere, and a reaction is performed.
The present invention also provides a water treatment method for treating water using the water treatment agent composition.
ADVANTAGEOUS EFFECTS OF INVENTION
In the present invention, by blending the inorganic sludge control agent, i.e., the hypobromite, with the sulfamic acid compound, and with the specific anticorrosive at pH13 or more, a significant decrease in sludge control performance (a significant decrease in oxidizing power) of the inorganic sludge control agent can be suppressed, and the inorganic sludge control agent, i.e., the hypobromite, can be made one-to-one with the specific anticorrosive.
Detailed Description
Embodiments of the present invention will be described below. The present embodiment is an example for carrying out the present invention, and the present invention is not limited to the present embodiment.
< Water treatment agent composition >
The present inventors have conducted intensive studies and, as a result, have found that: by compounding a hypobromous acid stabilizing composition formed of a "bromine-based oxidizing agent" or a "reactant of a bromine compound and a chlorine-based oxidizing agent" and an "sulfamic acid compound", with "a polymer comprising a monomer unit of the following formula (1), a polymer comprising a monomer unit of the following formula (2), a binary copolymer comprising a monomer unit of the following formula (1) and a monomer unit of the formula (3), a ternary copolymer comprising a monomer unit of the following formula (1) and a monomer unit of the formula (3) and a monomer unit of the formula (4), a phosphinocarboxylic acid copolymer of the following formula (5), a bis (poly-2-carboxyethyl) phosphinic acid of the following formula (6), a 2-phosphonobutane-1, 2, 4-tricarboxylic acid and a salt thereof of the following formula (7), and at least 1 specific anticorrosive agent among azole compounds" at a pH of 13 or more, thus, the hypobromite, which is an inorganic sludge control agent having a high oxidizing power, can be used as a single agent with the specific anticorrosive agent. Among the above-mentioned "specific anticorrosive agents", the "polymer comprising a monomer unit of the following formula (1), the polymer comprising a monomer unit of the following formula (2), the binary copolymer comprising a monomer unit of the following formula (1) and a monomer unit of the formula (3), the terpolymer comprising a monomer unit of the following formula (1), a monomer unit of the formula (3) and a monomer unit of the formula (4), the phosphinocarboxylic acid copolymer of the following formula (5), bis (poly-2-carboxyethyl) phosphinic acid of the following formula (6), 2-phosphonobutane-1, 2, 4-tricarboxylic acid of the following formula (7) and salts thereof" generally function as a metal anticorrosive agent for iron-based metals, and the azole compound generally functions as an anticorrosive agent for copper-based metals such as copper, copper alloys and the like.
The water treatment agent composition of the present embodiment contains a hypobromous acid stabilizing composition formed of a "bromine-based oxidizing agent" or a "reaction product of a bromine compound and a chlorine-based oxidizing agent" and a "sulfamic acid compound" and the "specific anticorrosive agent", and may contain a hypobromous acid stabilizing composition containing a "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound", a hypobromous acid stabilizing composition containing a "reaction product of a bromine compound and a chlorine-based oxidizing agent" and a sulfamic acid compound ", a" specific anticorrosive agent "and the" specific anticorrosive agent ".
(in the formula (1), R1Represents a hydrogen atom or a methyl group, X1Represents a hydrogen atom, a 1-or 2-valent metal atom, an ammonium group or an organic ammonium group. )
(in the formula (2), R2And R3Each independently represents a hydrogen atom or a methyl group, X2And X3Each independently represents a hydrogen atom, a 1-or 2-valent metal atom, an ammonium group or an organic ammonium group. )
(in the formula (3), R4Represents a hydrogen atom or a methyl group, X4The salt is a C1-10 alkylsulfonic acid group or a salt thereof, or a C6-10 arylsulfonic acid group or a salt thereof, and in the case of the salt, the salt is a 1-or 2-valent metal salt, ammonium salt or organic ammonium salt. )
(in the formula (4), R5Represents a hydrogen atom or a methyl group, X5And X6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and at least one is an alkyl group having 1 to 10 carbon atoms. )
(in the formula (5), Y represents a hydrogen atom or an alkali metal atom, and Z represents-CONHC (CH)3)2CH2SO3Na, h, l, m and n are respectively 0 or positive integers, and h + l + m + n is an integer of 1-100. )
(in the 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.)
(in the formula (7), Y1And Y2Each independently represents a hydrogen atom or an alkali metal atom. )
The organic ammonium salt in the formulae (1) to (3) is preferably, for example, an alkylammonium group or a (hydroxy) alkylammonium group having an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms.
Examples of the 1-or 2-valent metal salt in the formulae (1) to (3) include sodium salt, potassium salt, calcium salt, and magnesium salt.
As X in formula (3)4In the case of an alkylsulfonic acid group or a salt thereof, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms. As X4The aryl group in the case of an arylsulfonic acid group or a salt thereof is preferably an aryl group or arylalkyl group having 6 to 10 carbon atoms.
The alkyl group in the formula (4) is preferably an alkyl group having 1 to 8 carbon atoms.
The weight ratio of the monomer units in the binary copolymer comprising the monomer unit of formula (1) and the monomer unit of formula (3) is preferably 1 to 99: 99 to 1.
The weight ratio of the monomer units in the terpolymer comprising the monomer unit of formula (1), the monomer unit of formula (3), and the monomer unit of formula (4) is preferably 1 to 98: 1-98: 1-98.
The weight average molecular weight of the polymer containing the monomer units of the formulae (1) to (3) is preferably in the range of 500 to 100000. When the weight average molecular weight is less than 500 or more than 100000, the corrosion prevention performance may be lowered.
The weight average molecular weight of the phosphinocarboxylic acid copolymer of formula (5) is preferably in the range of 500 to 100000. When the weight average molecular weight is less than 500 or more than 100000, the corrosion prevention performance may be lowered. The weight average molecular weight of the bis (poly-2-carboxyethyl) phosphinic acid of formula (6) is preferably in the range of 500 to 100000. When the weight average molecular weight is less than 500 or more than 100000, the corrosion prevention performance may be lowered.
The alkali metal atom in the formulae (5), (6) and (7) is preferably a sodium atom or a potassium atom, and more preferably a sodium atom. Y of formula (7)1And Y2The 2-phosphonobutane-1, 2, 4-tricarboxylic acid which is a hydrogen atom is the following compound.
The azole compound generally functions as an anticorrosive agent for copper-based metals such as copper and copper alloys. Examples of the azole compound include 1,2, 3-benzotriazole, methylbenzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, imidazole, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole, and 1 kind of the azole compound may be used alone or 2 or more kinds may be used in combination. Among them, benzotriazole and methylbenzotriazole are preferable from the viewpoint of production cost and the like.
The ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" or the "reactant of the bromine compound and the chlorine-based oxidizing agent" is preferably 1 or more. When the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" or the "reactant of a bromine compound and a chlorine-based oxidizing agent" is less than 1, the amount of generated bromic acid in the reaction system may increase.
The effective bromine concentration contained in the composition is preferably in the range of 1 to 20 wt% based on the amount of the whole composition. When the effective bromine concentration is less than 1% by weight based on the total amount of the composition, the control of the biofouling may be poor, and when it exceeds 25% by weight, the amount of the generated bromic acid in the reaction system may be increased.
The bromine constituting the stabilized composition of hypobromous acid is required to be supplied as active bromine by any means, and bromine (liquid bromine) may be used as the bromine-based oxidizing agent, or active bromine produced by reacting a bromine compound with hypochlorite may be used, or active bromine via bromine chloride, bromate or the like may be used as the bromine-based oxidizing agent. Among them, most preferably, liquid bromine is used.
Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid, and the like.
Among these, a composition containing "a bromine and sulfamic acid compound" or "a reaction product of bromine and sulfamic acid compound" using bromine is more preferable because the stability of available bromine is high and by-production of bromic acid can be suppressed, compared with a composition containing "hypochlorous acid, a bromine compound and sulfamic acid" or a composition containing "bromine chloride and sulfamic acid".
That is, the water treatment agent composition of the present embodiment is preferably prepared by blending bromine as a bromine-based oxidizing agent, an aminosulfonic acid compound, and the anticorrosive agent at a pH of 13 or more.
Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Among them, sodium bromide is preferred in view of production cost.
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, and chlorinated isocyanuric acid or a salt thereof. Among them, examples of the salt include alkali metal hypochlorite salts such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal hypochlorite salts such as calcium hypochlorite and barium hypochlorite, alkali metal chlorite salts such as sodium chlorite and potassium chlorite, alkaline earth metal chlorite salts such as barium chlorite, other metal chlorite salts such as nickel chlorite, alkali metal chlorate salts such as ammonium chlorate, sodium chlorate and potassium chlorate, and alkaline earth metal chlorate salts such as calcium chlorate and barium chlorate. These chlorine-based oxidizing agents may be used alone in 1 kind or in combination with 2 or more kinds. As the chlorine-based oxidizing agent, sodium hypochlorite is preferably used in view of workability and the like.
The sulfamic acid compound is a compound represented by the following general formula (8).
R2NSO3H (8)
(wherein R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
Examples of the sulfamic acid compound which is considered to function as a stabilizer for an inorganic sludge control agent constituting a composition for stabilizing hypobromous acid include sulfamic acid (amidosulfuric acid) in which both of the 2R groups are hydrogen atoms, sulfamic acid compounds in which one of the 2R groups is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, such as N-methylaminosulfonic acid, N-ethylaminosulfonic acid, N-propylaminosulfonic acid, N-isopropylaminosulfonic acid, N-butylaminosulfonic acid, N-dimethylaminesulfonic acid, N-diethylaminosulfonic acid, N-dipropylaminosulfonic acid, N-dibutylaminosulfonic acid, N-methyl-N-ethylaminosulfonic acid, N-methyl-N-propylaminosulfonic acid, and sulfamic acid compounds in which both of the 2R groups are alkyl groups having 1 to 8 carbon atoms, N-dibutylaminosulfonic acid, N-methyl-N-ethylaminosulfonic acid, N-methyl-N-propylaminosulfonic acid, And sulfamic acid compounds such as N-phenyl sulfamic acid, wherein one of the 2R groups is a hydrogen atom, and the other is an aryl group having 6 to 10 carbon atoms, or salts thereof. 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, other metal salts such as manganese salt, copper salt, zinc salt, iron salt, cobalt salt and nickel salt, ammonium salt and guanidine salt. The sulfamic acid compounds and their salts may be used alone in 1 kind or in combination of 2 or more kinds. As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load and the like.
The water treatment agent composition of 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 temperature, etc., sodium hydroxide and potassium hydroxide may be used in combination. In addition, the base may be used in the form of an aqueous solution rather than a solid.
When the stabilizing composition of hypobromous acid is formulated with the anticorrosive agent, it is important to control the pH, and it is desirable that the pH is 13 or more before and after mixing the stabilizing composition of hypobromous acid with the anticorrosive agent. The pH of the composition is 13 or more, more preferably 13.2 or more, and still more preferably 13.5 or more. When the pH of the composition is less than 13.0, the stability of the stabilized composition of hypobromous acid changes, and liquefaction becomes difficult. When the anticorrosive agent is an azole compound, the composition has a pH of less than 13.2, and the stability of the stabilized composition of hypobromous acid changes to decompose the azole compound, so that liquefaction becomes difficult with time. This is greatly different from the one-dose formation of an azole compound and N-monochloroamino sulfonic acid formed from sodium hypochlorite and sulfamic acid as shown in patent document 2.
The content of bromate ions in the water treatment agent composition of the present embodiment is preferably 10mg/kg or less, more preferably 5mg/kg or less. When the bromate ion content exceeds 10mg/kg, the compatibility with the anticorrosive agent may be gradually deteriorated. When the anticorrosive agent is an azole compound, if the content of bromate ions exceeds 10mg/kg, the decomposition of the azole compound may be accelerated.
< preparation of water treatment agent composition >
The water treatment agent composition of the present embodiment can be obtained, for example, as follows: the bromine-based oxidizing agent may be mixed with the sulfamic acid compound, or a reaction product of the bromine compound and the chlorine-based oxidizing agent may be mixed with the sulfamic acid compound and then mixed with the anticorrosive agent, or may be further mixed with an alkali.
The process for producing a water treatment agent composition containing bromine, a sulfamic acid compound and the anticorrosive agent, or a reaction product of bromine and a sulfamic acid compound, and the anticorrosive agent preferably comprises the steps of: adding bromine to a mixed solution containing water, a base and a sulfamic acid compound in an inert gas atmosphere to cause a reaction; and then mixing the reactant with the anticorrosive agent. The bromate ion concentration in the composition becomes low by adding and reacting under an inert gas atmosphere.
The inert gas to be used is not limited, but at least 1 of nitrogen and argon is preferable from the viewpoint of production and the like, and nitrogen is particularly preferable from the viewpoint of production cost and the like.
The oxygen concentration in the reactor when bromine is added is preferably 6% or less, more preferably 4% or less, still more preferably 2% or less, and particularly preferably 1% or less. When the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of the generated bromic acid in the reaction system may increase.
The addition rate of bromine is preferably 25 wt% or less, more preferably 1 wt% or more and 20 wt% or less, based on the total amount of the composition. When the bromine addition rate exceeds 25% by weight based on the total amount of the composition, the amount of the generated bromic acid in the reaction system may increase. When the amount is less than 1% by weight, the sterilizing power is sometimes deteriorated.
The reaction temperature when bromine is added is preferably controlled to be in the range of 0 ℃ to 25 ℃ inclusive, and more preferably in the range of 0 ℃ to 15 ℃ inclusive from the viewpoint of production cost and the like. When the reaction temperature at the time of bromine addition exceeds 25 ℃, the amount of generated bromic acid in the reaction system may increase, and when it is lower than 0 ℃, it may freeze.
In the method for producing a water treatment agent composition according to the present embodiment, the main sulfamic acid-sodium hypobromite composition contains substantially no bromate ions, and can be safely treated. The method for producing a water treatment agent composition according to the present embodiment can provide a one-pack water treatment agent composition which contains substantially no bromate ions, has excellent bactericidal performance, and has excellent storage stability.
Water treatment method Using Water treatment agent composition
The water treatment agent composition of the present embodiment can be used in water treatment methods such as water treatment of industrial water systems such as cooling water and piping cleaning for promoting biofouling.
The effective bromine concentration in the water system to which the water treatment agent composition of the present embodiment is added is preferably 0.01 to 100 mg/L. If the concentration is less than 0.01mg/L, a sufficient sludge-inhibiting effect may not be obtained, and if the concentration is more than 100mg/L, corrosion of piping or the like may be caused.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
The examples and comparative examples were prepared by adding (adding in order from the table) the components (wt%) shown in tables 1 to 8 in the order of addition. The preparation is carried out by adding each chemical while cooling to room temperature or lower in a container made of PTFE (polytetrafluoroethylene) and stirring with a stirrer.
In tables 1 to 5, "PAA" is an acrylic acid homopolymer (weight average molecular weight of about 4500), "AABI" is an acrylic acid based binary copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight average molecular weight of about 4500), "PMAA" is a maleic acid homopolymer (weight average molecular weight of about 1000), "AATER" is an acrylic acid based ternary copolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and alkylacrylamide (weight average molecular weight of about 4500). "PCABI" is a phosphinocarboxylic acid copolymer of formula (5) (h + l + m + n has an average value of about 16), "BCAP" is a bis (poly-2-carboxyethyl) phosphinic acid of formula (6) (m + n has an average value of about 16), "PBTC" is 2-phosphonobutane-1, 2, 4-tricarboxylic acid, "HEDP" is 1-hydroxyethylidene-1, 1-diphosphonic acid.
In tables 1 to 8, stabilized hypobromous acids A, a, B and C are as follows.
[ stabilized hypobromous acid A ]
While controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel was maintained at 1%, 1436g of water and 361g of sodium hydroxide were added to a 2L four-necked flask sealed in a continuous flask and mixed, then 300g of sulfamic acid was added and mixed, and then 473g of liquid bromine was added while maintaining the temperature of the reaction solution at 0 to 15 ℃ and further 230g of 48% potassium hydroxide solution was added to obtain the target stabilized hypobromous acid A, wherein the weight ratio of sulfamic acid to bromine was 10.7%, bromine was 16.9%, and the ratio of the equivalents of sulfamic acid to the equivalents of bromine was 1.04. The pH of the resulting solution was measured by a glass electrode method and found to be 14.0. The bromine content of the resulting solution was measured by converting bromine into iodine with potassium iodide and then performing redox titration with sodium thiosulfate, and found to be 16.9%, which was 100.0% of the theoretical content (16.9%). The oxygen concentration in the reaction vessel at the time of bromine reaction was measured by using an "oxygen monitor JKO-02 LJDII" manufactured by JIKCO Ltd.
The pH was measured under the following conditions.
Electrode type: glass electrode type
A pH meter: IOL-30 type manufactured by DKK-TOA CORPORATION
And (3) correcting the electrodes: the pH of the sample was adjusted to 2 points using a neutral phosphate pH (6.86) standard solution (type 2) manufactured by Kanto chemical Co., Ltd and a borate pH (9.18) standard solution (type 2) manufactured by the same company
Measuring temperature: 25 deg.C
Measurement value: the electrode was immersed in the measurement solution, and the value after stabilization was defined as the measurement value, and the average value of 3 measurements
[ stabilized hypobromous acid a ]
The target stabilized hypobromous acid a was obtained in the same composition ratio and production method as those of the stabilized hypobromous acid a except that the reaction was carried out under the atmosphere without flowing a nitrogen gas. The pH of the stabilized hypobromous acid a was 14, and the bromine content was 16.9%.
[ stabilized hypobromous acid B ]
The composition is prepared by the following steps based on the contents described in Japanese patent application laid-open No. 11-506139. The stabilized hypobromous acid B had a pH of 14 and a bromine content of 9.2%.
(1) To 60.0 g of a 40 wt% sodium bromide pure water solution, 50.0 g of a 12% sodium hypochlorite solution was added and stirred.
(2) A stabilizing solution was prepared consisting of 20.6 g of pure water, 9.6 g of sulfamic acid, and 6.6g of sodium hydroxide.
(3) And (3) adding the stabilizing solution in the step (2) into the solution in the step (1) while stirring to obtain the target stabilized hypobromous acid B.
[ stabilized hypobromous acid C ]
It is a composition containing bromine chloride, sulfamic acid and sodium hydroxide. The stabilized hypobromous acid C had a pH of 14 and a bromine content of 15.5%.
In examples and comparative examples, the effective bromine concentration was determined by diluting a sample 2 ten thousand times, measuring the effective chlorine by an effective chlorine measuring method (DPD (diethyl-p-phenylenediamine) method) using a multinomial water quality analyzer DR/4000 available from HACH corporation, and then converting the molecular weight of chlorine and bromine into the effective bromine concentration. Further, for each water treatment agent composition, the effective bromine concentration after storage at 25 ℃ for 5 days or 14 days under light shielding was measured, and the residual ratio to the effective bromine concentration immediately after formulation was calculated.
The free halogen concentration and total halogen concentration were determined as follows: the sample was diluted 2 ten thousand times and measured by an effective chlorine measuring method (DPD (diethyl-p-phenylenediamine) method) using a multinomial water quality analyzer DR/4000 of HACH corporation. The free bromine concentration and the total bromine concentration are values calculated from the molecular weights of chlorine and bromine after values are obtained as the free chlorine concentration and the total chlorine concentration.
The residual ratio of the azole compound was represented by the residual ratio of each composition to the initial concentration of the azole compound after storage at 50 ℃ for 5 days in the dark. The azole compound was measured under the following conditions using a liquid chromatograph (8020 series) manufactured by tokyo co.
Column: TSKGEL ODS-80TS (made by Tosoh)
Eluent: acetonitrile 20% solution
Eluent flow rate: 1.0 mL/min
A detector: multi-wavelength detector
Measuring wavelength: 275nm
In addition, for the compositions of tables 2,3, 4, 7, and 8, bromate ion concentration was measured by the analysis method of "JWWA K120 (2008) sodium hypochlorite for water passage 5.4.5 bromate" and by post-column-ion chromatography.
When the free halogen concentration (free bromine concentration or free chlorine concentration) is 70% or more of the total halogen concentration (total bromine concentration or total chlorine concentration), it is judged that the sludge control performance, which is a high oxidizing power, is exhibited.
In addition, with respect to the compositions of tables 2 and 3, the presence or absence of precipitates was visually confirmed, and turbidity was measured by absorptiometry using a multinomial mesh water quality analyzer DR/4000 of HACH corporation.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
[ Table 7]
[ Table 8]
In the compositions of examples, by blending the inorganic sludge control agent, i.e., the hypobromite, with the sulfamic acid compound, and with the specific anticorrosive at pH13 or more, a significant decrease in the sludge control performance (a significant decrease in the oxidizing power) of the inorganic sludge control agent can be suppressed, and in addition, the inorganic sludge control agent, i.e., the hypobromite, can be made into one with the anticorrosive without generating white precipitates. As is clear from the results in Table 1, the effective bromine residual ratio became high at a pH of 13.0 or more. It is understood that the effective bromine concentration immediately after formulation in example 1-1 was 6.8% by weight, and that the free bromine was prepared in a state of high oxidation force as 6.7% by weight and the ratio of the free bromine in the total effective bromine was 98%. In addition, the compositions of examples 1 to 4 and 10 to 12, which particularly contain stabilized hypobromous acid a formed from "bromine" and "sulfamic acid compound", and the compositions of examples 5 to 9 and 13 to 15, which contain "bromine chloride and sulfamic acid" (stabilized hypobromous acid C), have higher stability of available bromine and can suppress by-production of bromic acid, compared with the compositions of "hypochlorous acid and bromine compound and sulfamic acid" (stabilized hypobromous acid B). Further, according to the comparison between examples 1 to 3, 5 to 7, 9 to 11, 13 and 14 and examples 4, 8, 12 and 15, the formulations of the compositions containing the anticorrosive agents 1 to 3, 5 and 6 have particularly low turbidity and can be formulations of high-quality water treatment agent compositions. When the case of using the stabilized hypobromous acid a (example 1-1) produced under a nitrogen atmosphere is compared with the case of using the stabilized hypobromous acid a (example 16) produced under an atmosphere (see table 4), it is understood that the by-production of the bromic acid can be suppressed when the stabilized hypobromous acid a produced under a nitrogen atmosphere is used. In addition, according to the results of table 5, even if the azole compound is further compounded, the stability of available bromine is high.
As is clear from the results in Table 6, the remaining ratio of the azole compound becomes high at a pH of 13.2 or more. In addition, the compositions of examples 20, 23 to 26, which particularly contained stabilized hypobromous acid a formed from "bromine" and "sulfamic acid compound", had higher residual rates of azole compound than the compositions of examples 21, 22, 27, and 28, which contained "hypochlorous acid and bromine compound and sulfamic acid" (stabilized hypobromous acid B) and "bromine chloride and sulfamic acid" (stabilized hypobromous acid C). The bromate ion concentration is low.
As for the difference, although the reason why the difference in stability of the azole compound is caused is not clearly elucidated, it is presumed that the azole compound is decomposed due to the bromate ion, because the bromate ion is not detected from the stabilized hypobromous acid a, and the bromate ion is detected from the stabilized hypobromous acid B, C.
In comparative example 7 (corresponding to patent document 2), since bound chlorine in which hypochlorous acid and sulfamic acid are strongly bound is formed, azole compounds are not easily decomposed, and the percentage of azole residues is high, but the percentage of free halogen is as low as 9.1%, and sludge control performance is low. When the case of using the stabilized hypobromous acid a produced under a nitrogen atmosphere (example 20-1) and the case of using the stabilized hypobromous acid a produced under an atmosphere (example 20-4) are compared (see table 8), it is understood that the use of the stabilized hypobromous acid a produced under a nitrogen atmosphere can further suppress the by-production of the bromic acid and the rate of the by-production of the azole compound is slightly high.
Claims (4)
1. A water treatment agent composition characterized by comprising a stabilized hypobromous acid composition comprising a bromine compound and an aminosulfonic acid compound, and
a polymer comprising a monomer unit of formula (1), a bipolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3), a terpolymer comprising a monomer unit of formula (1) and a monomer unit of formula (3) and a monomer unit of formula (4), a phosphinocarboxylic acid copolymer of formula (5), a bis (poly-2-carboxyethyl) phosphinic acid of formula (6), and at least 1 corrosion inhibitor of an azole compound
The composition is compounded at a pH of 13.2 or more to prepare a single preparation,
in the formula (1), R1Represents a hydrogen atom or a methyl group, X1Represents a hydrogen atom, a 1-or 2-valent metal atom, an ammonium group or an organic ammonium group,
in the formula (3), R4Represents a hydrogen atom or a methyl group, X4An alkylsulfonic acid group having 1 to 10 carbon atoms or a salt thereofA salt, or an arylsulfonic acid group having 6 to 10 carbon atoms or a salt thereof, wherein in the case of the salt, the salt is a 1-valent or 2-valent metal salt, an ammonium salt or an organic ammonium salt,
in the formula (4), R5Represents a hydrogen atom or a methyl group, X5And X6Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group having 1 to 10 carbon atoms,
in the formula (5), Y represents a hydrogen atom or an alkali metal atom, and Z represents-CONHC (CH)3)2CH2SO3Na, h, l, m and n are respectively 0 or positive integers, h + l + m + n is an integer of 1-100,
in the 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.
2. The water treatment agent composition according to claim 1,
the concentration of bromic acid in the water treatment agent composition is lower than 5 mg/kg.
3. A process for producing a water treatment agent composition according to claim 1 or 2,
the method comprises the following steps: bromine is added to a mixed solution containing water, a base and a sulfamic acid compound in an inert gas atmosphere, and a reaction is performed.
4. A water treatment method characterized by treating water with the water treatment agent composition according to claim 1 or 2.
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| CN1646011A (en) * | 2002-03-05 | 2005-07-27 | 亚古实验股份有限公司 | A method of preparing a biocide comprising stabilized hypochlorite and a bromide ion source and a method of controlling microbial fouling using the same |
| CN1655676A (en) * | 2002-05-22 | 2005-08-17 | 栗田工业株式会社 | Composition for prevention of slime and method for preventing slime |
| CN1708227A (en) * | 2002-10-28 | 2005-12-14 | 阿尔伯麦尔公司 | Active bromine containing biocidal compositions and their preparation |
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| JP3685800B1 (en) * | 2004-09-17 | 2005-08-24 | 東西化学産業株式会社 | Hypobromite formation in aqueous systems |
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| CN1655676A (en) * | 2002-05-22 | 2005-08-17 | 栗田工业株式会社 | Composition for prevention of slime and method for preventing slime |
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