WO2024116641A1 - 水処理剤及び水処理方法 - Google Patents

水処理剤及び水処理方法 Download PDF

Info

Publication number
WO2024116641A1
WO2024116641A1 PCT/JP2023/037910 JP2023037910W WO2024116641A1 WO 2024116641 A1 WO2024116641 A1 WO 2024116641A1 JP 2023037910 W JP2023037910 W JP 2023037910W WO 2024116641 A1 WO2024116641 A1 WO 2024116641A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
water treatment
salt
treatment agent
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/037910
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
惇 山口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Chemical Industries Ltd
Original Assignee
Sanyo Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Chemical Industries Ltd filed Critical Sanyo Chemical Industries Ltd
Priority to JP2024561244A priority Critical patent/JPWO2024116641A1/ja
Publication of WO2024116641A1 publication Critical patent/WO2024116641A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

Definitions

  • the present invention relates to a water treatment agent and a water treatment method. More specifically, the present invention relates to a water treatment agent and a water treatment method for removing water-soluble COD components from water containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge).
  • water-soluble COD components such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge).
  • Patent Document 2 proposes a water treatment method that can stably reduce water-soluble COD components even if an excessive amount of water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater.
  • the water treatment method includes a step of adding to the water to be treated a water treatment agent containing a copolymer having a weight average molecular weight of 10,000 to 600,000, which is obtained by polymerizing a monomer having a cationic functional group and a monomer having no cationic functional group in a specific molar ratio, and a water treatment agent containing at least one salt selected from the group consisting of silicates, phosphates, and borates.
  • a water treatment agent containing a copolymer having a weight average molecular weight of 10,000 to 600,000 which is obtained by polymerizing a monomer having a cationic functional group and a monomer having no cationic functional group in a specific molar ratio
  • the present invention has been made in consideration of the problems of the prior art, and the object of the present invention is to provide a water treatment agent and a water treatment method that can stably reduce water-soluble COD components even when an excessive amount of the water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater, and that is remarkably effective in reducing water-soluble COD components.
  • the present invention is a water treatment agent containing a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
  • A quaternary ammonium salt
  • S salt
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group
  • X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • the present invention also provides a water treatment method comprising a step (I) of adding a quaternary ammonium salt (A) represented by any one of the general formulae (1) to (3) to the water to be treated, and a step (II) of adding at least one salt (S) selected from the group consisting of silicates, phosphates, and borates to the water to be treated.
  • a quaternary ammonium salt A
  • S at least one salt
  • water-soluble COD component reduction effect means the effect of reducing the content of water-soluble COD components in water by forming water-insoluble complexes with the water-soluble COD components contained in the water to be treated, precipitating them, and separating and removing them.
  • 1 is a graph showing the relationship between the amount (mg/L) of solids of a quaternary ammonium salt (A) added in a water treatment agent and COD (mg/L).
  • the water treatment agent of the present embodiment contains a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
  • A quaternary ammonium salt
  • S salt
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group
  • X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • n is an integer of 5 to 17 representing the number of repeating methylene groups
  • X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
  • the water treatment agent of this embodiment may be a one-component water treatment agent that is a composition containing the quaternary ammonium salt (A) and the salt (S), or may be a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S).
  • the water treatment agent of this embodiment is preferably a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S).
  • the quaternary ammonium salt (A) is a compound having a structure represented by any one of the general formulas (1) to (3).
  • a compound having a structure represented by the general formula (1) will be referred to as compound (A1)
  • a compound having a structure represented by the general formula (2) will be referred to as compound (A2)
  • a compound having a structure represented by the general formula (3) will be referred to as compound (A3).
  • n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
  • linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A1) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
  • R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group.
  • X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
  • Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids (sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)).
  • X ⁇ is preferred.
  • the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
  • X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
  • the cation (ammonium ion) in the compound (A1) include hexyltrimethylammonium ion, heptyltrimethylammonium ion, octyltrimethylammonium ion, nonyltrimethylammonium ion, decyltrimethylammonium ion, undecyltrimethylammonium ion, dodecyltrimethylammonium (lauryltrimethylammonium) ion, tridecyltrimethylammonium ion, tetradecyltrimethylammonium (myristyltrimethylammonium) ion, pentadecyltrimethylammonium ion, hexadecyltrimethylammonium ion, heptadecyltrimethylammonium ion, octadecyltrimethylammonium (trimethylstearylammonium) ion, and mixtures thereof.
  • the hexadecyltrimethylammonium ion or octadecyltrimethylammonium (trimethylstearylammonium) ion is preferred.
  • n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
  • linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A2) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
  • X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
  • Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like.
  • X ⁇ is preferred.
  • the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
  • X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
  • cation (ammonium ion) in the compound (A2) include benzylhexyldimethylammonium ion, benzylheptyldimethylammonium ion, benzyloctyldimethylammonium ion, benzylnonyldimethylammonium ion, benzyldecyldimethylammonium ion, benzylundecyldimethylammonium ion, benzyldodecyldimethylammonium (benzyllauryldimethylammonium) ion, benzyltridecyldimethylammonium ion, benzyltetradecyldimethylammonium (benzylmyristyldimethylammonium) ion, benzylpentadecyldimethylammonium ion, benzylhexadecyldimethylammonium i
  • n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
  • linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A3) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
  • X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
  • Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like.
  • X ⁇ is preferred.
  • the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
  • X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
  • Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and from the viewpoint of the effect of reducing water-soluble COD components, a hydrogen atom or a methyl group is preferred.
  • cation (ammonium ion) in the compound (A3) include 1-hexylpyridinium ion, 1-hexyl-4-methylpyridinium ion, 1-heptylpyridinium ion, 1-heptyl-4-methylpyridinium ion, 1-octylpyridinium ion, 1-octyl-4-methylpyridinium ion, 1-nonylpyridinium ion, 1-nonyl-4-methylpyridinium ion, 1-decylpyridinium ion, 1-decyl-4-methyl ...
  • the salt (S) is at least one selected from the group consisting of silicates, phosphates, and borates.
  • the salt (S) may be used alone or in combination of two or more.
  • the silicate may be an alkali metal salt or an alkaline earth metal salt of silicic acid, or an alkali metal salt or an alkaline earth metal salt of condensed silicic acid.
  • the silicate is preferably at least one selected from the group consisting of lithium silicate, sodium silicate, potassium silicate, and calcium silicate, and more preferably sodium silicate.
  • the silicate may be in the form of a solid or an aqueous solution, and aqueous solutions of sodium silicate (No. 1, No. 2, No. 3, No. 4, No. 5), so-called water glass, may be used.
  • the phosphate salt may be an alkali metal salt or an alkaline earth metal salt of phosphoric acid, or an alkali metal salt or an alkaline earth metal salt of condensed phosphoric acid (polyphosphoric acid, metaphosphoric acid, etc.).
  • the phosphate salt is preferably at least one selected from the group consisting of monosodium phosphate, disodium phosphate, trisodium phosphate, potassium hydrogen phosphate, and sodium polyphosphate, and more preferably trisodium phosphate.
  • the borate salt may be an alkali metal salt or an alkaline earth metal salt of boric acid, an alkali metal salt or an alkaline earth metal salt of polyboric acid, or a hydrate thereof.
  • the borate salt is preferably at least one selected from the group consisting of trisodium borate, sodium metaborate, and sodium tetraborate, and more preferably sodium tetraborate decahydrate.
  • the salt (S) preferably contains the silicate, and more preferably contains sodium silicate.
  • the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) in the water treatment agent of this embodiment is preferably 0.01 to 30, more preferably 0.1 to 20, and even more preferably 1 to 10, from the viewpoints of the effect of reducing water-soluble COD components, the amount of sludge generated, and treatment costs.
  • the water treatment agent of this embodiment may further contain water in addition to the quaternary ammonium salt (A) and the salt (S) from the viewpoint of operability (handling ability) and the like.
  • the total content of the quaternary ammonium salt (A) and the salt (S) in the water treatment agent of this embodiment is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water.
  • the content of the quaternary ammonium salt (A) in the water treatment agent of this embodiment is preferably 0.1 to 30% by weight, more preferably 1 to 15% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water.
  • the total content of the quaternary ammonium salt (A), the salt (S), and water is preferably 90 to 100% by weight based on the weight of the water treatment agent.
  • the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P1) may contain water in addition to the quaternary ammonium salt (A).
  • the content of the quaternary ammonium salt (A) in the water treatment agent (P1) is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the water treatment agent (P1) from the viewpoint of operability and the effect of reducing water-soluble COD components.
  • the total content of the quaternary ammonium salt (A) and water in the water treatment agent (P1) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P1).
  • the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P2) may contain water in addition to the salt (S).
  • the content of the salt (S) in the water treatment agent (P2) is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the weight of the water treatment agent (P2) from the viewpoint of operability and the effect of reducing water-soluble COD components.
  • the content of the salt (S) in the water treatment agent (P2) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P2).
  • the water treatment agent of this embodiment may contain an organic coagulant to the extent that the effect of the present invention is not impaired in order to further improve the removal performance of water-soluble COD components.
  • the organic coagulant include polycondensates of epihalohydrin and amine and their hydrochlorides, polycondensates of epihalohydrin and alkylenediamine and their hydrochlorides, polyethyleneimine and its hydrochlorides, alkylenedihalide-alkylenepolyamine polycondensates and their hydrochlorides, aniline-formaldehyde polycondensates and their hydrochlorides, polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine and its hydrochlorides, (di)methyldi(meth)allylammonium chloride, and polyvinylimidazoline and its hydrochlorides.
  • the organic coagulant may be used alone or in combination of two or more types.
  • the organic coagulant may be contained in both or either of the
  • the method for producing the water treatment agent of this embodiment is not particularly limited, but it can be produced, for example, as follows.
  • the water treatment agent When the water treatment agent is a one-component type, it can be produced by mixing the quaternary ammonium salt (A) diluted with water as necessary, the salt (S) diluted with water as necessary, and additives as necessary.
  • the mixing method is not particularly limited, and for example, mixing may be performed using a stirrer in a container such as a bucket.
  • the quaternary ammonium salt (A) and the salt (S) may form a complex and become cloudy, but it can be used without problems by stirring and mixing again immediately before use.
  • the water treatment agent (P1) can be produced by mixing the quaternary ammonium salt (A), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced by mixing the salt (B), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced.
  • the method of diluting the quaternary ammonium salt (A) and/or the salt (S) with water is not particularly limited, but for example, a method can be used in which a predetermined amount of the quaternary ammonium salt (A) and/or the salt (S) is added to a previously measured amount of water while stirring it using a known stirring device (such as a jar tester), and the water is stirred for several hours (approximately 1 to 4 hours).
  • the quaternary ammonium salt (A) forms a water-insoluble complex with the water-soluble COD components contained in the water to be treated, causing them to become insoluble and precipitate, and the precipitate is separated and removed, thereby reducing the water-soluble COD components.
  • the water treatment agent further contains the salt (S)
  • the complex between the quaternary ammonium salt (A) and the water-soluble COD components is coarsened, facilitating the separation and removal of the precipitate, and a further reduction effect in the water-soluble COD components can be expected.
  • the salt (S) precipitates the excessively added quaternary ammonium salt (A), and the quaternary ammonium salt (A) itself becomes a water-soluble COD component and can suppress the increase in the water-soluble COD components, so it is presumed that a stable water-soluble COD reduction effect can be expressed.
  • the salt (S) can precipitate a complex of the water-soluble COD components dissolved in water and the quaternary ammonium salt (A), and is presumed to have an effect of reducing water-soluble COD components.
  • the water treatment agent of the present invention is very useful because, when added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steel, food, gravel, semiconductor-related and cleaning industries, etc.), sewage, purified water, sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress the increase in water-soluble COD components, even under conditions where the amount of water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and has a significantly excellent effect in reducing water-soluble COD components.
  • the water treatment method of this embodiment includes a step (I) of adding the quaternary ammonium salt (A) to water to be treated (hereinafter, in this specification, may be referred to as water to be treated) containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge), and a step (II) of adding the salt (S) to the water to be treated.
  • a step (I) of adding the quaternary ammonium salt (A) to water to be treated hereinafter, in this specification, may be referred to as water to be treated
  • water-soluble COD components such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge)
  • S salt
  • Step (I) The step (I) is a step of adding the quaternary ammonium salt (A) to the water to be treated.
  • the amount of the quaternary ammonium salt (A) added to the water to be treated can be adjusted depending on the type of water to be treated, the content of particles suspended in the water to be treated, the amount of water-soluble COD components, etc., and is not particularly limited. From the viewpoint of water-soluble COD component reduction performance, however, 1 mg to 10 g per 1 L of the water to be treated is preferable, 3 mg to 8 g is more preferable, 5 mg to 5 g is even more preferable, and 5 mg to 3 g is even more preferable.
  • step (I) the method for adding the quaternary ammonium salt (A) to the water to be treated is not particularly limited, and the quaternary ammonium salt (A) can be added to the water to be treated and mixed by a known method.
  • Step (II) is a step of adding the salt (S) to the water to be treated.
  • the amount of the salt (S) added to the water to be treated is preferably an amount such that the weight ratio of the salt (S) to the weight of the quaternary ammonium salt (A) [(S)/(A)] is 0.01 to 30, more preferably an amount such that the weight ratio is 0.1 to 20, and even more preferably an amount such that the weight ratio is 1 to 10.
  • step (II) the method for adding the salt (S) to the water to be treated is not particularly limited, and the salt (S) can be added to the water to be treated and mixed using a known method.
  • the steps (I) and (II) may be carried out separately or simultaneously.
  • the water treatment agent (P1) containing the quaternary ammonium salt (A) and the water treatment agent (P2) containing the salt (S) are added separately.
  • the steps (I) and (II) are carried out simultaneously, the quaternary ammonium salt (A) and the salt (S) are mixed in advance and added as a one-agent type water treatment agent. From the viewpoint of the effect of reducing water-soluble COD components, it is preferable to carry out the steps (I) and (II) separately, and it is more preferable to carry out the step (II) after carrying out the step (I).
  • the water treatment method of the present embodiment may further include, in addition to the step (I) and the step (II), a step (III) of adding an inorganic flocculant to the water to be treated.
  • the inorganic flocculants include aluminum sulfate, polyaluminum chloride, ferric chloride, polyferric sulfate, and hydrated lime. Each of the inorganic flocculants may be used alone or in combination of two or more.
  • the amount of inorganic flocculant added when the water treatment method of this embodiment includes step (III) varies depending on the type of sludge or wastewater, the size and content of suspended particles, the total sludge and the amount of water-soluble COD components in the wastewater, etc., but is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.8% by weight, and even more preferably 0.01 to 0.5% by weight based on the weight of the sludge or wastewater. If it is 0.001% by weight or more, the effect of reducing water-soluble COD components will be more pronounced, and if it is 1% by weight or less, the amount of sludge generated can be reduced.
  • the steps (I) to (III) may be performed separately or simultaneously.
  • the steps (I) to (III) are preferably performed in any one of the following procedures (i) to (iv).
  • Step (i) After step (I), step (III) is carried out, and then step (II) is carried out.
  • step (ii) After step (III), step (I) is carried out, and then step (II) is carried out.
  • Step (iii) and step (III) are carried out simultaneously ⁇ i.e., the quaternary ammonium salt (A) and the inorganic flocculant are mixed in advance and then added to the water to be treated ⁇ , and then step (II) is carried out.
  • Step (iv) After step (I), step (II) is carried out, and then step (III) is carried out.
  • the water treatment method of this embodiment includes the step (III), from the viewpoint of treatment costs, it is preferable to carry out the step (II) after carrying out the steps (I) and (III). In other words, it is preferable to carry out the steps (I) to (III) in any of the above procedures (i) to (iii).
  • pH adjustment step The pH of the water to be treated after the steps (I) and (II) have been performed, or after the steps (I) to (III) have been performed if the water treatment method of the present embodiment has the step (III), is preferably 1 to 12, more preferably 3 to 10, and even more preferably 5 to 8. In this range, the effects of the present invention, such as reduction of water-soluble COD components, can be more effectively achieved.
  • the water treatment method of the present embodiment may have a pH adjustment step of adding an inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an inorganic solid acidic substance (acidic sodium phosphate, acidic sulfuric acid, ammonium chloride, ammonium sulfate, ammonium bicarbonate, sulfamic acid, etc.), an organic acid (oxalic acid, succinic acid, malic acid, etc.), an inorganic alkaline substance (e.g., sodium hydroxide, potassium hydroxide, ammonia, etc.), and an organic alkaline substance (e.g., guanidine, etc.) or an aqueous solution thereof, in order to adjust the pH of the water to be treated after the steps (I) and (II), etc. have been performed.
  • an inorganic acid hydroochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
  • an inorganic solid acidic substance
  • the water treatment method of the present embodiment preferably further comprises a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after carrying out the steps (I) and (II) or, in the case where the water treatment method of the present embodiment comprises the step (III), after carrying out the steps (I) to (III) to form coarse flocs.
  • the polymer flocculant is not particularly limited, and any commonly used known polymer flocculant can be suitably used.
  • the polymer flocculant may be any of cationic, nonionic, anionic, and amphoteric polymer flocculants, and these may also be used in combination.
  • the cationic polymer flocculant may be a homopolymer of polyethyleneimine, a Mannich modified poly(meth)acrylamide, a quaternized dialkylaminoethyl (meth)acrylate, or a copolymer with other monomers such as (meth)acrylamide, or a copolymer containing the cationic monomer as a constituent unit.
  • the nonionic polymer flocculant may be polyacrylamide or the like with a Mw of more than 1,000,000.
  • the anionic polymer flocculant may, for example, be sodium poly(meth)acrylate, hydrolyzed poly(meth)acrylamide, (meth)acrylamide-sodium (meth)acrylate copolymer, (meth)acrylamide-sodium (meth)acrylate-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, (meth)acrylamide-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, and other (co)polymers containing the anionic monomers described above.
  • the amphoteric polymer flocculant may be a copolymer of a cationic monomer (such as dialkylaminoethyl (meth)acrylate quaternized products and other cationic monomers as described above) with an anionic monomer (such as (meth)acrylic acid (salt), 2-acrylamido-2-methylpropane-1-sulfonic acid (salt)), and, if necessary, a nonionic monomer (such as acrylamide).
  • a cationic monomer such as dialkylaminoethyl (meth)acrylate quaternized products and other cationic monomers as described above
  • anionic monomer such as (meth)acrylic acid (salt), 2-acrylamido-2-methylpropane-1-sulfonic acid (salt)
  • a nonionic monomer such as acrylamide
  • the polymer flocculant addition step there is no particular limitation on the method of adding the polymer flocculant.
  • the polymer flocculant may be added as is, but from the viewpoint of uniform mixing, it is preferable to add the polymer flocculant to the water to be treated after making it into an aqueous solution.
  • the concentration of the polymer flocculant is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight.
  • the amount of polymer flocculant added varies depending on the type of water to be treated, the size and content of suspended particles, and the molecular weight of the polymer flocculant, but from the viewpoint of general flocculation performance, it is preferably 0.0001 to 0.5% by weight, more preferably 0.0002 to 0.3% by weight, even more preferably 0.0003 to 0.2% by weight, and even more preferably 0.0004 to 0.1% by weight based on the weight of the water to be treated.
  • the water treatment method of this embodiment may include a solid-liquid separation step of removing precipitates precipitated in the water to be treated that has been treated in the step (I), the step (II), and the like, from the water to be treated.
  • methods for separating the solid and liquid can be used, such as gravity settling, membrane filtration, column filtration, pressure flotation, concentrators (e.g., thickeners, etc.), and dehydrators (e.g., centrifuges, belt press dehydrators, filter press dehydrators, etc.).
  • Example (1) After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, a solid-liquid separation step is carried out.
  • Example (2) After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is carried out, and further, the solid-liquid separation step is carried out.
  • Example (3) The steps (I), (II) and (III) are carried out, and the pH adjustment step is carried out as necessary, and then the solid-liquid separation step is carried out.
  • Example (4) After carrying out the steps (I), (II) and (III) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is further carried out, and then the solid-liquid separation step is further carried out.
  • examples (2) and (4) are preferred from the viewpoint of forming coarser flocs and facilitating solid-liquid separation.
  • the water treatment method of this embodiment may also include an activated carbon treatment step in which the water to be treated after the solid-liquid separation step is treated with activated carbon.
  • the COD of the treated wastewater may be measured directly, but the effect of reducing COD can also be evaluated using TOC (total organic carbon), which is commonly used in the field of wastewater treatment as an alternative means of monitoring COD and can be measured more easily than COD.
  • TOC total organic carbon
  • the raw materials represented by each symbol in Tables 1 to 5 are as follows.
  • the amount of each raw material ⁇ quaternary ammonium salt (A), comparative quaternary ammonium salt (comparative A), cationic polymer (M) and salt (S) ⁇ added in Tables 1 to 5 is the amount (mg) of solids (components excluding water and volatile solvents) of each raw material added per 1 L of water to be treated (wastewater from chemical plant B described below).
  • A1-1 Hexyl trimethyl ammonium chloride (A1-2): Lauryl trimethyl ammonium chloride (A1-3): Hexadecyl trimethyl ammonium chloride (A1-4): Trimethylstearyl ammonium chloride (A1-5): Tetradecyl trimethyl ammonium chloride (A1-6): Tetradecyl trimethyl ammonium bromide (A1-7): Hexadecyl trimethyl ammonium bromide (A1-8): Hexadecyl trimethyl ammonium hydroxide (A2-1): Benzyl hexyl dimethyl ammonium chloride (A2-2): Benzyl lauryl dimethyl ammonium chloride (A2-3): Benzyl Benzylhexadecyldimethylammonium chloride (A2-4): Benzyldimethylstearylammonium chloride (A3-1): 1-hexyl
  • Comparative Production Example 1 Production of cationic polymer (M-1) and comparative water treatment agent (Comparative PM-1) A four-neck flask equipped with a stirrer, a temperature sensor, a cooling tube, a dropping funnel and a mantle heater was charged with 190 parts of isopropyl alcohol (hereinafter abbreviated as "IPA”) and 69 parts of ion-exchanged water, and heated to reflux under stirring.
  • IPA isopropyl alcohol
  • a mixed solution of 80 parts of IPA, 20 parts of ion-exchanged water, and 0.7 parts of azobisisobutyronitrile (hereinafter abbreviated as "AIBN”) was added as an initiator solution from the dropping port, and a homogeneous mixture of 80% by weight of trimethyl-2-methacryloyloxyethylammonium chloride aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 352 parts, styrene (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 48 parts, IPA 180 parts, and ion-exchanged water 60 parts was added dropwise to the flask simultaneously over 4 hours while stirring the flask at 80 to 85 ° C.
  • AIBN azobisisobutyronitrile
  • the aqueous solution was diluted with ion-exchanged water to a solid content of 10.0 wt %, to obtain a comparative water treatment agent (PM-1) containing a cationic polymer (M-1).
  • the comparative water treatment agent (PM-1) had a solid content of 40.0 wt %, a pH of 4.5, and the Mw (weight average molecular weight measured by GPC) of the cationic polymer (M-1) was 180,000, and the colloid equivalent value (colloid equivalent value measured by colloid titration using potassium polyvinyl sulfate) was 4.1.
  • Example 1 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-1) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
  • P1-1 250 mg of quaternary ammonium salt (A) solid content equivalent
  • Examples 2 to 30, 35 to 36, 38 to 43, and 59 to 62> The supernatant was filtered in the same manner as in Example 1, except that the types and amounts of the quaternary ammonium salt (A) and the water treatment agent (P1) and the salt (S) and the water treatment agent (P2) were changed to those shown in Table 1, Table 2, Table 3, or Table 4.
  • the COD and TOC of the filtrate were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 4.
  • Example 31 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
  • P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
  • Example 32 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 31, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) ⁇ the water treatment agent (P1-3) was replaced with (P1-4) ⁇ , were measured.
  • the COD was 6 mg/L and the TOC was 9 mg/L.
  • Example 33 1 L of wastewater from B chemical plant containing an anionic surfactant was collected in a beaker, and under stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] as an inorganic flocculant was added in an amount to a solid content concentration of 50 mg/L.
  • Example 34 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 33, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) ⁇ the water treatment agent (P1-3) was replaced with (P1-4) ⁇ , were measured.
  • the COD was 7 mg/L and the TOC was 10 mg/L.
  • Example 37 50 parts of an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added to a 100 ml beaker. 50 parts of an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added and mixed under stirring to obtain a one-form water treatment agent (P-37) containing (A1-3) and (S-1).
  • A1-3 quaternary ammonium salt
  • Example 44 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-4) ⁇ the water treatment agent (P2-1) was replaced with (P2-4) ⁇ , were measured.
  • the COD was 7 mg/L and the TOC was 10 mg/L.
  • Example 45 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-5) ⁇ the water treatment agent (P2-1) was replaced with (P2-5) ⁇ , were measured.
  • the COD was 6 mg/L and the TOC was 9 mg/L.
  • Example 46 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-6) ⁇ the water treatment agent (P2-1) was replaced with (P2-6) ⁇ , were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • Example 47 The same procedure as in Example 3 was repeated except that the salt (S-1) was replaced with the salt (S-7) ⁇ the water treatment agent (P2-1) was replaced with the water treatment agent (P2-7) ⁇ , and the COD and TOC of the filtrate of the supernatant were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • Example 48 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with aluminum sulfate (manufactured by Taimei Chemical Industry Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • Example 49 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with polyferric sulfate (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
  • the COD was 6 mg/L and the TOC was 9 mg/L.
  • Example 50 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with ferric chloride (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • Example 51 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-5) ⁇ the water treatment agent (P1-3) was replaced with (P1-5) ⁇ , were measured.
  • the COD was 7 mg/L and the TOC was 10 mg/L.
  • Example 52 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-6) ⁇ the water treatment agent (P1-3) was replaced with (P1-6) ⁇ , were measured.
  • the COD was 9 mg/L and the TOC was 13 mg/L.
  • Example 53 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-7) ⁇ the water treatment agent (P1-3) was replaced with (P1-7) ⁇ , were measured.
  • the COD was 8 mg/L and the TOC was 12 mg/L.
  • Example 54 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-8) ⁇ the water treatment agent (P1-3) was replaced with (P1-8) ⁇ , were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • ⁇ Example 55 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
  • P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
  • Example 56 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
  • P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
  • Example 57 The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the anionic polymer flocculant "Sunfloc AH-400P (manufactured by Sanyo Chemical Industries, Ltd.),” and the COD and TOC of the filtrate of the supernatant were measured. The COD was 4 mg/L and the TOC was 6 mg/L.
  • Example 58 The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the nonionic polymer flocculant "Sunfloc NOP (manufactured by Sanyo Chemical Industries, Ltd.),” and the COD and TOC of the filtrate of the supernatant were measured.
  • the COD was 5 mg/L and the TOC was 7 mg/L.
  • Example 63 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of an acrylamide-diallyldimethylammonium chloride copolymer, "Unisense FCA1000L (manufactured by Senka Corporation)," which is an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
  • the COD was 4 mg/L and the TOC was 6 mg/L.
  • Example 64 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of poly(diallyldimethylammonium chloride), an organic coagulant, "Unisense FPA100L (manufactured by Senka Corporation)" was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
  • the COD was 4 mg/L and the TOC was 6 mg/L.
  • Example 65 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dimethylamine-ammonia-epichlorohydrin condensate "Unisense KHE100L (manufactured by Senka Corporation)" as an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
  • the COD was 7 mg/L and the TOC was 10 mg/L.
  • Example 66 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-formalin condensate, "Unisense KHF11L (manufactured by Senka Corporation),” an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010,” manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
  • the COD was 8 mg/L and the TOC was 11 mg/L.
  • Example 67 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-diethylenetriamine condensate "Unisense KHP10P (manufactured by Senka Corporation)" which is an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
  • the COD was 7 mg/L and the TOC was 10 mg/L.
  • ⁇ Comparative Example 7 1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and 1,000 mg (100 mg of quaternary ammonium salt (A) solid content equivalent) of a water treatment agent (P1-7) was added under stirring, which was an aqueous solution in which a quaternary ammonium salt (A2-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 50 mg/L, and the TOC was 76 mg/L.
  • FIG. 1 shows a graph plotting the COD (mg/L) values against the amount (mg/L) of the solids of the quaternary ammonium salt (A) in the water treatment agent or comparative water treatment agent for combination (1) [combination of Examples 3, 38, 39] containing the same quaternary ammonium salt (A) (water treatment agent (A2-3)) and salt (S) (salt (S-1)), combination (2) [combination of Examples 7, 40, 41] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), combination (3) [combination of Examples 11, 42, 43] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), and combination (4) [combination of Comparative Examples 7, 8, 9] containing the same quaternary ammonium salt (A) (comparative treatment agent (ratio P)) but not
  • the COD decreased up to an addition amount of 250 mg of quaternary ammonium salt (A), and the COD increased when the addition amount was further increased, and it can be seen that there is an optimum point for the addition amount of quaternary ammonium salt (A).
  • the water treatment agent of the example containing salt (S) no increase in COD was observed even when an amount of quaternary ammonium salt (A) exceeding 250 mg, which was the optimum point for the comparative water treatment agent, was used.
  • the COD value and TOC value before treatment in the above formula are 80 mg/L and 122 mg/L, respectively, as described in Comparative Example 1.
  • the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) is shown in Tables 1 to 5.
  • Tables 1 to 5 show that the water treatment agents according to Examples 1 to 67 have higher COD removal rates and TOC removal rates than the water treatment agents according to the comparative examples, and are significantly more effective at reducing water-soluble COD components. Furthermore, the results of (1) Examples 3, 38, and 39, (2) Examples 7, 40, and 41, and (3) Examples 11, 42, and 43 in Figure 1 show that the water treatment agent of the present invention can achieve a stable water-soluble COD reduction effect over a wide range of added amounts of the water treatment agent (addition amount of quaternary ammonium salt (A) in the water treatment agent).
  • the water treatment agent of the present invention is very useful because, by being added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steelmaking, food, gravel extraction, semiconductor-related, and cleaning industries, etc.), sewage, purified water, and sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress an increase in water-soluble COD components, even under conditions where the amount of the water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and can exhibit a significantly excellent effect of reducing water-soluble COD components.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
PCT/JP2023/037910 2022-11-30 2023-10-19 水処理剤及び水処理方法 Ceased WO2024116641A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024561244A JPWO2024116641A1 (enrdf_load_stackoverflow) 2022-11-30 2023-10-19

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022191446 2022-11-30
JP2022-191446 2022-11-30

Publications (1)

Publication Number Publication Date
WO2024116641A1 true WO2024116641A1 (ja) 2024-06-06

Family

ID=91323611

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/037910 Ceased WO2024116641A1 (ja) 2022-11-30 2023-10-19 水処理剤及び水処理方法

Country Status (2)

Country Link
JP (1) JPWO2024116641A1 (enrdf_load_stackoverflow)
WO (1) WO2024116641A1 (enrdf_load_stackoverflow)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004344829A (ja) * 2003-05-26 2004-12-09 Sanyo Chem Ind Ltd 有機凝結剤及び高分子凝集剤
WO2014001078A1 (en) * 2012-06-26 2014-01-03 Unilever N.V. Water clarification composition and process
JP2019214037A (ja) * 2018-06-07 2019-12-19 三洋化成工業株式会社 水処理方法及び水処理剤
CN111807483A (zh) * 2020-08-06 2020-10-23 中科乐美环保科技有限公司 一种絮凝灭菌双功能水处理剂及其制备方法
CN111847545A (zh) * 2020-08-04 2020-10-30 武汉世纪瑞科环保科技有限公司 一种工业污水除臭剂及其制备方法
CN112939170A (zh) * 2021-02-02 2021-06-11 淄博正河净水剂有限公司 工业废水絮凝剂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004344829A (ja) * 2003-05-26 2004-12-09 Sanyo Chem Ind Ltd 有機凝結剤及び高分子凝集剤
WO2014001078A1 (en) * 2012-06-26 2014-01-03 Unilever N.V. Water clarification composition and process
JP2019214037A (ja) * 2018-06-07 2019-12-19 三洋化成工業株式会社 水処理方法及び水処理剤
CN111847545A (zh) * 2020-08-04 2020-10-30 武汉世纪瑞科环保科技有限公司 一种工业污水除臭剂及其制备方法
CN111807483A (zh) * 2020-08-06 2020-10-23 中科乐美环保科技有限公司 一种絮凝灭菌双功能水处理剂及其制备方法
CN112939170A (zh) * 2021-02-02 2021-06-11 淄博正河净水剂有限公司 工业废水絮凝剂及其制备方法

Also Published As

Publication number Publication date
JPWO2024116641A1 (enrdf_load_stackoverflow) 2024-06-06

Similar Documents

Publication Publication Date Title
KR100189045B1 (ko) 표백된 화학-열 기계적 펄프/화학-열 기계적 펄프 폐수의 처리방법
JP5364298B2 (ja) 分散剤含有水の処理方法
US7722841B2 (en) Polymeric chelant and coagulant to treat metal-containing wastewater
JP5528660B2 (ja) 高分子凝集剤
TWI510456B (zh) 製備新穎無鹵素陰離子之四級銨鹽單體的方法、其聚合方法及所得聚合物之使用方法
JP2011131166A (ja) 廃水の凝集処理方法
JP6852113B2 (ja) 水処理方法及び水処理剤
WO2024116641A1 (ja) 水処理剤及び水処理方法
JP5560626B2 (ja) 両性有機凝結剤および廃水処理方法
JP2014159018A (ja) 含油洗浄廃水の凝集処理方法
JP7094517B2 (ja) 有機性汚泥の脱水方法
JP4479095B2 (ja) 高分子凝集剤及び汚泥の脱水方法
JP3633726B2 (ja) 汚泥の処理方法
JP6755503B2 (ja) 有機質汚泥の脱水方法
JP2019118853A (ja) 有機性汚泥の脱水方法、有機性汚泥の脱水に用いる処理装置、有機凝結剤
JP5709086B2 (ja) 有機凝結剤
JP2991588B2 (ja) カルシウム化合物含有汚泥の脱水方法
JP2011078882A (ja) 高分子凝集剤
JP4553519B2 (ja) 古紙排水の処理方法
JP2005066596A (ja) 有機凝結剤および高分子凝集剤
JP2014184406A (ja) 粉末状有機凝結剤
JP6177737B2 (ja) 高分子凝集剤
JP2005125214A (ja) 有機汚泥の脱水方法
JP2012157819A (ja) 高分子凝集剤
JP2003251364A (ja) 乳化重合系ポリマーを含有する廃液の処理方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23897298

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024561244

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE