JP2005213343A - Organic coagulant and polymer flocculant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic coagulant which has excellent coagulating and decoloring effects, and to provide a polymer flocculant which has excellent characteristics such as flock coarsening, flock strength increase, the reduction in the water content of dehydrated cake, and the decolorization, COD reduction, and the like of a filtrate. <P>SOLUTION: This organic coagulant is characterized by comprising a water-soluble (co)polymer containing a monomer represented by the general formula (1): CH<SB>2</SB>=CR<SP>1</SP>-CO-X-Q-N<SP>+</SP>R<SP>2</SP>R<SP>3</SP>R<SP>4</SP>×Z<SP>-</SP>(X is O or NH; Q is a 1 to 4C alkylene or 2 to 4C hydroxyalkylene; R<SP>1</SP>is H or methyl; R<SP>2</SP>is a 7 to 30C aralkyl or alkylaryl; R<SP>3</SP>and R<SP>4</SP>are each independently H, a 1 to 16C alkyl, a 7 to 30C aralkyl or alkylaryl; Z<SP>-</SP>is a counter anion) as an essential constituting unit, and the polymer flocculant is characterized by comprising the polymer coagulant and one or more other water-soluble (co)polymers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to organic or inorganic sludge such as sewage or human waste (hereinafter abbreviated as sewage) and factory wastewater or organic coagulant or polymer flocculant used in the treatment of waste water, and sludge using the polymer flocculant. Or it relates to a method for treating wastewater.

Conventionally, in the coagulation and decolorization treatment of inorganic sludge, suspended water, colored water, paper mill wastewater and other aqueous solutions such as organic sludge such as sewage and factory wastewater, inorganic coagulants (for example, sulfuric acid bands, Polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime) and organic coagulants [for example, polycondensates of epihalohydrin and amines (for example, see Patent Document 1)] are widely used. .
In addition, for the dehydration treatment of these organic and inorganic sludges or wastewater, a method using a condensed polyamine organic coagulant and an amphoteric polymer flocculant in combination (for example, see Patent Document 2) has been proposed. ing.

Japanese Examined Patent Publication No. 38-26794 (first page) JP 2000-225400 A

However, the inorganic coagulants currently used require enormous amounts of addition to the suspension water, colored water and other aqueous solutions, and there is a problem that the amount of sludge after solid-liquid separation increases. In addition, the increase in circulating wastewater COD (chemical oxygen demand) due to the closed water used in paper mills and contamination of residual coloring components can lead to increased drainage, filler yield and paper strength enhancement effects, and It was a coloring factor. In addition, the organic coagulant may be added in a lower amount than the inorganic coagulant and the amount of sludge can be greatly reduced, but the effect of coagulation and decoloration is insufficient. Furthermore, with the recent tightening of drainage regulations, there is an increasing need to reduce COD components in effluent water, and further improvement in the performance of organic coagulants is particularly desired.
In addition, in the above-mentioned sludge or wastewater dewatering treatment, from the viewpoint of improving the processing speed accompanying the recent increase in the amount of sludge and wastewater, from the viewpoint of the ability to form stronger flocs, and the cost of incineration or landfill disposal of the dewatered cake There is a demand for a polymer flocculant that has the ability to significantly reduce the moisture content in a dehydrated cake, and further has the ability to decolorize separation water and reduce COD after the dehydration step. However, the proposed polymer flocculant cannot satisfy these performances, and the method using the proposed organic coagulant and the polymer flocculant has not been sufficient.
An object of the present invention is to provide an organic coagulant having excellent coagulation and decoloring effects, and high properties excellent in characteristics such as coarse flocs, increased floc strength, low moisture content of dehydrated cake, and decolorization and COD reduction of filtrate. It is to provide a molecular flocculant.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, this invention consists of the water-soluble (co) polymer (A) which has the monomer (a1) represented by General formula (1) as an essential structural unit, The organic coagulant characterized by the above-mentioned.

^{_{CH 2 = CR 1 -CO-X}} -Q-N + R 2 R 3 R 4 · Z - (1)

[Wherein, X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ¹ is H or a methyl group; R ² is aralkyl having 7 to 30 carbon atoms; An alkylaryl group, R ³ and R ⁴ are each independently H, an alkyl group having 1 to 16 carbon atoms, an aralkyl or alkylaryl group having 7 to 30 carbon atoms; and Z ⁻ represents a counter anion. ]
A polymer flocculant comprising a combination of the organic coagulant and another water-soluble (co) polymer (B); after adding and mixing the organic coagulant to sludge or wastewater, ) Is added and mixed to form a floc and solid-liquid separation is performed, and the polymer flocculant is added to and mixed with sludge or wastewater to form a floc. In the sludge or wastewater treatment method comprising the steps of solid-liquid separation, the polymer flocculant is used.

The organic coagulant of the present invention exhibits excellent coagulability and COD reduction effect when added to and mixed with COD-containing wastewater such as paper mill wastewater, and has the effect of removing colored components. Molecular flocculants are extremely useful because they have the following effects.
(1) By adding and mixing with sludge or wastewater, flocs with strong and large particle size are formed.
(2) Since the flocs once formed are not easily broken or redispersed, there is no recontamination during agglomeration or dehydration treatment, and the stability of the agglomeration or dehydration treatment and the processing speed can be significantly improved.
(3) Since the flocs formed above are dense and the moisture content of the cake after dehydration is low, the amount of waste generated and incineration costs can be greatly reduced.
(4) The COD of the filtrate generated during the dehydration step of the formed floc can be reduced and the coloring component can be removed.

The organic coagulant of this invention consists of the water-soluble (co) polymer (A) which has the monomer (a1) represented by the said General formula (1) as an essential structural unit.
In the general formula (1), R ¹ represents H or a methyl group, and H is preferred from the viewpoint of the condensation performance and decolorization performance of (A).
Q represents an alkylene group having 1 to 4 carbon atoms (hereinafter abbreviated as C) or a hydroxyalkyl group having 2 to 4 carbon atoms. When C of Q exceeds 4, the solubility of (A) in water becomes poor.
C1-4 alkylene groups of Q include methylene, ethylene, n- and i-propylene, 1,2-, 1,3- and 2,3-butylene groups and tetramethylene groups; C2-4 The hydroxyalkylene groups include hydroxyethylene, 1- and 2-hydroxypropylene, 1-hydroxy-i-propylene, 1- and 2-hydroxytetramethylene, 2-hydroxymethylpropylene and 2-methyl-2-hydroxypropylene groups Is included.

R ² represents a C7-30 aralkyl or alkylaryl group. When C of R ² is less than 7, the setting performance and decoloring performance of (A) are deteriorated, and when it exceeds 30, the solubility of (A) in water is deteriorated.
Examples of the aralkyl group in R ² include a C7-30 monocyclic arylalkyl group [for example, benzyl, phenethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 7-phenylheptyl, 8-phenyloctyl, 10-phenyldecyl and 12-phenyldodecyl groups] and C11-50 polycyclic arylalkyl groups [for example, naphthylmethyl, naphthylethyl, naphthylpropyl, anthranylmethyl and anthranylethyl groups].
Examples of the alkylaryl group include C7-30 monocyclic alkylaryl groups [for example, toluyl, xylyl, ethylphenyl, cumyl and octylphenyl groups] and C11-50 polycyclic alkylaryl groups [for example, 2-methylnaphthyl, 2- Methyl anthranyl and poly (n = 2 to 4) styrenated cumyl group] and the like.
Of these R ² , monocyclic arylalkyl groups and monocyclic alkylaryl groups are preferred from the viewpoint of water solubility, more preferred are benzyl, phenethyl, 3-phenylpropyl, toluyl and xylyl groups, and particularly preferred are benzyl and A phenethyl group, most preferably a benzyl group.

R ³ and R ⁴ each independently represent H, a C1-16 alkyl group, a C7-30 aralkyl or alkylaryl group. When C of the alkyl group exceeds 16, the solubility of (A) in water becomes poor. When C of the aralkyl or alkylaryl group is less than 7, the setting performance and decoloring performance of (A) are deteriorated, and when it exceeds 30, the solubility of (A) in water is deteriorated.
Examples of the alkyl group for R ³ or R ⁴ include methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, n-, i-, sec- and t-amyl and lauryl. Group, and examples of the aralkyl group and the alkylaryl group include the same groups as those described above for R ² .

Examples of Z ⁻ include the following anions.
(1) inorganic acids such as hydrogen halides (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid (2) sulfate esters, eg C1-30 sulfate esters [eg alkyl or alkenyl sulfates (eg methyl sulfate) , Ethyl sulfate, lauryl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate, oleyl sulfate, linole sulfate and cetyl sulfate) and higher alcohols (C10-20) ethylene oxide (hereinafter abbreviated as EO) 1-60 mol adduct Sulfate]

(3) Sulfonic acids such as C1-30 sulfonic acids [eg alkyl (C1-10) sulfonic acids (eg methylsulfonic acid and ethylsulfonic acid), alkylaryl (C7-30) sulfonic acids [alkylbenzenesulfonic acid, alkylphenolsulfone Acid and alkyl naphthalene sulfonic acid], higher alkyl (C10-30) sulfonic acid, higher fatty acid ester (C10-30) sulfonic acid, higher alcohol ether (C10-30) sulfonic acid, sulfosuccinic acid ester, higher fatty acid amide (C10 30) alkylsulfonic acid, alkyldiphenyl ether sulfonic acid and alkylbenzimidazolesulfonic acid]

(4) Phosphate esters, such as mono- and dialkyl (C1-30) phosphate esters, mono- and dialkenyl (C1-30) phosphate esters, (poly) oxyalkylenes [EO 1-60 mol addition and / or propylene oxide (Hereinafter abbreviated as PO) 1-60 mol addition] alkyl (C1-30) ether phosphate ester, sugar phosphate ester (for example, glucose-phosphate ester, glucoseamine phosphate ester, maltose-1-phosphate and sucrose) Phosphate esters) and glycerin phosphate (eg phosphatidic acid)

(5) Phosphonic acids, such as C1-30 phosphonic acids [eg alkyl (C1-10) phosphonic acids (eg methylphosphonic acid and ethylphosphonic acid), alkylaryl (C7-30) phosphonic acids (eg alkylbenzene phosphonic acid and alkylphenol phosphones) Acid), higher alkyl (C10-30) phosphonic acid, phosphonic acid of higher fatty acid ester (C10-30), phosphonic acid of higher alcohol ether (C10-30), alkyl phosphonic acid of higher fatty acid amide (C10-30), Alkyl diphenyl ether phosphonic acid and alkylbenzimidazole phosphonic acid]
(6) Carboxylic acids such as aliphatic [C1-30 mono- and dicarboxylic acids such as formic acid, oxalic acid, acetic acid, propionic acid, maleic acid, fumaric acid and adipic acid]; alicyclic [C4-30 mono -And dicarboxylic acids such as cyclopentane (di) carboxylic acid and cyclohexane (di) carboxylic acid]; and aromatics [C7-30 mono- and dicarboxylic acids such as benzoic acid and phthalic acid]

Among these Z ⁻ , the anion of sulfonic acid is preferable from the viewpoint of the coagulation performance and decolorization performance of (A), and more preferable are sulfuric acid, halogen (for example, Cl ⁻ and Br ⁻ ) and sulfuric acid ester (for example, alkyl and Alkenyl sulfate anions), particularly preferred are sulfuric acid, Cl ⁻ , methylsulfuric acid and ethylsulfuric acid anions, most preferred is Cl ⁻ .

Examples of (a1) include the following and mixtures thereof.
(A11) Amine salt of (meth) acrylate type [when X in general formula (1) is O] Secondary amino group-containing (meth) acrylate [C10-33, such as benzylaminoethyl (meth) acrylate, benzylaminopropyl (Meth) acrylates and toluylaminoethyl (meth) acrylates] and tertiary amino group-containing (meth) acrylates [C11-34, such as methylbenzylaminoethyl (meth) acrylate and ethylbenzylaminopropyl (meth) acrylate], inorganic A quaternary ammonium salt obtained by quaternizing an acid (above) salt, an organic acid (above) salt or an amine (salt) thereof with a quaternizing agent (for example, methyl chloride, dimethyl sulfate and benzyl chloride)

(A12) Amine salt of (meth) acrylamide type [when X in formula (3) is N] Secondary amino group-containing (meth) acrylamide [eg benzylaminoethyl (meth) acrylamide and benzylaminopropyl (meth) acrylamide ] And tertiary amino group-containing (meth) acrylamides [e.g. methylbenzylaminoethyl (meth) acrylamide and ethylbenzylaminopropyl (meth) acrylamide] inorganic acid salts (above), organic acid salts (above) and A quaternary ammonium salt obtained by quaternizing the amine with a quaternizing agent (as described above).

Among these, a (meth) acrylate amine salt in which X is O is preferable from the viewpoint of easy industrial production, and more preferable is R ² is benzyl, R ³ is CH ₃ , and R ⁴ is H. Methylbenzylaminoethyl (meth) acrylate hydrochloride or methylbenzylaminoethyl (meth) acrylate sulfate in which Z and Z are Cl or 1 / 2SO ₄ and an amine (salt) in which R ³ and R ⁴ are CH ₃ are salified A quaternary ammonium salt formed by quaternization with benzyl.

(A) is one or more monomers (a2) selected from the group consisting of (a1) and the monomer (a21), (meth) acrylamide and (meth) acrylic acid represented by the following general formula (2) May be copolymerized.

^{_{CH 2 = CR 5 -CO-X}} -Q-N + R 6 R 7 R 8 · Z - (2)

[Wherein X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ⁵ is H or a methyl group; R ⁶ , R ⁷ and R ⁸ are each independently H or an alkyl group having 1 to 16 carbon atoms; Z ⁻ represents a counter anion. ]

In the general formula (2), examples of Q and Z ⁻ are the same as those in the general formula (1).
Examples of the C1-16 alkyl group represented by R ⁶ , R ⁷ or R ⁸ include methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, n-, i- and sec. -And t-amyl and lauryl groups are mentioned.

Examples of (a21) include the following and mixtures thereof.
(A211) Amine salt of (meth) acrylate type [when X in general formula (2) is O] Primary amino group-containing (meth) acrylate [C5-20, such as aminoethyl (meth) acrylate and aminopropyl (meth) ) Acrylate] secondary amino group-containing (meth) acrylate [C6-20, eg methylaminoethyl (meth) acrylate, methylaminopropyl (meth) acrylate and aminoethyl (meth) acrylate) and tertiary amino group-containing (meta) ) Acrylate [C7-20, eg dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate], inorganic acid (above) salts, organic acid (above) salts and their amines (salts) Quaternized with a quaternizing agent (as described above) Monium salt

(A212) amine salt of (meth) acrylamide system [when X in general formula (2) is N] primary amino group-containing (meth) acrylamide [for example, aminoethyl (meth) acrylamide and aminopropyl (meth) acrylamide], Secondary amino group-containing (meth) acrylamide [eg methylaminoethyl (meth) acrylamide and methylaminopropyl (meth) acrylamide] and tertiary amino group-containing (meth) acrylamide [eg dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (Meth) acrylamide] inorganic acid salt (as described above), organic acid salt (as described above), and quaternary ammonium salt obtained by quaternizing the above amine with a quaternizing agent (as described above).

Of these, a (meth) acrylate amine salt in which X is O is preferable from the viewpoint of easy industrial production, and more preferable are R ⁶ and R ⁷ are both CH ₃ and R ⁸ is H. , Dimethylaminoethyl (meth) acrylate hydrochloride or dimethylaminoethyl (meth) acrylate sulfate, wherein Z is Cl or 1 / 2SO ₄ , and these amines (salts) with 4 quaternizing agents (as described above). It is a quaternary ammonium salt obtained by grading.

The monomer constituting (A) may be used in combination with another water-soluble unsaturated monomer (b).
(B) includes the following (b1) to (b3) and mixtures thereof.
(B1) Nonionic monomer The following, and mixtures thereof (b11) (Meth) acrylate derivatives Molecular weight 40 to number average molecular weight [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC)] 3, 000, for example, hydroxyl group-containing (meth) acrylate [for example, hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (degree of polymerization 3-50) mono (meth) acrylate and polyglycerol (degree of polymerization 1-10) mono (Meth) acrylate] and 2-cyanoethyl (meth) acrylate (b12) (meth) acrylamide derivatives C4-30, such as N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-methylol ( Data) acrylamide (b13) nitrogen atoms other than the above-containing vinyl monomers C3～30, such as acrylonitrile, N- vinylformamide, N- vinyl-2-pyrrolidone, vinylimidazole, N- vinyl succinimide and N- vinylcarbazole

(B2) Cationic monomer The followings, salts thereof (for example, salts of the inorganic acid or organic acid and quaternary ammonium salts) and mixtures thereof (b21) vinyl compounds having an amino group C2-30, such as vinylamine, Compounds having vinylaniline, (meth) allylamine, di (meth) allylamine, p-aminostyrene, 2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine and vinylmorpholine (b22) amine imide groups C4-30, for example 1,1 , 1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth) acryl Imido and 1,1,1-trimethylamine (meth) acryl Imide

(B3) Anionic monomer The following acids, salts thereof [for example, alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts and amines (C1-20, for example, methyl) Amines, ethylamines and ethanolamines), and mixtures thereof

(B31) Unsaturated carboxylic acids Monocarboxylic acids [C3-30, such as vinylbenzoic acid and allylic acetic acid] and poly (2-4) carboxylic acids [C4-30, such as (anhydrous) maleic acid, fumaric acid and itaconic acid]

(B32) Unsaturated sulfonic acid Alkene sulfonic acid [C2-20, such as vinyl sulfonic acid and (meth) allyl sulfonic acid], unsaturated aromatic sulfonic acid [C6-20, such as styrene sulfonic acid and α-methylstyrene sulfonic acid ], Alkenyl and alkyl (C1-18) alkenyl esters of sulfocarboxylic acids (eg α-sulfoalkanoic acids and sulfosuccinic acids) [C3-20, eg methylvinyl, propyl (meth) allyl and stearyl (meth) allylsulfosuccinate And (meth) allylsulfolaurate], sulfonic acid group-containing (meth) acrylate [C4-30, such as sulfoalkyl (C2-20) (meth) acrylate [for example, 2- (meth) acryloyloxyethanesulfonic acid, 2 -(Meth) acryloyl Xipropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2- Dimethylethanesulfonic acid and p- (meth) acryloyloxymethylbenzenesulfonic acid]], sulfonic acid group-containing (meth) acrylamide [C4-30, such as 2- (meth) acryloylaminoethanesulfonic acid, 2- (meth) acryloyl Aminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid And p- (meth) acryloylaminomethylbenzenesulfonic acid] and alkyl (C1-20) (meth) allylsulfosuccinic acid ester [eg methyl (meth) allylsulfosuccinic acid ester]
(B33) (Meth) acryloyl polyoxyalkylene (C1-6) sulfate ester (for example, (meth) acryloyl polyoxyethylene (degree of polymerization 2 to 50) sulfate ester

  Among (b), (b11) and (b22) are preferable from the viewpoint of the setting performance of (A), and (b12), (b13), (b31), and (b32) are particularly preferable. Are acrylonitrile, N-vinylformamide, (anhydrous) maleic acid (salt), itaconic acid (salt), 2- (meth) acryloyloxyethanesulfonic acid (salt), 2- (meth) acryloyloxypropanesulfonic acid (salt) ), 3- (meth) acryloyloxypropanesulfonic acid (salt), 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid (salt), most preferably (anhydrous) maleic acid (salt), 2 -(Meth) acryloylamino-2,2-dimethylethanesulfonic acid (salt). The salt here refers to an alkali metal (same as above) salt.

In addition to the above (a1), (a2) and (b), the monomer constituting (A) may be used in combination with a water-insoluble monomer (c) as long as it does not inhibit the effects of the present invention. .
(C) includes the following (c1) to (c6) and mixtures thereof.
(C1) C4-23 (cyclo) alkyl (meth) acrylate [C1-20 aliphatic and alicyclic alcohol (meth) acrylates [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)] Acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate and cyclohexyl (meth) acrylate]
(C2) C4-20 epoxy group-containing (meth) acrylate [for example, glycidyl (meth) acrylate]

(C3) Poly (degree of polymerization 2-50) propylene glycol [monoalkyl (C1-20)-, monocycloalkyl (C3-12)-or monophenyl ether] unsaturated carboxylic acid monoester [eg C1-20 mono (Meth) acrylic acid esters of all PO adducts [eg ω-methoxy-, ω-ethoxy-, ω-propoxy-, ω-butoxy-, ω-cyclohexoxy- and ω-phenoxypolypropylene glycol mono (meth) acrylates And (meth) acrylic acid esters of diol PO adducts [eg, ω-hydroxyethyl (poly) oxypropylene mono (meth) acrylate]]

(C4) C2-30 unsaturated hydrocarbon monomers [e.g. ethylene, nonene, styrene and 1-methylstyrene]
(C5) Carboxylic acid (C2-20, eg acetic acid, octylic acid and lauric acid) esters of unsaturated alcohols [C2-8, eg vinyl alcohol and (meth) allyl alcohol] (eg vinyl acetate, vinyl octylate and lauric acid) vinyl)
(C6) Halogen-containing monomer (C2-8, such as vinyl chloride)

  The lower limit of the proportion of (a1) in all monomers constituting (A) is preferably 1 mol%, more preferably 10 mol%, particularly preferably 20 mol% from the viewpoint of setting performance, and (A) to water. From the viewpoint of solubility, the upper limit is preferably 100 mol%, more preferably 99 mol%, particularly preferably 95 mol%; the proportion of (a2) is preferably 90 mol% or less, more preferably 80 mol, from the viewpoint of setting performance. %, Particularly preferably 0 to 70 mol%; the proportion of (b) is preferably 50 mol% or less, more preferably 30 mol% or less, particularly preferably 0 to 20 mol%, from the viewpoint of setting performance; The proportion of (c) is preferably 40 mol% or less, more preferably 20 mol% or less, particularly preferably 0 to 10 mol% from the viewpoint of the solubility of (A) in water.

The production method (A) is not particularly limited, and known radical polymerization methods such as aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization, precipitation polymerization, and reverse phase emulsion polymerization can be employed. Among these, preferred from the industrial viewpoint are reversed-phase suspension polymerization and reversed-phase emulsion polymerization, and more preferred are aqueous solution polymerization and photopolymerization.
As aqueous solution polymerization, a known method, for example, a method in which an aqueous monomer solution is placed in a container in which heat does not enter and exit from the outside, and adiabatic polymerization (for example, Japanese Patent Publication No. 59-40843) and an aqueous monomer solution can be controlled from the outside. A method (for example, Japanese Patent Laid-Open No. 3-189000) for carrying out constant temperature polymerization in a simple container can be used.

Also for photopolymerization, a known method, for example, a method in which (a1) and other monomers as necessary are further added with a photosensitizer as necessary and polymerized by irradiation with light having a wavelength of 300 to 500 nm (for example, Japanese Examined Patent Publication 45-45). 37033) can be used.
Photosensitizers include peroxides (benzoyl peroxide, etc.), azo compounds (azobisisobutyronitrile, etc.), carbonyl compounds (diacetyl, dibenzyl, etc.), sulfur compounds (diphenyl mono- and disulfides, dibenzoyl mono). -And disulfides), halogen compounds (carbon tetrachloride, etc.), and metal salts (iron trichloride, etc.).

Also for the reverse phase suspension polymerization, a known method, for example, a method in which an aqueous solution of a water-soluble vinyl monomer is dispersed in a water-in-oil type and polymerized using an oil-soluble polymer substance or a nonionic surfactant as a dispersion stabilizer (for example, a special method) No. 56-53111) can be used.
Examples of the oil-soluble polymer substance include cellulose ether (Mn 100 to 100,000, such as ethyl cellulose and ethyl hydroxyethyl cellulose), a copolymer of alkene and α, β-unsaturated polyvalent carboxylic acid (anhydride), or a derivative thereof. [Mn 100-100,000, for example, C20-40 1-olefin and (anhydrous) maleic acid copolymer].
Nonionic surfactants include, for example, sucrose fatty acid esters (C13-100, such as sucrose distearate and sucrose tristearate), sorbitan fatty acid esters (C7-100, such as sorbitan monostearate and sorbitan monooleate) and ( Poly) glycerin fatty acid esters (C6-100, such as glycerin monostearate).
The amount of the oil-soluble polymer substance to be used is based on the weight of the below-mentioned dispersion medium (organic solvent) to be used, the lower limit is usually 0.1%, preferably 0.2% from the viewpoint of stabilizing the dispersed particle diameter, Preferably, it is 0.5%, the upper limit is usually 10%, preferably 5%, more preferably 3% from the viewpoint of reducing the viscosity of the reaction system.
The use amount of the nonionic surfactant is usually 0.1% based on the weight of the below-mentioned dispersion medium (organic solvent) to be used, preferably 0.2% from the viewpoint of stabilizing the dispersed particle diameter, Preferably, it is 0.5%, the upper limit is usually 5%, preferably 3%, more preferably 1% from the viewpoint of reducing the viscosity of the reaction system.
Examples of the dispersion medium (organic solvent) to be used include aliphatic hydrocarbons [C6-30, such as hexane, heptane, n-decane, paraffin (for example, n- and i-paraffin), mineral oil (for example, kerosene, light oil, and medium oil). And alicyclic hydrocarbons (C6-30, such as cyclohexane and decalin) and aromatic hydrocarbons (C6-12, such as benzene, toluene, and xylene) and mixtures thereof.
The amount of the dispersion medium used is preferably 25%, more preferably 40%, particularly preferably 65%, from the viewpoint of the viscosity of the dispersion, based on the total weight of the aqueous monomer solution from the viewpoint of the stability of the dispersion. The upper limit is 1,000%, more preferably 400%, particularly preferably 200%.

Also for reverse phase emulsion polymerization, a known method, for example, a method of polymerizing an aqueous solution of a water-soluble vinyl monomer by using a surfactant to form a water-in-oil emulsion (for example, Japanese Patent No. 2676483 and JP-A-9). -208802).
Examples of the dispersion medium to be used include the same ones as in the reverse phase suspension polymerization. The use amount of the dispersion medium is preferably 20%, more preferably 30%, particularly preferably 40% based on the total weight of the monomer aqueous solution from the viewpoint of emulsion stability, and the preferred upper limit from the viewpoint of the viscosity of the emulsion. 80%, more preferably 70%, particularly preferably 60%.
As the surfactant used for emulsification, for example, known ones described in Japanese Patent No. 2676483 and JP-A-9-208802 can be used, and among these, from the viewpoint of stability of the emulsion, It is a nonionic surfactant.

Examples of the nonionic surfactant include higher fatty acid esters (for example, sorbitan monostearate, sorbitan distearate, sorbitan monooleate and oleic acid sorbitan ester EO adduct), polyoxyethylene long chain alkyl ether (for example, lauryl alcohol). Polyoxyethylene ethers and polyoxyethylene nonylphenyl ethers) and long-chain alkyl alkanolamides such as N, N-dihydroxyethyllaurylamide.
Based on the weight of the dispersion medium, the lower limit is usually 0.05%, preferably 0.1%, more preferably 0.12%, and the upper limit is usually 0.12% from the viewpoint of stabilizing the dispersed particle size. From the viewpoint of reducing the viscosity of the reaction system, it is preferably 0.5%, more preferably 0.25%.
In addition, when diluting a water-in-oil emulsion with water, a phase inversion agent is added to the water-in-oil emulsion in advance so that the water-in-oil emulsion can be poured into water and quickly phase-inverted and dissolved in water. May be. As the phase inversion agent, a highly hydrophilic surfactant [for example, HLB (Hydrophile-Lipophile Balance, an index indicating a balance between hydrophilicity and lipophilicity, based on the Griffin's HLB theory) of 9 to 20] For example, cationic surfactants and / or nonionic surfactants described in Japanese Patent No. 2676483 and JP-A-9-208802 can be used.

Examples of the radical polymerization initiator in the radical polymerization method include known ones such as water-soluble azo initiators [for example, azobisamidinopropane (salt) [for example, 2,2′-azobis (2-methylpropionamidine) dihydrochloride. ], Azobiscyanovaleric acid (salt) and 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] (salt)], oil-soluble azo initiators (eg azobiscyano Valeronitrile, azobisisobutyronitrile and azobiscyclohexanecarbonitrile), water-soluble peroxides (eg hydrogen peroxide, peracetic acid and t-butyl peroxide), oil-soluble peroxides (eg benzoyl peroxide and cumene) Hydroxyperoxides) and inorganic peroxides (eg ammonium persulfate and persulfate) Thorium), and the like.
The above peroxides may be used as a redox initiator in combination with a reducing agent, such as bisulfite (eg, sodium bisulfite, potassium bisulfite and ammonium bisulfite), reducing metal salts [eg, iron sulfate] (II)], tertiary amines [eg dimethylaminobenzoic acid (salt) and dimethylaminoethanol], amine complexes of transition metal salts [eg pentamethylenehexamine complex of cobalt (III) chloride and diethylenetriamine complex of copper (II) chloride And an organic reducing agent (for example, ascorbic acid). Further, the azo initiator, peroxide initiator, and redox initiator may be used alone or in combination of two or more initiators.

  The use amount of the radical polymerization initiator is preferably 0.01%, more preferably 0.05%, particularly preferably from the viewpoint of obtaining an optimum molecular weight as (A) based on the total weight of the monomers. The upper limit is preferably 0.1%, most preferably 0.2%, more preferably 30%, still more preferably 20%, particularly preferably 10%, most preferably 5%.

Moreover, you may use the chain transfer agent for radical polymerization as needed. The chain transfer agent for radical polymerization is not particularly limited, for example, a compound having one or more hydroxyl groups in the molecule [molecular weight 32 to Mn 50,000, such as methanol, ethanol, isopropyl alcohol, ethylene glycol, Propylene glycol, polyethylene glycol (molecular weight 100 to Mn 50,000) and polyethylene polypropylene glycol (molecular weight 100 to Mn 50,000)], compounds having one or more amino groups in the molecule [for example, ammonia and amines (C1 30, such as methylamine, dimethylamine, triethylamine and propanolamine)] and compounds having one or more thiol groups in the molecule (described below).
Among these, a compound having one or more thiol groups in the molecule is preferable from the viewpoint of molecular weight control.

Compounds having a thiol group in the molecule include the following, salts thereof [alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts, amines (C1- 20) salts and inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts], and mixtures thereof.
(1) Monovalent thiol Aliphatic thiol [C1-20, such as methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, 1-thioglycerol, thioglycolic acid monoethanolamine), 1-thioglycerol, thioglycolic acid monoethanolamine, thiomaleic acid, cysteine and 2-mercaptoethylamine], alicyclic thiols (C5-20) For example, cyclopentanethiol and cyclohexanethiol) and aromatic (aliphatic) thiols (C6-12, such as benzenethiol and benzyl mercaptan and thiosalicylic acid).

(2) polyvalent thiol dithiol [aliphatic (C2-40) dithiol (for example, ethanedithiol, diethylenedithiol, triethylenedithiol, propanedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol, Neopentanedithiol, etc.), alicyclic (C5-20) dithiols (eg cyclopentanedithiol and cyclohexanedithiol) and aromatic (C6-16) dithiols (eg benzenedithiol, biphenyldithiol).

  In the case of using the chain transfer agent for radical polymerization, the preferred lower limit is 0.001% based on the total weight of the monomers, more preferably 0.001%, from the viewpoint of obtaining the optimum molecular weight as (A). 005%, particularly preferably 0.01%, most preferably 0.05%, and a preferred upper limit is 10%, more preferably 5%, particularly preferably 3%, most preferably 1%.

  The monomer concentration in the aqueous monomer solution in radical polymerization is usually 1% based on the total weight of the aqueous monomer solution in aqueous polymerization, preferably 5%, more preferably 10%, particularly preferably from the viewpoint of reducing residual monomer. Is 15%, most preferably 20%, the upper limit is usually 80%, preferably 75% based on the temperature control during polymerization, more preferably 70%, particularly preferably 65%, most preferably 60%; In the phase suspension polymerization, the lower limit is usually 30%, preferably 40%, more preferably 45%, particularly preferably 50%, most preferably 55%, and the upper limit is usually 90% based on the viewpoint of reducing the residual monomer. Preferably 85%, more preferably 80%, particularly preferably 78%, most preferably from the viewpoint of temperature control at the time. Or 75%; in reverse phase emulsion polymerization, the lower limit is usually 10%, preferably 20%, more preferably 30%, particularly preferably 40%, most preferably 55%, and the upper limit is from the viewpoint of reducing residual monomers. Usually 90%, preferably 80%, more preferably 75%, particularly preferably 70%, most preferably 65% based on temperature control during polymerization.

  In the reverse phase suspension polymerization, the amount of the dispersion medium used is preferably 25%, more preferably 40%, particularly preferably 65%, based on the total weight of the aqueous monomer solution from the viewpoint of dispersion stability. From the viewpoint of the viscosity of the system, the preferable upper limit is 1,000%, more preferably 400%, particularly preferably 200%; in reverse phase emulsion polymerization, the preferable lower limit is based on the total weight of the aqueous monomer solution from the viewpoint of emulsion stability. Is 20%, more preferably 30%, particularly preferably 40%, and from the viewpoint of the viscosity of the emulsion, the preferable upper limit is 80%, more preferably 70%, particularly preferably 60%.

  In aqueous solution polymerization, the lower limit of the polymerization temperature is usually −10 ° C., preferably 0 ° C., more preferably 5 ° C., particularly preferably 10 ° C., most preferably 15 ° C. from the viewpoint of obtaining an optimal molecular weight as (A). The upper limit is usually 150 ° C., preferably 130 ° C., more preferably 120 ° C., particularly preferably 100 ° C., and most preferably 80 ° C. from the same viewpoint as described above. Further, during polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep a predetermined temperature constant (for example, a predetermined polymerization temperature ± 5 ° C.), or adiabatic polymerization may be performed in a glass heat insulating container or the like. .

The polymerization temperature in the photopolymerization is preferably 0 ° C. at the lower limit, preferably 5 ° C., more preferably 10 ° C., particularly preferably 15 ° C., most preferably 20 ° C., upper limit from the viewpoint of obtaining the optimum molecular weight as (A). Is usually 100 ° C., preferably 95 ° C., more preferably 90 ° C., particularly preferably 80 ° C., most preferably 70 ° C. from the same viewpoint as described above.
Further, during the polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C), or the polymerization may be performed at a relatively low temperature (for example, 15 to 35 ° C). It may be started and heated (for example, 55 to 80 ° C.) after polymerization for a certain time (for example, 1 to 3 hours).

The polymerization temperature in the reverse phase suspension polymerization is usually at least 10 ° C., preferably 20 ° C., more preferably 30 ° C., particularly preferably 40 ° C., most preferably from the viewpoint of obtaining the optimum molecular weight as (A). The upper limit is usually 95 ° C, preferably 90 ° C, more preferably 80 ° C, particularly preferably 70 ° C, and most preferably 60 ° C.
Further, during polymerization, it is preferable to adjust by appropriately heating and cooling so that the predetermined polymerization temperature is kept constant (for example, predetermined polymerization temperature ± 5 ° C.). In order to keep the polymerization temperature constant, the monomer may be added dropwise to the dispersion medium that has been previously adjusted to a predetermined polymerization temperature under stirring. The dropping time at that time varies depending on the monomer concentration and the amount of heat generated by the polymerization reaction, but is usually 0.5 to 20 hours, preferably 1 to 10 hours.
The lower limit of the polymerization temperature in the inverse emulsion polymerization is usually 0 ° C., preferably 5 ° C., more preferably 10 ° C., particularly preferably 15 ° C., most preferably 20 ° C. from the viewpoint of obtaining an optimal molecular weight as (A). The upper limit is usually 95 ° C., preferably 90 ° C., more preferably 80 ° C., particularly preferably 70 ° C., and most preferably 55 ° C. from the same viewpoint as described above.
Further, during the polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep the predetermined polymerization temperature constant (for example, the predetermined polymerization temperature ± 5 ° C), or the polymerization may be performed at a relatively low temperature (for example, 15 to 35 ° C). It may be started and heated (for example, 55 to 80 ° C.) after polymerization for a certain time (for example, 1 to 3 hours).

The end point of the polymerization can be confirmed at the time when the heat generation due to the polymerization disappears, but the polymerization time is usually 1 to 24 hours from the time when the start of the polymerization is confirmed by the heat generation. From this viewpoint, it is preferably 2 to 12 hours.
As in the case of reverse phase suspension polymerization, when the monomer is dropped at any time, it is preferable to carry out the polymerization for the above time after completion of the dropping.
The monomer concentration, polymerization temperature, and polymerization time can be appropriately adjusted depending on the monomer composition, polymerization method, initiator type, and the like.

  The pressure at the time of polymerization (unit: kPa, hereinafter indicates absolute pressure) is not particularly limited, but is usually carried out under normal pressure. In the case of reverse phase suspension polymerization, the pressure at which the dispersion medium boils or the pressure at which the hydrophobic dispersion medium and water azeotrope is preferably used at the polymerization temperature because the temperature can be easily adjusted during the polymerization. . Specifically, the preferred lower limit is 5 kPa, more preferably 12 kPa, particularly preferably 25 kPa, and the preferred upper limit is 95 kPa, more preferably 80 kPa, and particularly preferably 65 kPa.

  The pH of the aqueous monomer solution at the time of polymerization is not particularly limited, but is preferably 1 to 8, more preferably 2 to 7, particularly preferably 3 to 6.5 from the viewpoint of the polymerization rate and the solubility of the obtained (A). It is. The pH adjuster used for adjusting the pH is not particularly limited. When the monomer aqueous solution is alkaline, an inorganic acid (for example, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid), an inorganic solid acidic substance (for example, Acid sodium phosphate, acid sodium nitrate, ammonium chloride, ammonium sulfate, ammonium bisulfate and sulfamic acid) and organic acids (eg oxalic acid, succinic acid and malic acid), and inorganic alkaline substances (if the aqueous monomer solution is acidic) Examples include sodium hydroxide, potassium hydroxide and ammonia) and organic alkaline substances (eg guanidine). The pH is a value measured using a pH meter or the like at room temperature (20 ° C.) for the stock solution of the monomer aqueous solution used in the polymerization.

  In addition, (A) may be prepared in advance by the above method and then polymer-modified. As the polymer modification reaction, for example, when a water-soluble unsaturated monomer (b) having a hydrolyzable functional group in its molecule such as acrylamide is used, a caustic alkali (for example, sodium hydroxide and potassium hydroxide) is used during or after polymerization. ) Or alkali carbonate (for example, sodium carbonate and potassium carbonate) to partially hydrolyze the amide group of monomer (b) (hydrolysis rate is about 1 to 60 mol% based on total moles of all monomers) ) To introduce a carboxyl group (for example, JP-A-56-16505), for example, formaldehyde, dialkyl (C1-12) amine and halogenated (for example, chloride, bromide and iodide) alkyl (C1-12) ) (For example methyl chloride and ethyl chloride) and partially by the Mannich reaction A method for introducing a thione group, and a method for forming an amidine ring in a molecule by a ring-closing reaction between a nitrile group such as acrylonitrile and an amino group obtained by hydrolysis of vinylformamide or the like (for example, JP-A-5-192513) ).

  Moreover, when using 2 or more types of (A), you may mix after manufacturing each previously, may manufacture one beforehand and may add at the time of the other manufacture.

The molecular weight of (A) is the intrinsic viscosity (unit dl / g, the same applies hereinafter) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, and the preferred lower limit is from the viewpoint of the condensation performance and COD reduction performance of (A). The upper limit is preferably 3, more preferably 2, and particularly preferably 1 from the viewpoint of the setting speed of 01, more preferably 0.05, particularly preferably 0.1, and (A).

The polymer flocculant of the present invention is characterized by combining the organic coagulant and other water-soluble (co) polymer (B).
(B) includes those in which the monomer (a2) is an essential constituent and, if necessary, one or more monomers selected from the group consisting of (b) and (c) are copolymerized. .
Examples of the monomer constituting (B), (a2), (b), and (c) include those used in the above (A), and preferred ones are also the same.

  The proportion of (a2) in the total monomer constituting (B) is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and particularly preferably 20 to 100 mol% from the viewpoint of aggregation. ) Is preferably from 0 to 50 mol%, more preferably from 0 to 30 mol%, particularly preferably from 0 to 20 mol% from the same viewpoint; and the proportion of (c) to the water of (B) From the viewpoint of solubility, it is usually 40 mol% or less, preferably 0 to 30 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%.

  Of the above (B), a (co) polymer having the monomer (a21) as an essential constituent unit is more preferable from the viewpoint of cohesion, and (a21 in all monomers constituting (B) from the same viewpoint. ) Is preferably 1 mol%, more preferably 10 mol%, particularly preferably 20 mol%, and from the viewpoint of high molecular weight, the preferable upper limit is 100 mol%, more preferably 90 mol%, particularly preferably 80 mol%. %.

The production method (B) is not particularly limited, and known production methods such as aqueous polymerization, reverse phase suspension polymerization, precipitation polymerization and reverse phase emulsion polymerization can be used. Of these, preferred from the industrial viewpoint are reversed-phase emulsion polymerization, and more preferred are aqueous solution polymerization and reversed-phase suspension polymerization.
As the aqueous solution polymerization, reverse phase suspension polymerization, and reverse phase emulsion polymerization, the known methods mentioned in the above (A) can be used.

As the radical polymerization initiator in the radical polymerization method, those mentioned in (A) can be used.
The use amount of the radical polymerization initiator is preferably 0.001%, more preferably 0.005%, particularly preferably from the viewpoint of obtaining the optimum molecular weight as (B) based on the total weight of the monomers. 0.01%, most preferably 0.02%, the upper limit is preferably 1%, more preferably 0.5%, particularly preferably 0.1%, most preferably 0.05%.

Moreover, you may use the chain transfer agent for radical polymerization as needed. As the chain transfer agent for radical polymerization, those mentioned in (A) can be used.
In the case of using a chain transfer agent for radical polymerization, the preferred lower limit is 0.0001% based on the total weight of monomers, more preferably 0.001%, from the viewpoint of obtaining an optimum molecular weight as (B). 0005%, particularly preferably 0.001%, most preferably 0.005%, and a preferable upper limit is 10%, more preferably 5%, particularly preferably 3%, most preferably 1%.

  The monomer concentration in the monomer aqueous solution in the radical polymerization is usually 20% based on the total weight of the monomer aqueous solution in the aqueous solution polymerization, preferably 25%, more preferably 30%, particularly preferably based on the viewpoint of reducing the residual monomer. Is 40%, most preferably 50%, the upper limit is usually 80%, preferably 75% based on temperature control during polymerization, more preferably 70%, particularly preferably 65%, most preferably 60%; In the phase suspension polymerization, the lower limit is usually 30%, preferably 40%, more preferably 45%, particularly preferably 50%, most preferably 55%, and the upper limit is usually 90% based on the viewpoint of reducing the residual monomer. 85%, more preferably 80%, particularly preferably 78%, most preferably based on the viewpoint of temperature control at the time. Preferably 75%; in reverse phase emulsion polymerization, the lower limit is usually 10%, preferably 20%, more preferably 30%, particularly preferably 40%, most preferably 55%, and the upper limit is from the viewpoint of reducing residual monomers. Usually 90%, preferably 80%, more preferably 75%, particularly preferably 70%, most preferably 65% based on temperature control during polymerization.

  The amount of the dispersion medium used in the reverse phase suspension polymerization and the reverse phase emulsion polymerization is the same as in the case of (A), and preferable conditions are also the same as in (A).

In aqueous solution polymerization, the lower limit is usually −10 ° C., and preferably 0 ° C., more preferably 5 ° C., particularly preferably 10 ° C., most preferably 15 ° C. from the viewpoint of obtaining an optimal molecular weight as (B). The upper limit is usually 50 ° C., preferably 40 ° C. from the same viewpoint, more preferably 30 ° C., particularly preferably 25 ° C., and most preferably 20 ° C. Further, during polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep a predetermined temperature constant (for example, a predetermined polymerization temperature ± 5 ° C.), or adiabatic polymerization may be performed in a glass heat insulating container or the like. . In the adiabatic polymerization, it is preferable to adjust the starting temperature so that the boiling point of water (100 ° C.) or higher is not exceeded due to the heat of polymerization.
The polymerization temperature in the reverse phase suspension polymerization is the same as in the case of (A), and preferable conditions are also the same as in (A).

  The polymerization time at the time of polymerization, the pressure at the time of polymerization, and the pH of the monomer aqueous solution are the same as in the case of (A), and preferable conditions are also the same. Similarly to (A), (B) may be prepared in advance by the above method and then polymer-modified.

  Moreover, when using 2 or more types of (B), you may mix after manufacturing each previously, may manufacture one beforehand and may add at the time of the other manufacture.

When the molecular weight of (B) is expressed in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, the lower limit is usually 1, and preferably from the viewpoint of agglomeration performance (particularly, increase in floc particle size). 1.5, more preferably 2, particularly preferably 4, most preferably 6, the upper limit is usually 40, preferably 30 from the viewpoint of agglomeration performance (particularly improvement of floc strength), more preferably 20, particularly preferably 15, Most preferably 12.

  The organic coagulant and / or polymer flocculant of the present invention is, as necessary, an antifoaming agent, a chelating agent, a pH adjuster, a surfactant, an anti-blocking agent, and an antioxidant within the range not impairing the effects of the present invention. An additive selected from the group consisting of an agent, an ultraviolet absorber and a preservative can be used in combination.

Antifoaming agents include silicones (eg Mn 100-100,000 dimethylpolysiloxane), mineral oils (eg spindle oil and kerosene), C12-22 metal soaps (eg calcium stearate);
Chelating agents include C6-12 aminocarboxylic acids (eg ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid and triethylenetetraminehexaacetic acid), polyvalent carboxylic acids (eg maleic acid, polyacrylic acid). Acid (Mn 1,000-10,000) and isoamylene-maleic acid copolymer (Mn 1,000-10,000)], C3-10 hydroxycarboxylic acids (eg citric acid, gluconic acid, lactic acid and malic acid), Condensed phosphoric acid (eg tripolyphosphoric acid and trimetaphosphoric acid) and their salts [eg alkali metal (eg sodium and potassium) salts, alkaline earth metal (eg calcium and magnesium) salts, ammonium salts, C1-2 Alkylamine (e.g. methylamine, ethylamine and octylamine) salts and alkanolamine C2-12 (e.g. mono -, di- - and triethanolamine) salts];

  pH adjusters include caustic (eg caustic soda), amines (eg mono-, di- and triethanolamine), inorganic acids (salts) [eg inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid and Carbonates), and their metals (eg, alkali and alkaline earth metal) salts (eg, sodium carbonate, potassium carbonate, sodium sulfate, sodium hydrogen sulfate and monosodium phosphate) and ammonium salts (eg, ammonium carbonate and ammonium sulfate)] Organic acids (salts) [eg organic acids (eg carboxylic acids, sulfonic acids and phenols) and their metal (same as above) salts (eg sodium acetate and sodium lactate) and ammonium salts (eg ammonium acetate and ammonium lactate) ];

As the surfactant, surfactants described in US Pat. No. 4,331,447 such as polyoxyethylene nonylphenol ether and sodium dioctylsulfosuccinate];
Anti-blocking agents include polyether-modified silicone oils such as polyethylene oxide-modified silicones and polyethylene oxide / polypropylene oxide-modified silicones;

  Antioxidants include phenol compounds [eg hydroquinone, methoxyhydroquinone, catechol, 2,6-di-t-butyl-p-cresol (BHT) and 2,2′-methylenebis (4-methyl-6-t-butylphenol). )], Sulfur-containing compounds [eg thiourea, tetramethylthiuram disulfide, dimethyldithiocarbamic acid and its salts [eg metal (same as above) and ammonium salts], sodium sulfite, sodium thiosulfate, 2-mercaptobenzothiazole and Salts thereof (same as above), dilauryl 3,3′-thiodipropionate (DLTDP) and distearyl 3,3′-thiodipropionate (DSTDP)], phosphorus-containing compounds [eg triphenyl phosphite, triethyl phosphite Fight, sodium phosphite Lithium, sodium hypophosphite, triphenyl phosphite (TPP) and triisodecyl phosphite (TDP)] and nitrogenous compounds [amines such as octylated diphenylamine, Nn-butyl-p-aminophenol and N, N-diisopropyl-p-phenylenediamine), urea, guanidine, and the above inorganic acid salts of guanidine];

Examples of ultraviolet absorbers include benzophenone (for example, 2-hydroxybenzophenone and 2,4-dihydroxybenzophenone), salicylate (for example, phenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t). -Butyl-4-hydroxybenzoate), benzotriazoles [eg (2'-hydroxyphenyl) benzotriazole and (2'-hydroxy-5'-methylphenyl) benzotriazole] and acrylics [eg ethyl-2-cyano- 3,3-diphenyl acrylate and methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate];
Examples of the preservative include benzoic acid, p-hydroxybenzoic acid ester and sorbic acid.

These additives may be contained in either the organic coagulant and / or (B), or added after mixing the organic coagulant and (B) to obtain a polymer flocculant (C). You may let them. Further, additives other than the antiblocking agent may be preliminarily contained in the aqueous monomer solution before polymerization of (A) and / or (B) as long as the effects of the present invention are not impaired.
The total amount of the additive used is based on the weight of the organic coagulant and / or (B) or (C) when the additive is contained in the organic coagulant and / or (B) or (C). In addition, when it is previously contained in the monomer aqueous solution, it is usually 30% or less based on the monomer weight, and preferably 0 to 10% from the viewpoint of the effect of the present invention (condensation performance or aggregation performance).
About the usage-amount of each additive, based on the weight similar to the above, an antifoamer is 5% or less normally, Preferably it is 1-3%, a chelating agent is 30% or less normally, Preferably it is 2-10%, The pH adjuster is usually 10% or less, preferably 1 to 5%, the surfactant and the antiblocking agent are usually 5% or less, preferably 1 to 3%, respectively, the antioxidant, the ultraviolet absorber and the preservative are usually used. 5% or less, preferably 0.1 to 2%.

  When the organic coagulant and (B) are combined and applied to sludge or wastewater, the organic coagulant may be in any form such as powder, flakes, oil, paste, aqueous solution, emulsion or suspension. .

The ratio of the organic coagulant based on the total weight of the organic coagulant and (B) is preferably 0.5% from the viewpoint of the coagulant performance and the effect of improving the clarification of the filtrate (for example, COD reduction and decolorization). Preferably, it is 1%, particularly preferably 3%, most preferably 5%. From the viewpoint of flocculant performance, the upper limit is preferably 70% or less, more preferably 60% or less, particularly preferably 50%, most preferably 30%. .
The method of mixing the organic coagulant and (B) is not particularly limited as long as the organic coagulant and (B) can be mixed, and after obtaining (A) and (B) by polymerization, for example, a blender or the like. A method of mixing using a stirrer and a method of adding (B) or (A) before, during or after polymerization of (A) or (B) are included.

The polymer flocculant of the present invention exhibits an unprecedented specific coagulation effect and an effect of improving the clarification of the filtrate (for example, COD reduction and decolorization), so that organic sludge produced by treatment of sewage or factory wastewater or the like Alternatively, it can be used as a polymer flocculant for dewatering treatment of inorganic sludge, and particularly preferably used for dewatering treatment of organic sludge.
In the case of organic sludge, the size of the suspended particles is relatively large, and the surface of the suspended particles is negatively charged in water. From the viewpoint that the molecular flocculant and / or the amphoteric polymer flocculant, and further, the above-mentioned effects that are the characteristics of the present invention can be further exhibited, the amphoteric polymer flocculant is more preferable.

Here, the cationic polymer flocculant is a polymer flocculant having a cationic group in the molecule, that is, a polymer flocculant exhibiting a cationic property when dissolved in water. , A polymer flocculant having a cationic group and an anionic group in the molecule or a mixture of a polymer flocculant having a cationic group in the molecule and a polymer flocculant having an anionic group in the molecule, that is, dissolved in water It is a polymer flocculant that exhibits cationic and anionic properties.
The cationicity or anionicity of these polymer flocculants in water can be evaluated using the colloid equivalent value (meq / g) as a guide. That is, the cationic group equivalent value in the cationic flocculant can be determined as the cation colloid equivalent value, and the cationic group equivalent value and the anionic group equivalent value in the amphoteric flocculant are the cationic colloid equivalent value and the anionic colloid respectively. It can be determined as an equivalent value.

Among the polymer flocculants of the present invention, the cation colloid equivalent value (meq / g) based on the total weight of the organic flocculant and (B) of the cationic polymer flocculant is preferably 0 from the viewpoint of aggregation performance. .1, more preferably 0.5, particularly preferably 1, most preferably 1.5, and from the same viewpoint, the upper limit is preferably 20, more preferably 12, particularly preferably 8, and most preferably 6. In addition, the cation colloid equivalent value (meq / g) in the amphoteric polymer flocculant is preferably the lower limit of 1, more preferably 1.5, particularly preferably 2, and the preferable upper limit of 6, from the same viewpoint as described above. Further preferred is 5, particularly preferred is 4.5.
The lower limit of the anionic colloid equivalent value (meq / g) is preferably -5, more preferably -4, particularly preferably -3 from the viewpoint of the solubility of the polymer flocculant in water, and the upper limit preferable from the viewpoint of aggregation. Is -0.1, more preferably -0.3, particularly preferably -0.5.

The colloid equivalent value can be determined by the colloid titration method shown below. The subsequent measurement is performed at room temperature (about 20 ° C.).
(1) Preparation of measurement sample (50 ppm aqueous solution) A sample 0.2 g (converted to solid content) is precisely weighed and taken in a 200 ml Erlenmeyer flask, and the total weight (total weight of sample and ion-exchanged water) is After adding ion-exchanged water so that it may become 100 g, it stirs for 3 hours with a magnetic stirrer (1,000 rpm), and melt | dissolves completely, and a 0.2 weight% polymer flocculant solution is prepared. Further, 10.00 g of the prepared solution was accurately weighed into a 500 ml glass beaker using a balance capable of measuring to the second decimal place, and the total weight (total weight of 10 ml of solution and ion-exchanged water) was 400. Add ion-exchanged water to 0.000 g, and stir again with a magnetic stirrer (1,000 to 1,200 rpm) for 30 minutes to obtain a uniform measurement sample.
The solid content of the polymer flocculant is the residual weight after weighing about 1.0 g of sample in a petri dish (W1) and drying at 105 ± 5 ° C. for 90 minutes in a circulating drier (W2). Is a value calculated from the following equation.

Solid content (% by weight) = (W2) × 100 / (W1)

(2) Measurement of cation colloid equivalent value 100.0 g of a measurement sample is placed in a 200 ml glass conical beaker, and a 0.5% by weight sulfuric acid aqueous solution is gradually added to adjust to pH 3 while stirring. Next, add 2-3 drops of toluidine blue indicator (TB indicator) and titrate with N / 400 potassium potassium sulfate (N / 400 PVSK) reagent. The titration rate is 2 ml / min, and the end point is the time when the measurement sample changes from blue to magenta and is held for 30 seconds.
(3) Measurement of anion colloid equivalent value 100.0 g of a measurement sample was placed in a 200 ml glass conical beaker and 0.5 ml of an N / 10 aqueous sodium hydroxide solution was added while stirring with a magnetic stirrer (500 rpm). After adding 5 ml of 200 methyl glycol chitosan aqueous solution using a 5 ml whole pipette, it is stirred for 5 minutes (pH at that time is about 10.5). Add 2-3 drops of TB indicator and titrate as in (2).
(4) Blank test The same operation as (2) and (3) is performed except that 100.0 g of ion-exchanged water is used instead of the measurement sample.
(5) Calculation method Cation or anion colloid equivalent value (meq / g) = 1/2 × (sample titration-blank titration) × (N / 400 PVSK titer)

  The form of the polymer flocculant of the present invention may be any known form such as powder (for example, crushed, true spherical and kitchen), film, aqueous solution, w / o emulsion, and suspension.

  The organic coagulant of the present invention is suitably used for decolorization treatment of colored water, particularly dye wastewater, among factory wastewater. As the decoloring treatment method, for example, an organic coagulant is added to and mixed with dyeing waste water, and after the dye component is coagulated with the organic coagulant, a polymer flocculant is added and mixed to form a flock, and solid-liquid separation is performed. The method of performing is mentioned.

The organic sludge such as sewage using the polymer flocculant of the present invention or the inorganic sludge such as factory wastewater or the wastewater treatment method is a combination of an organic coagulant and a water-soluble (co) polymer (B). Or it will not specifically limit if it is the method of adding and mixing to wastewater, forming a floc, and performing solid-liquid separation.
Among the above-mentioned treatment methods, from the viewpoint of exhibiting the effects of the present invention described later (for example, high floc strength, increase in floc particle diameter, low water content of dehydrated cake and COD reduction and decolorization effect of filtrate), 1) A method in which an organic coagulant is added to and mixed with sludge or waste water, and then (B) is further added and mixed to form a floc, and a solid-liquid separation is performed, and (2) an organic coagulant and (B) A method of preliminarily mixing to obtain a polymer flocculant (C), then adding (C) to sludge or waste water, mixing to form flocs, and performing solid-liquid separation, more preferably method (1) is there.

In the method of (1), the organic coagulant is preferably added to the waste water from the viewpoint of uniform mixing, but it is preferable to add the organic coagulant to an aqueous solution and then add it to sludge or waste water and sufficiently stir. The agent may be added to the waste water as it is and stirred and mixed. When the organic coagulant is used as an aqueous solution, the concentration of the organic coagulant is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight.
The method for dissolving the organic coagulant and the method for diluting after the dissolution are not particularly limited. For example, a predetermined amount of the organic coagulant is added while stirring water previously measured using a stirring device such as a jar tester described later. A method of stirring and dissolving for several hours (about 1 to 4 hours) can be employed.

  The amount of the organic coagulant used in the method (1) varies depending on the type of sludge or wastewater, the content of suspended particles, the molecular weight of (A), etc., and is not particularly limited. Based on the weight of the product (hereinafter abbreviated as TS), the lower limit is preferably 0.01%, more preferably 0.05%, particularly preferably 0.1%, and most preferably from the viewpoint of improving the clarity of the filtrate. The upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 2% from the viewpoint of aggregation performance.

  Moreover, when using the organic coagulant of this invention for sludge or wastewater, you may use together 1 or more types of well-known inorganic and organic coagulants. When these are used in combination, the organic coagulant of the present invention is added in advance to the organic coagulant of the present invention, or the organic coagulant of the present invention and a known inorganic and / or organic coagulant are separately added to sludge or waste water in random order. Any of the methods may be adopted.

Known inorganic coagulants include, for example, sulfate bands, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime.
Known organic coagulants include, for example, a polycondensate of epihalohydrin and amine (or its hydrochloride, hereinafter abbreviated as hydrochloride), a polycondensate of epihalohydrin and alkylenediamine (hydrochloride), and polyethyleneimine (hydrochloride). , Alkylene dihalide-alkylene polyamine polycondensate (hydrochloride), aniline-formaldehyde polycondensate (hydrochloride), polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine (hydrochloride), (di) methyldi (meth) allylammonium chloride and Polyvinyl imidazoline (hydrochloride) is mentioned.
These known inorganic and organic coagulants may be used alone or in combination of two or more, or both may be used in combination.

  When the known coagulant is added to the organic coagulant of the present invention in advance, the amount of the known inorganic coagulant is usually 100% or less, preferably 5 based on the weight of the organic coagulant of the present invention. -50%, more preferably 10-30%, known organic coagulants are usually 20 or less, preferably 1-10%, more preferably 2-5%.

  When a known inorganic and / or organic coagulant is added to the wastewater separately from the organic coagulant of the present invention, the amount used is the type of sludge or wastewater, the size of suspended particles, TS in the wastewater, etc. Depending on the TS in the wastewater, the lower limit is preferably 0.5%, more preferably 1%, particularly preferably 2%, and the upper limit is preferable from the same viewpoint. Is 10%, more preferably 8%, particularly preferably 5%. In the known organic coagulants, the lower limit is preferably 0.01%, more preferably 0.05%, particularly preferably 0 from the viewpoint of cohesiveness. From the same viewpoint, the upper limit is preferably 5% or less, more preferably 3% or less, and particularly preferably 1%.

In the method (1), the method for adding (B) to the sludge or wastewater treated with the organic coagulant of the present invention is not particularly limited, and (B) may be added to the sludge or wastewater as it is. However, from the viewpoint of uniform mixing, the method of adding (B) to an aqueous solution and then adding it to the sludge or wastewater is preferred. When (B) is used as an aqueous solution, the concentration of (B) is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight.
The dissolution method and the dilution method after dissolution are not particularly limited, and are the same as in the case of the organic coagulant. In particular, when powdered (B) is dissolved in water, adding (B) all at once is not preferable because it causes dents and makes it difficult to dissolve in water.

  In the method (1), the amount of (B) used when added to sludge or wastewater varies depending on the type of sludge or wastewater, the content of suspended particles, the molecular weight of (B), etc. However, from the viewpoint of coagulation performance based on the sludge or TS in the wastewater, the preferred lower limit is 0.01%, more preferably 0.1%, particularly preferably 1%, most preferably 1.5%, the same From the viewpoint, the preferable upper limit is 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.

Further, the method for adding the polymer flocculant (C) of the present invention to the sludge or wastewater in the method (2) is not particularly limited, and (C) may be added to the wastewater as it is, From the viewpoint of the above, a method of adding (C) to an aqueous solution and then adding it to sludge or wastewater is preferred. When (C) is used as an aqueous solution, the concentration is preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight.
The dissolution method and the dilution method after dissolution are not particularly limited, and are the same as in the case of the organic coagulant and (B).

  The amount of (C) used when adding to sludge or wastewater in the method (2) depends on the type of sludge or wastewater, the content of suspended particles, the molecular weight of the polymer flocculant, etc., and is not particularly limited. However, based on the TS in the sludge or wastewater, from the viewpoint of coagulation performance, the preferred lower limit is 0.01%, more preferably 0.1%, particularly preferably 1%, most preferably 1.5%, and the like From this viewpoint, the upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.

  Moreover, as a dehydration method (solid-liquid separation method) of floc sludge formed by the processing method of (1) or (2) above, for example, gravity sedimentation, membrane filtration, column filtration, pressurized flotation, and a concentration device ( For example, a method using a thickener) and a dehydrator (for example, a centrifugal dehydrator, a belt press dehydrator, a filter press dehydrator, and a capillary dehydrator) can be mentioned. Among these, preferred from the viewpoint of high floc strength, which is the specific aggregation performance of the polymer flocculant of the present invention, is a method using a dehydrator, particularly a centrifugal dehydrator, a belt press dehydrator and a filter press dehydrator. .

  Other uses of the polymer flocculant of the present invention include, for example, a flocculant for excavation and muddy water treatment, a papermaking agent (for example, a formation aid for paper industry, drainage yield improver, drainage improver and paper strength Enhancing agents), crude oil production additives (crude oil secondary and tertiary recovery additives), dispersants, scale inhibitors, coagulants, decoloring agents, thickeners, antistatic agents and textile treatment agents, Of these, a flocculant for excavation and muddy water treatment, a papermaking chemical, and an additive for increasing crude oil production are preferable.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%. The intrinsic viscosity [η] (dl / g) is a value measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution. The colloidal equivalent value and solid content of the polymer flocculant were measured by the methods described above. In addition, TS (evaporation residue weight) and organic content (ignition loss) in sludge or wastewater were performed according to the analysis method described in the sewer test method (Japan Sewerage Association, 1984 version).
Further, the floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD, filtrate clarity, coagulation property, and decolorization property in this example were evaluated according to the following methods.

<Flock particle size>
Jar tester [Miyamoto Riken Kogyo Co., Ltd., model JMD-6HS-A, and so on. ] Are attached to the stirring rod in the form of a cross in the shape of a cross, and sludge or waste water [or in advance (A) 200 ml of sludge or waste water mixed and mixed] is put into a 500 ml beaker and set in a jar tester. While rotating the jar tester at 120 rpm and slowly stirring the sludge or wastewater, a predetermined amount of 0.2 wt% aqueous polymer flocculant solution [or 0 in the case of sludge or wastewater mixed with (A) in advance is mixed. .2 wt% (B)] was added at a time and stirred for 30 seconds, and then the stirring was stopped and the size of the aggregate was visually observed (the floc particle size at 120 rpm is shown in the table). .
Subsequently, the rotational speed is set to 300 rpm, and after stirring for 30 seconds, the stirring is stopped and the size of the aggregate is visually observed again (the floc particle size at the rotational speed of 300 rpm is shown in the table).

<Amount of filtrate>
T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, graduated cylinder that can measure 300 ml, set sludge after the above floc particle size test and filter at once Then, using a stopwatch, measure the filtrate amount 60 seconds after immediately after the addition.
<Filter cloth peelability>
Part of the filtered sludge is removed with a spatula and subjected to a dehydration test (2 kg / cm ² , 60 seconds) using a press filter tester, and the peelability of the dewatered cake from the filter cloth after the test is evaluated according to the following criteria: To do.
A: Very easy to peel off (almost no filter cloth deposits)
○: Easy to peel off (Slightly attached filter cloth)
Δ: Slightly difficult to peel off (there is a filter cloth deposit, slightly sticking to the inside of the filter cloth)
×: Hard to peel off (attaches to the inside of the filter cloth)

<Moisture content of cake>
About 3.0 g of the dehydrated cake after the filter cloth peelability test is weighed into a petri dish (W3) and dried in a circulating drier until the water has completely evaporated (for example, at 105 ± 5 ° C. for 8 hours). After that, the weight of the dry cake remaining on the petri dish is set as (W4), and the moisture content of the cake is calculated from the following formula.

Cake moisture content (% by weight) = {(W3) − (W4)} × 100 / (W3)

<COD>
Using the filtrate after measuring the filtrate amount, COD is measured according to the COD _Mn analysis method described in JIS K-0102 (1998 version).
<Filtrate clarity>
Using the filtrate after measuring the above filtrate amount, an absorbance meter [manufactured by Shimadzu Corporation, UV-1200, the same shall apply hereinafter. ], The absorbance at wavelengths of 590 nm and 700 nm is measured, and the filtrate clarity is evaluated. The numerical value (%) of absorbance indicates a value when the absorbance of ion-exchanged water is 100%.
<Coagulability>
Using the same apparatus as the floc particle size evaluation method, 200 ml of sludge or waste water is taken into a 500 ml beaker and set in a jar tester. The rotation number of the jar tester was set to 120 rpm, and while stirring sludge or waste water slowly, a predetermined amount of 0.2 wt% organic coagulant aqueous solution was added at once and stirred for 30 seconds. Thereafter, the sludge or waste water is centrifuged (TOMY SEIKO CO.). LTD. Manufactured, type LC06], and centrifuged at 2,000 rpm for 10 minutes, and the volume% of sludge that has condensed and settled with respect to the total amount of sludge or wastewater is calculated to evaluate the setting property.
<Decolorization>
Using the filtrate after centrifugation, the absorbance at wavelengths of 430 nm and 700 nm is measured with an absorptiometer to evaluate decolorization. The numerical value (%) of absorbance indicates a value when the absorbance of ion-exchanged water is 100%.

Example 1
After putting 500 parts (100 mol%) of a 60% aqueous solution of a quaternary ammonium salt obtained by reacting benzyl chloride with N, N-dimethylaminoethyl methacrylate in a reaction vessel equipped with a stirrer, a temperature sensor and a temperature control device. Further, 500 parts of ion-exchanged water was added so that the total amount of monomers in the system was 30%, and the mixture was stirred until the inside of the system became a uniform solution. While further stirring, the pH of the monomer aqueous solution (20 ° C.) was adjusted to 4.0 using sulfuric acid while monitoring with a pH meter. After sufficiently replacing the system with nitrogen (purity 99.999% or more), 50 parts of a 10% aqueous solution of sodium persulfate as an initiator was added with stirring. The inside of the system was gradually heated from the outside, polymerization started at 50 ° C., and heat generation was observed. Therefore, the system was cooled from the outside and polymerized at a content temperature of 50 to 60 ° C. for 10 hours. Thereafter, the mixture was heated from the outside and aged at 80 ° C. for 1 hour to complete the polymerization. After completion of the polymerization, the content was taken out, 2,000 parts of acetone was added thereto, and the mixture was stirred for 30 minutes with a commercially available juicer mixer to obtain a precipitate. After the precipitate was taken out by vacuum filtration (using JIS standard 2 types of filter paper), the solvent was distilled off in a vacuum dryer (vacuum degree 1.3 kPa, 40 ° C. × 2 hours) to form a powder. 294 parts of polymer (A1) was obtained (yield 95%, solid content 97%).

Example 2
In Example 1, instead of 500 parts of a 60% aqueous solution of a quaternary ammonium salt obtained by reacting N, N-dimethylaminoethyl methacrylate with benzyl chloride, 380 parts (70 mol%) of the same aqueous solution and N, N-dimethylamino 297 parts of a powdery polymer (A2) were obtained in the same manner as in Example 1 except that 118 parts (30 mol%) of a 60% aqueous solution of a quaternary ammonium salt obtained by reacting methyl methacrylate with ethyl methacrylate was used ( (Yield 96%, solid content 97%).

Example 3
In Example 1, instead of 500 parts of a 60% aqueous solution of quaternary ammonium salt obtained by reacting benzyl chloride with N, N-dimethylaminoethyl methacrylate, 440 parts (65 mol%) of the same aqueous solution and a 50% aqueous solution of acrylamide 61 297 parts of a powdery polymer (A3) were obtained in the same manner as in Example 1 except that 5 parts (30 mol%) and 5 parts (5 mol%) acrylic acid were used (yield 96%, solid content) 97%).

Comparative Example 1
50 parts of a commercially available dimethylamine and epichlorohydrin polycondensate (manufactured by Yokkaichi Synthesis Co., Ltd., Kathiomaster PD-7, 50% solids concentration aqueous solution) is added to 2,000 parts of acetone and stirred for 30 minutes with a mixer to precipitate. I got a thing. Thereafter, the same treatment as in Example 1 was carried out to obtain 24 parts of a powdered polycondensate (ratio A1) (yield 94%, solid content 98%).

Production Example 1
After adding 115 parts (100 mol%) of an 80% aqueous solution of a quaternary ammonium salt obtained by reacting N, N-dimethylaminoethyl methacrylate with methyl chloride into Kolben equipped with a stirrer, the total amount of monomers in the system was further increased. 192 parts of ion-exchanged water was added so that it might become 30%, and it stirred until the inside of a system became a uniform solution. While further stirring, the pH of the monomer aqueous solution (20 ° C.) was adjusted to 4.0 using sulfuric acid while monitoring with a pH meter. Next, the temperature of the solution was adjusted to 40 ° C. in a constant temperature bath at 40 ° C., and the system was sufficiently substituted with nitrogen (purity 99.999% or more) (gas phase oxygen concentration 10 ppm or less). Next, 0.46 part of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride as an initiator was added all at once with stirring. After about 1 minute, polymerization started and exotherm was observed, but the mixture was cooled from the outside and polymerized at a content temperature of 40 to 50 ° C. for 10 hours. Thereafter, the mixture was heated from the outside and aged at 70 ° C. for 1 hour to complete the polymerization. During the polymerization, the content became highly viscous and stirring became difficult, so stirring was stopped halfway.
After the completion of the polymerization, the contents were taken out, and then treated in the same manner as in Example 1 to obtain 95 parts of a powdered water-soluble polymer (B1) (yield 98%, solid content 95%).

Production Example 2
In Production Example 1, instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 80% aqueous solution 74 of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl acrylate 74 97 parts of a powdery water-soluble polymer (B2) were obtained in the same manner as in Production Example 1 except that 65 parts (60 mol%) of acrylamide and 65 parts (60 mol%) of an acrylamide solution were used. 98%, solid content 93%).

Production Example 3
In Production Example 1, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 10 parts (5 mol%) of the same aqueous solution, methyl of N, N-dimethylaminoethyl acrylate Powder as in Production Example 1 except that 58 parts (30 mol%) of an 80% aqueous solution of chloride salt, 51 parts (45 mol%) of 50% aqueous solution of acrylamide and 12 parts (20 mol%) of acrylic acid were used. 95 parts of a water-soluble polymer (B3) was obtained (yield 96%, solid content 93%).

Example 4
9 parts of (B1) and 1.3 parts of (A1) were placed in a glass bottle capable of being sealed and shaken well until uniform to obtain 10.3 parts of a polymer flocculant (C1).

Example 5
In the same manner as in Example 4 except for using 9 parts of (B2) instead of (B1) and 0.42 part of (A2) instead of (A1), 9.42 parts of the polymer flocculant (C2) were added. Obtained.

Example 6
In the same manner as in Example 4 except that 9 parts of (B3) was used instead of (B1) and 0.84 part of (A2) was used instead of (A1), 9.84 parts of polymer flocculant (C3) was added. Obtained.

Comparative Example 2
9.84 parts of the polymer flocculant (C4) in the same manner as in Example 4 except that 9 parts of (B3) instead of (B1) and 0.84 part of (Ratio A1) instead of (A1) were used. Got.

  Table 1 shows the compositions and intrinsic viscosities of (A1) to (A3), (B1) to (B3), and (Ratio A1). Table 2 shows the compositions, blending amounts, colloid equivalent values, and intrinsic viscosities of (C1) to (C3) and (C4).

ＢＤＡＭＱ ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレートのベンジルクロライド４
級アンモニウム塩
ＭＤＡＭＱ ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレートのメチルクロライド４級
アンモニウム塩
ＡＡＭ ：アクリルアミド
ＡＡｃ ：アクリル酸

BDAMQ: benzyl chloride 4 of N, N-dimethylaminoethyl methacrylate
Grade ammonium salt MDAMQ: Methyl chloride quaternary of N, N-dimethylaminoethyl methacrylate
Ammonium salt AAM: Acrylamide AAc: Acrylic acid

ＡＡＭ ：アクリルアミド
ＭＤＡＡＱ ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートのメチルクロライド４級ア
ンモニウム塩
ＭＤＡＭＱ ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレートのメチルクロライド４級
アンモニウム塩
ＡＡｃ ：アクリル酸

AAM: Acrylamide MDAAQ: N, N-dimethylaminoethyl acrylate methyl chloride quaternary acrylate
Numonium salt MDAMQ: Methyl chloride quaternary of N, N-dimethylaminoethyl methacrylate
Ammonium salt AAc: Acrylic acid

Examples 7 and 8, Comparative Example 3
(A1), (A2), (Ratio A1) and (B3) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 500 ml of waste water collected from the F dyeing factory [pH 6.6, TS 2.0%, organic content 33%] in a 1 L beaker, and 25 ml of each aqueous solution of (A1), (A2) and (ratio A1) (solid content) The addition amount was 0.5% / TS), and the mixture was sufficiently stirred and mixed with a hand mixer. 40 ml of the above (B3) aqueous solution was further added to 200 ml of the waste water [solid content addition amount of (B3) 2.0% / TS], and the mixture was stirred and mixed. The fabric peelability, cake moisture content, COD and filtrate clarity were evaluated. The results are shown in Table 3.
From Table 3, in Examples 7 and 8, compared to Comparative Example 3, flocs having a large particle diameter are formed, and the flocs once formed are not easily broken even under high agitation (300 rpm) (the floc strength is strong). Further, it can be seen that excellent effects are exhibited in filter cloth peelability, dewaterability (cake water content), COD reduction characteristics, and filtrate clarification.

Example 9, Comparative Examples 4, 5
(C3), (C4) and (B3) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 45 ml of each aqueous solution was added to digested sludge collected from K sewage treatment plant [pH 6.1, TS 1.9%, organic content 63%] (solid content added amount 2.4% / TS). In the same manner as in Comparative Example 3, the performance was evaluated by mixing. The results are shown in Table 4.
From Table 4, in Example 9, compared to Comparative Examples 4 and 5, flocs having a large particle diameter are formed, and the flocs once formed are not easily broken even under high agitation (300 rpm) (the floc strength is strong). Further, it can be seen that excellent effects are exhibited in filter cloth peelability, dewaterability (cake water content), COD reduction characteristics, and filtrate clarification.

Example 10 and Comparative Example 6
(C1) and (B1) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 50 ml of each aqueous solution was added to excess sludge [pH 6.4, TS 2.7%, organic content 72%] collected from the H sewage treatment plant (solid content added 2.1% / TS). The performance was evaluated by mixing in the same manner. The results are shown in Table 5.
From Table 5, in Example 10, compared to Comparative Example 6, flocs having a large particle diameter were formed, and the flocs once formed were not easily broken (high flock strength) even under high agitation (300 rpm). It can be seen that it has excellent effects in cloth peelability, dewaterability (cake water content), COD reduction characteristics and filtrate clarity.

Example 11, Comparative Examples 7 and 8
(C2), (C4) and (B2) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 30 ml of each aqueous solution was added to surplus sludge [pH 7.0, TS 1.3%, organic content 58%] collected from M Food Factory (solid content added 2.0% / TS). The performance was evaluated by mixing in the same manner as in Comparative Example 3. The results are shown in Table 6.
From Table 6, in Example 11, compared to Comparative Examples 7 and 8, flocs having a large particle diameter were formed, and the flocs once formed were not easily broken even under high agitation (300 rpm) (the floc strength was strong). Further, it can be seen that excellent effects are exhibited in filter cloth peelability, dewaterability (cake water content), COD reduction characteristics, and filtrate clarification.

Examples 12-14, Comparative Example 9
(A1) to (A3) and (Ratio A1) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. 500 ml of waste water [pH 6.2, TS 0.05%, COD 560 ppm] collected from the N dyeing factory was taken in a 1 L beaker, and 5 ml of each of the aqueous solutions (A1) to (A3) and (Ratio A1) (solid content added amount 0) .5% / TS) was added, and the mixture was sufficiently stirred and mixed with a hand mixer, and the coagulation property, COD, and decolorization property were evaluated by the above methods. The results are shown in Table 7.
From Table 7, it can be seen that Examples 12 to 14 are superior in setting performance as compared with Comparative Example 9, and show excellent effects in COD reduction characteristics and decolorization.

The organic coagulant of the present invention is used for COD reduction treatment such as paper mill waste water, and for decolorization of coloring components, as well as dye fixing agents, paper making agents (for example, formation aids for paper industry, drainage yield) Improvers, drainage improvers and paper strength enhancers), sludge dehydration treatment agents, dispersants, scale inhibitors, antistatic agents and fiber treatment agents.
Further, the polymer flocculant of the present invention can be used for dehydration treatment of organic sludge or inorganic sludge generated by treatment of sewage or factory wastewater, etc., and particularly suitable for dehydration treatment of organic sludge. A wide range of uses, such as dispersants, scale inhibitors, coagulants, decolorizers, thickeners, antistatic agents, fiber treatment agents, and especially flocculants for drilling and muddy water treatment, papermaking chemicals (eg papermaking) It is suitably used for industrial formation formation aids, drainage yield improvers, drainage improvers and paper strength enhancers) and crude oil production additives (crude oil secondary and tertiary recovery additives).

Claims (11)

An organic coagulant comprising a water-soluble (co) polymer (A) having the monomer (a1) represented by the general formula (1) as an essential constituent unit.

^{_{CH 2 = CR 1 -CO-X}} -Q-N + R 2 R 3 R 4 · Z - (1)

[Wherein, X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ¹ is H or a methyl group; R ² is aralkyl having 7 to 30 carbon atoms; An alkylaryl group, R ³ and R ⁴ are each independently H, an alkyl group having 1 to 16 carbon atoms, an aralkyl or alkylaryl group having 7 to 30 carbon atoms; and Z ⁻ represents a counter anion. ] The organic coagulant according to claim 1, wherein the proportion of (a1) in the monomer constituting (A) is 1 to 100 mol%. Claim (A) further comprises one or more monomers (a2) selected from the group consisting of monomer (a21), (meth) acrylamide and (meth) acrylic acid represented by formula (2) as a constituent unit. Item 3. The organic coagulant according to Item 1 or 2.

^{_{CH 2 = CR 5 -CO-X}} -Q-N + R 6 R 7 R 8 · Z - (2)

Wherein X is O or NH; Q is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ⁵ is H or a methyl group; R ⁶ , R ⁷ and R ⁸ are each independently H or an alkyl group having 1 to 16 carbon atoms; Z ⁻ represents a counter anion. ] The organic coagulant according to claim 3, wherein the proportion of (a1) in the constituent monomers is 1 to 100 mol% and the proportion of (a2) is 0 to 90 mol%. The organic coagulant according to any one of claims 1 to 4, wherein the intrinsic viscosity of (A) measured in 1N-NaNO ₃ at 30 ° C is 0.01 to 3 (dl / g). The organic coagulant according to any one of claims 1 to 5, which is for COD reduction treatment of papermaking wastewater. A polymer flocculant comprising the organic coagulant according to any one of claims 1 to 6 and another water-soluble (co) polymer (B) excluding (A). The polymer flocculant according to claim 7, wherein (B) is a cationic (co) polymer (B1) and / or an amphoteric (co) polymer (B2). The polymer flocculant according to claim 7 or 8, wherein (B) is a (co) polymer having the monomer (a21) as an essential constituent unit. The organic coagulant according to any one of claims 1 to 6 is added to and mixed with sludge or waste water, and then (B) is further added and mixed to form a floc for solid-liquid separation. Item 10. A method for using the polymer flocculant according to any one of Items 7 to 9. The polymer flocculant according to any one of claims 7 to 9, wherein the polymer flocculant is added to and mixed with sludge or wastewater to form flocs and solid-liquid separation. A method for treating sludge or wastewater, characterized by being used.