JP6571483B2 - Organic coagulant - Google Patents

Description

  The present invention relates to an organic coagulant used for sludge or wastewater treatment such as sewage or human waste and factory wastewater.

Conventionally, in the coagulation and decoloration 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, sulfate bands, Aluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime) and organic coagulants [for example, polymer of dimethylaminoethyl methacrylate methyl chloride quaternary salt (Patent Documents 1 and 2)] Has been.
In addition, these organic and inorganic sludges or wastewaters are dehydrated using an amphoteric or cationic polymer flocculant after adding an organic or inorganic coagulant. . For example, a method using an organic coagulant of condensed polyamine and an amphoteric polymer flocculant (Patent Document 3) has been proposed.

Japanese Patent No. 3697630 JP 2012-115790 A JP 2000-225400 A

However, the inorganic coagulant requires a huge amount of addition to the sludge or waste water, and there is a problem that the amount of sludge after solid-liquid separation increases. In addition, with the recent tightening of wastewater regulations, there is an increasing need to reduce COD (chemical oxygen demand) in effluent water, and further improvement in the performance of organic coagulants is particularly desired.
In addition, in the dehydration process, a stronger floc-forming ability is desired from the viewpoint of improving the processing speed associated with the recent increase in the amount of sludge and wastewater. From the viewpoint of the cost of incineration or landfill disposal of the dehydrated cake, Therefore, a polymer flocculant having the ability to decolorize separated water after the dehydration step and to reduce COD is desired.
The organic coagulant described above requires a lower amount of addition than the inorganic coagulant, and although the amount of sludge can be greatly reduced, the effect of coagulation and dehydration was insufficient. In addition, the method using the above-mentioned organic coagulant and polymer coagulant has not been sufficient.

  The object of the present invention is an organic coagulant having excellent coagulation and decolorization effects, and coagulation and coagulation performance such as floc coarsening, floc strength increase, low moisture content of dehydrated cake, and filtrate decolorization and COD reduction. The object is to provide an excellent setting and coagulation treatment agent.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention comprises a water-soluble cationic monomer (a1) represented by the following general formula (1) and an unsaturated monomer (a) containing a divalent unsaturated monomer (b) as a structural unit ( An organic coagulant (P) comprising a (co) polymer (A); a combination of the (P) and a polymer flocculant (Q) comprising a water-soluble (co) polymer (B) A coagulation and coagulation treatment agent (Z) for sludge or wastewater.

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

[Wherein R ¹ is H or CH ₃ ; R ^{2 to} R ⁴ are H; X ¹ is O or NH; Q is a divalent hydrocarbon group having 2 to 4 carbon atoms which may have a hetero atom. Z ⁻ represents a residue excluding H ⁺ of the protonic acid. ]

The organic coagulant (P) of the present invention has the following effects.
(1) Excellent condensation performance against sludge or wastewater.
(2) The coagulation and coagulation treatment agent (Z) obtained by combining the organic coagulant and the polymer coagulant (Q) exhibits excellent coagulation and coagulation performance.
In the present invention, the coagulation performance refers to the performance of neutralizing the surface charge of dispersed suspended particles to coagulate the suspended particles, and the supernatant liquid clarity, coagulability, and supernatant liquid decolorization described later. It can be evaluated by sex and COD. The agglomeration performance refers to the ability to agglomerate the agglomerated fine particles by cross-linking adsorption action to form coarse flocs. The floc particle size, sludge volume ratio, filtrate COD, filtrate clarification, and cake water content described later Can be evaluated by rate.

[Water-soluble cationic monomer (a1)]
The water-soluble cationic monomer (a1) in the present invention is represented by the following general formula (1). In the present invention, the water-soluble monomer or water-soluble (co) polymer means that the solubility in water is 1 g or more / 100 g of water (20 ° C.), and the water-insoluble monomer described later means the solubility in water. Is less than 1 g / 100 g water (20 ° C.).

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

In general formula (1), R ¹ is H or CH ₃ (preferably CH ₃ ), R ^{2 to} R ⁴ are H, X ¹ is O or NH (preferably O), and Q has a hetero atom. A divalent hydrocarbon group having 2 to 4 (preferably 2 to 3) carbon atoms (hereinafter sometimes abbreviated as C), and Z ⁻ represents a residue other than H ⁺ of the protonic acid.
Moreover, in General formula (1), the thing of C of Q is less than 2 does not exist, and when it exceeds 5, the coagulation performance of the organic coagulant (P) containing (A) mentioned later will worsen.
Examples of Q include an alkylene (ethylene, 1,3-propylene, 1,2-propylene, etc.) group, a hydroxyalkylene (hydroxyethylene, hydroxypropylene, etc.) group, and the like. From the viewpoint of the coagulation performance of the organic coagulant (P), Q is preferably an alkylene group, more preferably an ethylene group.

Examples of Z ⁻ include residues other than H ⁺ of the following protonic acids (1) to (6).
(1) inorganic acids such as hydrogen halides (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid;
(2) Sulfate esters such as C1-30 sulfates [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 1 to 10 mol adduct sulfate of ethylene oxide (hereinafter abbreviated as EO) of alcohol (C10-20)];

(3) Sulfonic acids such as C1-30 sulfonic acids [eg alkyl (C1-10) sulfonic acids (eg methanesulfonic acid and ethanesulfonic acid), alkylaryl (C7-30) sulfonic acids (eg alkylbenzene sulfonic acid, alkylphenol) Sulfonic acids and alkylnaphthalene sulfonic acids), higher alkyl (C10-30) sulfonic acids, higher fatty acid esters (C10-30) sulfonic acids, higher alcohol ethers (C10-30) sulfonic acids, sulfosuccinic acid esters, higher fatty acid amides (C10) To 20) alkyl (C1-10) sulfonic acid, alkyl (C1-10) diphenyl ether sulfonic acid and alkyl (C1-10) benzimidazole sulfonic acid];
(4) Phosphate esters such as C1-30 phosphate esters [eg mono- and dialkyl (alkyl C1-30) phosphate esters, mono- and dialkenyl (alkenyl C1-30) phosphate esters, (poly) oxyalkylenes [EO 1-14 mol addition and / or propylene oxide (hereinafter abbreviated as PO) 1-9 mol addition] alkyl (C1-30) ether phosphate ester, sugar phosphate ester (eg glucose-phosphate ester, glucose amine phosphorus) Acid esters, 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 of higher fatty acid amide (C10-20) (C1 10) phosphonic acid, alkyl (C1-10) diphenyl ether phosphonic acid and alkyl (C1-10) benzimidazolephosphonic acid];
(6) Carboxylic acids such as C1-30 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]; Cyclic [C4-30 mono- and dicarboxylic acids such as cyclopentane (di) carboxylic acid and cyclohexane (di) carboxylic acid]; and aromatic (aliphatic) [C7-30 mono- and dicarboxylic acids such as benzoic acid , Phthalic acid, xylylene dicarboxylic acid].

  Of the above protonic acids, from the viewpoint of the coagulation performance of (A), preferred are inorganic acids, sulfuric esters and sulfonic acids, more preferred are hydrochloric acid, sulfuric acid and methanesulfonic acid, and particularly preferred are sulfuric acid and methanesulfonic acid. .

[Unsaturated monomer (a)]
The unsaturated monomer (a) in the present invention contains other water-soluble monomers (a2) to (a4) in addition to the water-soluble cationic monomer (a1) and the divalent unsaturated monomer (b) described later. be able to. Examples of the other water-soluble monomers include cationic monomers (a2) other than (a1), nonionic monomers (a3), anionic monomers (a4), and mixtures thereof.

(A2) Cationic monomer The following, these salts [for example, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, methyl chloride salts, dimethyl sulfate salts, benzyl chloride salts, etc.], and mixtures thereof are mentioned. It is done.

(A21) Nitrogen-containing (meth) acrylates having C5-30, such as N, N-dialkyl (alkyl group is C1-2) aminoalkyl (C2-3) (meth) acrylate [N, N-dimethylaminoethyl and -Propyl (meth) acrylate, N, N-diethylaminoethyl and -propyl (meth) acrylate and the like], heterocycle-containing (meth) acrylate [N-morpholinoethyl (meth) acrylate and the like];

(A22) (Substituted) Ethylenically unsaturated compounds having an amino group or an ammonium group C5-30, such as N, N-dialkyl (C1-2) aminoalkyl (C2-3) (meth) acrylamide [N, N -Dimethylaminoethyl (meth) acrylamide etc.], vinylamine, vinylaniline, (meth) allylamine, p-aminostyrene etc .;
(A23) Compound having amine imide group C5-30, such as 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1 -(2'-Phenyl-2'-hydroxyethyl) amine (meth) acrylimide.

  Among the above (a2), (a21) and (a22) are preferable from the viewpoint of setting performance and industry, and N, N-dialkyl (C1-2) aminoalkyl (C2-3) (meth) acrylate is more preferable. Salt, vinylamine, (meth) allylamine, particularly preferred is N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate salt, vinylamine, (meth) allylamine, most preferred Is a salt of N, N-dimethylaminoethyl (meth) acrylate, vinylamine. Further, among the salts of N, N-dimethylaminoethyl (meth) acrylate, preferred are inorganic acid salts and methyl chloride salts, and particularly preferred are methyl chloride salts.

(A3) Nonionic monomer The following are mentioned, and these mixtures.
(A31) (Meth) acrylate C4 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method described later. ] 5,000 or less, such as hydroxyl group-containing (meth) acrylates [for example, hydroxyethyl-, diethylene glycol mono-, polyethylene glycol (polymerization degree 3-50) mono- and (poly) glycerol (polymerization degree 1-10) mono ( Meth) acrylate] and alkyl acrylate (alkyl group is C1-2) ester (C4-5, such as methyl acrylate, ethyl acrylate);
(A32) (Meth) acrylamide and its derivatives C3-30, such as (meth) acrylamide, N-alkyl (C1-3) (meth) acrylamide [N-methyl and -isopropyl (meth) acrylamide etc.], N- Alkylol (meth) acrylamide [N-methylol (meth) acrylamide etc.], N-alkylol (C1-2) (meth) acrylamide alkylene oxide (C2-3, hereinafter abbreviated as AO) 1-8 mol adduct ;
(A33) Nitrogen-containing ethylenically unsaturated compounds other than (a1) and (a2), those having C3-30, such as acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinylimidazole, N- AO2 to 10 mol adduct of vinylsuccinimide, N-vinylcarbazole and 2-cyanoethyl (meth) acrylate, hydroxyethylmaleimide.

  Of the above (a3), from the viewpoint of setting performance, (a32) and (a33) are preferable, and acrylonitrile, N-vinylformamide, and (meth) acrylamide are more preferable.

(A4) Anionic monomer The following, these salts [alkali metal (lithium, sodium, potassium, etc., the same shall apply hereinafter) salt, alkaline earth metal (magnesium, calcium, etc., the same shall apply hereinafter) salt, ammonium salt and amine (C1-20) salts and the like], and mixtures thereof.

(A41) unsaturated carboxylic acids of C3-30, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, vinylbenzoic acid, allyl acetic acid;
(A42) Unsaturated sulfonic acid C2-20 aliphatic unsaturated sulfonic acid (such as vinyl sulfonic acid), C6-20 aromatic unsaturated sulfonic acid (such as styrene sulfonic acid), sulfonic acid group-containing (meth) acrylate [ Sulfoalkyl (C2-20) (meth) acrylate [2- (meth) acryloyloxyethane, -propane and -butanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc.], sulfonic acid group-containing (meth) acrylamide [2- (meth) acryloylaminoethanesulfone Acid, 2- and 3- (meth) acryloylaminopropane Sulfonic acid, 2- and 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.], alkyl ( C1-20) (meth) allylsulfosuccinic acid ester [methyl (meth) allylsulfosuccinic acid ester and the like] and the like;
(A43) (Meth) acryloyl polyoxyalkylene (alkylene group is C1-3) sulfate ester (meth) acryloyl polyoxyethylene (EO) addition mole number 2-50] sulfate ester and the like.

  Of the above (a4), from the viewpoint of setting performance, (a41) is more preferable, and (meth) acrylic acid and (anhydrous) maleic acid are more preferable.

The GPC measurement of Mn and the weight average molecular weight (Mw) described later in the present invention shall conform to the following measurement conditions.
<GPC measurement conditions>
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: 2 TSKgel GMHXL
+ TSKgel Multipore HXL-M, manufactured by Tosoh Corporation Column temperature: 40 ° C
Solvent: Tetrahydrofuran (THF)
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandard
POLYSTYRENE), manufactured by Tosoh Corporation

The proportion of (a1) based on the total number of moles of (a1) to (a4) in the unsaturated monomer (a) is preferably 40 to 100 moles from the viewpoint of the setting performance of the organic coagulant (P) described later. %, More preferably 60 to 100 mol%, particularly preferably 80 to 100 mol%;
The proportion of (a2) is preferably 60 mol% or less, more preferably 40 mol% or less, particularly preferably 20 mol% or less from the same viewpoint;
The proportion of (a3) is preferably 60 mol% or less, more preferably 40 mol% or less, particularly preferably 20 mol% or less from the same viewpoint;
The proportion of (a4) is preferably 60 mol% or less, more preferably 40 mol% or less, and particularly preferably 20 mol% or less from the viewpoint of the solubility of (A) in water.

[Divalent unsaturated monomer (b)]
The divalent unsaturated monomer (b) in the present invention has two polymerizable unsaturated groups. The acrylate monomer (b1), the methacrylate monomer (b2), and two or more of these are described below. A mixture of the above is included.
As (b), a diunsaturated monomer represented by the following general formula (2) can be preferably used.
^{_{CH 2 = CR 5 -CO-OCH}} 2 CH 2 -X 2 -CO-CR 6 = CH 2 (2)

In the general formula (2), R ⁵ and R ⁶ represent H or a methyl group (preferably a methyl group); X ² represents O or NH.

Examples of (b1) include methacryloyloxyethyl acrylate, ethylene glycol diacrylate, and acryloylaminoethyl acrylate.
Examples of (b2) include ethylene glycol dimethacrylate and methacryloylaminoethyl methacrylate.

  Of the above, (b2) is preferable from the viewpoint of setting performance, ethylene glycol dimethacrylate and methacryloylaminoethyl methacrylate are more preferable, and methacryloylaminoethyl methacrylate is particularly preferable.

  The divalent unsaturated monomer (b) is preferably 0.00001 to 0.000 based on the unsaturated monomer (a) from the viewpoints of coagulation performance and water solubility of the water-soluble (co) polymer (A) described later. 5 mol%, more preferably 0.0001 to 0.12 mol%, particularly preferably 0.001 to 0.06 mol%.

The unsaturated monomer (a) is water-insoluble if necessary in addition to the water-soluble cationic monomers (a1) and (a1) other than the water-soluble cationic monomers (a1) and (a1) as long as the effects of the present invention are not impaired. Monomer (x) may be used in combination.
Examples of the water-insoluble monomer (x) include the following (x1) to (x5) and mixtures thereof.
(X1) C6-23 (meth) acrylate (meth) acrylate of aliphatic or cycloaliphatic alcohol (C3-20) [propyl-, butyl-, lauryl-, octadecyl- and cyclohexyl (meth) acrylate etc.] and epoxy Group (C4-20) -containing (meth) acrylate [glycidyl (meth) acrylate and the like];

(X2) Unsaturated carboxylic acid of [monoalkoxy (C1-20)-, monocycloalkoxy (C3-12)-or monophenoxy] polypropylene glycol (polypropylene glycol is hereinafter abbreviated as PPG) (degree of polymerization 2-50) Monoester Monool (C1-20) or monohydric phenol (C6-20) propylene oxide (hereinafter abbreviated as PO) adduct (meth) acrylate ester [ω-methoxy PPG mono (meth) acrylate, ω-ethoxy PPG mono (meth) acrylate, ω-propoxy PPG mono (meth) acrylate, ω-butoxy PPG mono (meth) acrylate, ω-cyclohexyl PPG mono (meth) acrylate, ω-phenoxy PPG mono (meth) acrylate, etc.] and diol (C2-20) or 2 (Meth) acrylic acid ester [ω-hydroxyethyl (poly) oxypropylene mono (meth) acrylate etc.] etc. of PO adduct of polyhydric phenol (C6-20);

(X3) C2-30 unsaturated hydrocarbon ethylene, nonene, styrene, 1-methylstyrene and the like;
(X4) carboxylic acid (C2-30) ester (such as vinyl acetate) of unsaturated alcohol [of C2-4, such as vinyl alcohol, (meth) allyl alcohol];
(X5) Halogen-containing monomer (C2-30, such as vinyl chloride).

  The amount of (x) that may be used in combination with the unsaturated monomer (a) as necessary as long as the effects of the present invention are not impaired is based on the total number of moles of the unsaturated monomer (a). From the viewpoint of solubility in water, it is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less.

[Water-soluble (co) polymer (A)]
In the water-soluble (co) polymer (A) in the present invention, the unsaturated monomer is prepared by known aqueous solution polymerization (for example, adiabatic polymerization, thin film polymerization, spray polymerization, etc. described in JP-A No. 55-133413), In addition, various polymerization methods including known reverse phase suspension polymerization (for example, those described in JP-B-54-30710, JP-A-56-26909, and JP-A-1-5808) [solution dropping polymerization ( For example, JP-A-6-211942), photopolymerization (for example, the one described in JP-B-6-804), precipitation polymerization (for example, the one described in JP-A-61-212310), reverse phase emulsion polymerization (for example, JP And the like described in Japanese Utility Model Laid-Open No. 58-197398] and the like] using a radical polymerization initiator (d). Among the polymerization methods, the solution dropping polymerization method is preferable from the industrial viewpoint and the molecular weight control viewpoint.
As the solution dropping polymerization method, for example, it can be produced using a method of dropping a monomer, a solvent and a radical polymerization initiator solution under the boiling point of the solvent. When an organic solvent is used as the solvent, handling danger and It is usually produced by removing the solvent and adding water if necessary from the viewpoint of environmental protection.

Examples of the solvent (g) used in the solution dropping polymerization method include water, alcohol (methanol, ethanol, isopropyl alcohol, etc.), ketone (methyl ethyl ketone, acetone, etc.), tetrahydrofuran (THF), dimethylformamide (DMF), and mixtures thereof. Or a nonpolar solvent such as toluene or xylene.
Of these, water or a mixed solvent of water and alcohol is preferable from the viewpoints of solubility of the monomer and initiator and removal of the solvent after polymerization. More preferred is water or a mixed solvent of water and isopropyl alcohol.

Examples of the radical polymerization initiator (d) include various compounds such as azo compounds [water-soluble compounds [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.]) and oil-soluble compounds (azobiscyano). Valeronitrile, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.]] and peroxides [water-soluble [peracetic acid, t-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, persulfate] Potassium etc.] and oil-soluble [benzoyl peroxide, cumene hydroxy peroxide, etc.]].
Examples of the salt in the azo compound include inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, alkali metal (lithium, sodium, potassium, etc.) salts, ammonium salts, and the like.

The above peroxide may be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salts [iron sulfate (II ), Etc.], amine complexes of transition metal salts [pentamethylenehexamine complexes of cobalt (III) chloride, diethylenetriamine complexes of copper (II) chloride, etc.], organic reducing agents [ascorbic acid, tertiary amine [dimethylaminobenzoic acid ( Salt), dimethylaminoethanol and the like] and the like.
Further, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more.
Among these, an azo compound is preferable from the viewpoint of reducing the water-insoluble matter of (A).
(D) is usually contained in the aqueous phase of the polymerization system, but depending on the polymerization method, it may be present in either the aqueous phase (or dispersed phase) and / or the oil phase (or continuous phase).

  From the viewpoint of obtaining an optimum molecular weight, the amount of (d) used is preferably 0.001 to 1.0%, more preferably 0.8%, based on the total weight of unsaturated monomers constituting (A). 005 to 0.5%, particularly preferably 0.01 to 0.2%, most preferably 0.02 to 0.15%.

In the polymerization, a chain transfer agent (e) can be used.
Examples of (e) include those having a chain transfer constant of 0.01 to 100, preferably 0.05 to 50, particularly preferably 0.1 to 10.
Chain transfer constants are defined by J. Brandrup and E. Etch Inmargut, “Polymer Handbook (4th edition)”, published by John Willeand and Sons (Polymer Handbook, edited by J. Brandrup and EH Immergut).
(Fourth edition, JOHN WILEY & SONS), pages 97-98.
The chain transfer constant in the present invention is measured using a general method described in “Experimental Methods for Polymer Synthesis” [Chemical Doujin Co., Ltd., published in 1993] and the like. It shall be a chain transfer constant.

  As (e), a compound having one or more amino groups in the molecule [C0-60, such as ammonia, methylamine, dimethylamine, triethylamine, n- and i-propanolamine], molecule A compound having one or more thiol groups therein and a (hypo) phosphite compound [phosphorous acid, hypophosphorous acid, and salts thereof [alkali metal (Na, K, etc.) salts, etc.], and These derivatives etc.] etc. are mentioned. Among these, compounds having one or more thiol groups in the molecule and (hypo) phosphite compounds are preferable from the viewpoint of molecular weight control.

  The amount of (e) used is preferably 0.0001 to 10%, more preferably 0 based on the total weight of unsaturated monomers constituting (A), from the viewpoint of reducing water insolubles and increasing the molecular weight. 0.001 to 5%, particularly preferably 0.01 to 3%, and most preferably 0.05 to 1%.

  The unsaturated monomer concentration in the aqueous monomer solution in the radical polymerization method is usually 1% based on the total weight of the aqueous monomer solution in aqueous solution polymerization, preferably 5% from an industrial viewpoint, more preferably 10%, particularly preferably. Is 15%, most preferably 20%, the upper limit is usually 80%, and preferably 75%, more preferably 70%, particularly preferably 65% from the viewpoint of temperature control during polymerization; %, Preferably 10%, more preferably 15%, particularly preferably 20%, most preferably 25%, the upper limit is usually 90%, preferably 85%, more preferably from the same viewpoint as described above. 80%, particularly preferably 75%, most preferably 70%; in reverse phase suspension polymerization, the lower limit is usually 30%, Preferably 40%, more preferably 45%, particularly preferably 50%, most preferably 55%, the upper limit is usually 90%, preferably 85%, more preferably 80%, particularly preferably 78% from the same viewpoint as described above. %, Most preferably 75%; in reverse phase emulsion polymerization, the lower limit is usually 10%, preferably 20%, more preferably 30%, particularly preferably 40%, most preferably 55%, upper limit from the same viewpoint as above. Is usually 90%, preferably 80% from the same viewpoint as described above, more preferably 75%, particularly preferably 70%, most preferably 65%.

  The pH of the aqueous monomer solution at the time of polymerization is not particularly limited, but is preferably 1 to 8, more preferably 1.5 to 7, particularly preferably 1. from the viewpoint of polymerization rate and solubility of the resulting water-soluble polymer. 8 to 6.5.

The molecular weight of the water-soluble (co) polymer (A) is represented by the intrinsic viscosity [η] (dl / g, a value measured at 30 ° C. in a 1N-NaNO ₃ aqueous solution, the same shall apply hereinafter). Is preferably from 0.1 to 3.0, more preferably from 0.15 to 2.5, and particularly preferably from 0.2 to 2.0, from the viewpoint of decolorization of the supernatant and clarity of the filtrate. In the present invention, the intrinsic viscosity [η] is a value measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution.

  The viscosity (unit: mPa · s, 25 ° C., hereinafter referred to as Vw) of a 1.0% by weight aqueous solution of the water-soluble (co) polymer (A) is preferably 1. from the viewpoints of coagulation performance and filtrate clarity. It is 0-100, More preferably, it is 2.0-80, Most preferably, it is 3.0-60. In the present invention, the 1.0% aqueous solution viscosity [Vw] is an aqueous solution adjusted with a jar tester or the like so that the water-soluble (co) polymer (A) is 1.0% by weight. The value was measured at a rotor rotational speed of 30 rpm using a B-type viscometer.

  The ratio Vw / [η] of the Vw of the water-soluble (co) polymer (A) to the intrinsic viscosity [η] of (A) is preferably 10 to 50, from the viewpoints of coagulation performance and filtrate clarity. Preferably it is 12-30.

  The Vw is controlled by, for example, the weight ratio of the diunsaturated monomer (b) to the weight of all monomers constituting (A), and the Vw increases as the weight ratio of (b) increases. [Η] is controlled by the weight ratio of the chain transfer agent for radical polymerization (e) used during polymerization to the weight of all monomers constituting (A), and as the weight ratio of (e) increases, [η] Becomes smaller. Therefore, in order to increase the Vw / [η], it is possible to control by increasing (b) and / or (e). Conversely, when Vw / [η] is decreased, (b) and / or ( Control can be achieved by reducing e).

[Organic coagulant (P)]
The organic coagulant (P) of the present invention contains the water-soluble (co) polymer (A).
The organic coagulant (P) is usually used in the form of a powder of (A), an aqueous solution of (A) or a dispersion of (A), preferably an aqueous solution or a dispersion.
The content (% by weight) of (A) in the aqueous solution or dispersion is preferably 5 to 80%, more preferably 10 to 75%, particularly preferably 15 to 70% from the viewpoints of industrial and handling properties. It is.

Examples of a method for treating sludge or wastewater in which the organic coagulant (P) and sludge or wastewater are mixed include the following methods.
As a method of adding the organic coagulant (P) to sludge or wastewater, from the viewpoint of uniform mixing, the aqueous solution or dispersion of (A) is further diluted to an aqueous solution and then added to sludge or wastewater and sufficiently stirred. Although it is preferable, (A) may be added to sludge or wastewater as it is and stirred and mixed.
When (A) is used as a dilute aqueous solution, the concentration (% by weight) of (A) is preferably 0.01 to 20%, more preferably 0.1 to 5%.
As a dissolution method of (A) and a dilution method after dissolution, for example, a predetermined amount of (A) is added while stirring water previously weighed using a stirring device such as a jar tester described later, and several hours ( A method of stirring and dissolving for about 1 to 4 hours can be employed.

  The amount of (A) used as an organic coagulant (P) when added to sludge or wastewater varies depending on the type of sludge or wastewater, the content of suspended particles, etc., but evaporation residue in wastewater and sludge Based on the weight of the product (hereinafter abbreviated as TS), from the viewpoint of the effect of improving the clarity of the filtrate and the coagulation performance, it is preferably 0.005 to 10%, more preferably 0.01 to 8%, and particularly preferably 0. 0.05 to 5%, most preferably 0.1 to 2%.

(P) can be used in combination with a coagulant (C) other than (P) if necessary as long as it does not impair the effects of the present invention when applied to sludge or wastewater. Examples of the coagulant include a known inorganic coagulant (C1) and a known organic coagulant (C2).
Examples of the known inorganic coagulant (C1) include sulfuric acid band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime.
Examples of the known organic coagulant (C2) include aniline-formaldehyde polycondensate hydrochloride, polyvinylbenzyltrimethylammonium chloride, dimethyldi (meth) allylammonium chloride, (di) (meth) allylaminemaleic acid copolymer, Examples thereof include di) (meth) allylamine citraconic acid copolymer, (di) (meth) allylamine itaconic acid, and (di) (meth) allylamine fumaric acid copolymer.
These known inorganic and organic coagulants may be used alone or in combination of two or more, or both may be used in combination.

  In the case of a known organic coagulant, the amount of the known coagulant (C) is based on the TS in the sludge or wastewater from the viewpoint of the coagulation property during sludge or wastewater treatment and the effect of improving the clarification of the filtrate. Preferably it is 0.01 to 10%, More preferably, it is 0.05 to 8%, Especially preferably, it is 0.1 to 5%, Most preferably, it is 0.2 to 2%. In the case of a known inorganic coagulant from the same viewpoint, it is preferably 0.1 to 10%, more preferably 0.5 to 9%, particularly preferably 1 to 8%, most preferably, based on TS in sludge or wastewater. Preferably it is 2 to 7%.

  When the known coagulant (C) is used in combination, it is preliminarily mixed with the organic coagulant (P) of the present invention and applied to sludge or waste water, or (P) and the known coagulant are separately used. Any method of applying to sludge or wastewater in any order may be adopted.

The organic coagulant (P) of the present invention comprises an antifoaming agent, a chelating agent, a pH adjuster, an antioxidant, an ultraviolet absorber and an antiseptic as long as it does not inhibit the effects of the present invention. One or more additives selected from the group can be used in combination.
Among these additives, additives other than the antiblocking agent may be preliminarily contained in the aqueous monomer solution before the production of (A) as long as the effects of the present invention are not impaired.

Based on the weight of (A), the total amount of the above additives is usually 50% or less, preferably 1 to 40%, more preferably 2 to 30% from the viewpoint of the addition effect and the setting performance.
About the usage-amount of each additive, based on the same weight as the above, normally, an antifoamer is 5% or less, a chelating agent is 30% or less, a pH adjuster is 10% or less, surfactant and blocking prevention Each of the agents is 5% or less, each of the antioxidant, the ultraviolet absorber and the preservative is 5% or less; preferably from the same viewpoint as described above, the antifoaming agent is 1 to 3%, the chelating agent is 2 to 10%, The pH adjuster is 1 to 5%, the surfactant and the antiblocking agent are 1 to 3%, respectively, and the antioxidant, the ultraviolet absorber and the preservative are 0.1 to 2%.

  Organic coagulant (P) is sludge (wastewater from various factories such as paper pulp, dyeing, automobiles, metal processing, iron making, food, gravel collection, semiconductor-related and cleaning industries) and sewage ( By adding it to organic sludge or inorganic sludge), it exhibits a unique condensation effect, an effect of improving the clarification of the filtrate (COD reduction, decolorization), a cake generation amount, and a cake moisture content.

[Polymer flocculant (Q)]
The polymer flocculant (Q) in the present invention is a water-soluble (co) polymer having a structural unit of at least one selected from the group consisting of the monomers (a1), (a2), (a3) and (a4). B).

In the (co) polymer (B), the divalent unsaturated monomer (b) is preferably 0.1 based on the total monomers from the viewpoint of aggregation performance and water solubility of the water-soluble (co) polymer (B). It is not more than mol%, more preferably 0.00001 to 0.06 mol%, particularly preferably 0.00001 to 0.006 mol%.
As the monomers (a1) to (a4) and the water-insoluble monomer (x) constituting (B), those used for the (co) polymer (A) can be mentioned, and preferred ones are also the same.

  In addition to the water-soluble monomers (a1) to (a4) and the water-insoluble monomer (x), the monomer constituting the component (B) may be a known crosslinking other than the component (b) as long as the effects of the present invention are not impaired. The monomer (y) may be used in combination.

When the molecular weight of (B) is expressed in terms of intrinsic viscosity [η] (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, the lower limit is usually 3.1, and the aggregation performance (especially increases in floc particle size) In view of the above, preferably 4, more preferably 4.8, particularly preferably 5.4, most preferably 6, the upper limit is usually 40, preferably 30 from the viewpoint of agglomeration performance (especially improvement of floc strength), more preferably 20, particularly preferably 15, and most preferably 12.

  The water-soluble (co) polymer (B) includes a cationic water-soluble (co) polymer (B1), an amphoteric water-soluble (co) polymer (B2), and an anionic water-soluble (co) polymer (B3). And a nonionic water-soluble (co) polymer (B4).

The cationic water-soluble (co) polymer (B1) has the cationic monomer (a1) and / or (a2) as an essential constituent unit, and if necessary, the nonionic monomer (a3) and / or the monomer (x), ( It is a (co) polymer further containing y) as a structural unit, and is a (co) polymer that exhibits cationic properties when dissolved in water.
From the viewpoint of charge neutralization on the sludge particle surface, the total of (a1) and (a2) is preferably 40% or more, based on the total mole number of unsaturated monomers constituting (B1). More preferably, it is 60 to 100%, (a3) is preferably 60% or less, more preferably 0 to 40%.

The amphoteric water-soluble (co) polymer (B2) comprises the cationic monomer (a1) and / or (a2) and the anionic monomer (a4) as essential constituent units, and a nonionic monomer (a3) as necessary. It is a copolymer further containing monomers (x) and (y) as structural units.
The molar ratio (mol%) based on the total number of moles of unsaturated monomers constituting (B2) is preferably 5 to 90%, more preferably 10 from the viewpoint of aggregation performance. -80%, (a3) is preferably 5-90%, more preferably 10-80%, and (a4) is preferably 5-50%, more preferably 10-40%.

Among (B), the anionic water-soluble (co) polymer (B3) comprises the anionic monomer (a4) as an essential constituent unit, and if necessary, the nonionic monomer (a3) and / or the monomer (x), ( It is a polymer further containing y) as a structural unit, and is a polymer that exhibits anionic properties when dissolved in water.
From the viewpoint of aggregation performance, (a4) is preferably 70% or more, more preferably 80 to 100%, (a3) based on the total mole number of unsaturated monomers constituting (B3). Is preferably 30% or less, more preferably 0 to 20%.

  The nonionic water-soluble (co) polymer (B4) is a copolymer containing the nonionic monomer (a3) as an essential constituent unit and further containing monomers (x) and (y) as constituent units as necessary. .

  Of the above (co) polymer (B), from the viewpoint of the coagulation performance and coagulation performance of the coagulation and coagulation treatment agent (Z) described below, the cationic (co) polymer (B1) and the amphoteric (co) are preferred. It is a polymer (B2).

As a method of adding the polymer flocculant (Q), (Q) may be added as it is, but from the viewpoint of uniform mixing, the method of adding (Q) to an aqueous solution and then adding it to sludge or wastewater is preferable. is there.
When (Q) is used as an aqueous solution, the concentration (% by weight) of (Q) is preferably 0.05 to 1%, more preferably 0.1 to 0.5% from the viewpoints of cohesiveness and industry. is there.
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 (P). In particular, when the powdery polymer flocculant (Q) is dissolved in water, adding (Q) at a time is not preferable because it causes the formation of dents and makes it difficult to dissolve in water.

  The production method of (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. Among these, aqueous solution polymerization, reverse phase suspension polymerization and reverse phase emulsion polymerization are preferable from an industrial viewpoint, and aqueous solution polymerization and reverse phase suspension polymerization are more preferable.

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

Moreover, you may use a chain transfer agent (e) as needed. As the chain transfer agent (e), those listed in (A) can be used.
In the case of using the chain transfer agent (e), the preferable lower limit is 0.0001% based on the total weight of the monomers, more preferably 0.001%, from the viewpoint of obtaining the optimum molecular weight as (B). 0005%, particularly preferably 0.001%, most preferably 0.005%, the preferred 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.

  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 the predetermined temperature constant (for example, the predetermined polymerization temperature ± 5 ° C.), or may not be adjusted. Moreover, you may carry out adiabatic polymerization in a heat insulation container etc. 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 pH of the aqueous monomer solution during polymerization is the same as in the case of (A), and preferred conditions are also the same.

  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.

[Coagulation and flocculation agent (Z) for sludge or wastewater treatment]
The coagulation and flocculation agent (Z) for sludge or waste water of the present invention is a combination of the organic coagulant (P) and the polymer coagulant (Q).
An organic sludge such as sewage or an inorganic sludge such as factory wastewater or a wastewater treatment method using the coagulation and agglomeration treatment agent (Z) of the present invention includes sludge or wastewater and agglomeration and agglomeration for sludge or wastewater treatment. There is no particular limitation as long as the processing agent (Z) is mixed to form a floc and is subjected to solid-liquid separation.
Examples of the method for treating sludge or wastewater using the treating agent (Z) include the following (1) and (2).
(1) First, sludge or waste water and an organic coagulant (P) are mixed and coagulated, and further, a polymer flocculant (Q) is added and mixed to coagulate to form flocs. A processing agent (Z) for the purpose of liquid separation.
(2) The organic coagulant (P) and the polymer flocculant (Q) are dissolved and mixed in advance, and then mixed with sludge or waste water to coagulate and coagulate to form flocs, and then solid-liquid separation is performed. Treatment agent (Z) for the purpose;
Of the above-mentioned treatment methods, the method (1) is preferable from the viewpoint of exhibiting the coagulation and aggregation performance (for example, increasing the floc particle size and reducing the moisture content of the dehydrated cake).

  In the method of (1), as a method of adding the organic coagulant (P) to sludge or wastewater, from the viewpoint of uniform mixing, (P) is made into a dilute aqueous solution and then added to sludge or wastewater and sufficiently stirred. However, (P) may be added to the waste water as it is and stirred and mixed. When (P) is used as a dilute aqueous solution, the concentration of (P) is preferably 0.02 to 10% by weight, more preferably 0.2 to 2.0% by weight.

  In the method (1), (Q) is not particularly limited as a method for adding (Q) to the sludge or wastewater treated with the organic coagulant (P) of the present invention, and (Q) is directly added to the sludge or wastewater. However, from the viewpoint of uniform mixing, a method of adding (Q) to an aqueous solution and adding it to the sludge or wastewater is preferable. The concentration of (Q) when (Q) is used as an aqueous solution is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight.

  Further, the method for adding the coagulation and flocculation agent (Z) of the present invention to the sludge or waste water in the method (2) is not particularly limited, and (Z) may be added to the waste water as it is, but it is uniform. Preferred from the viewpoint of mixing is a method in which (Z) is made into an aqueous solution and then added to sludge or waste water. When (Z) is used as an aqueous solution, the concentration of (Z) is preferably 0.1 to 6.0% by weight, more preferably 0.15 to 2% by weight.

  In both of the above (1) and (2), the ratio of (P) based on the total weight of (P) and (Q) is preferably from the viewpoint of the coagulation performance and coagulation performance of the coagulation and aggregation treatment agent (Z). It is 0.2 to 90%, more preferably 2 to 80%, particularly preferably 10 to 75%, and most preferably 20 to 65%.

  The use amount of the coagulation and flocculation treatment agent (Z) of the present invention varies depending on the type of sludge or waste water, the content of suspended particles, the molecular weight of the coagulation and flocculation treatment agent (Z), etc., but is not particularly limited. Or, based on TS in wastewater, usually 0.01 to 10%, and the preferable lower limit from the viewpoint of aggregation performance is 0.1%, more preferably 0.5%, particularly preferably 1%, preferable from the viewpoint of treatment efficiency The upper limit is 5%, more preferably 3%, particularly preferably 2%.

  The coagulation and flocculation agent (Z) of the present invention is an antifoaming agent, a chelating agent, a pH adjuster, a surfactant, an antiblocking agent, an antioxidant, as long as it does not inhibit the effects of the present invention. An additive selected from the group consisting of ultraviolet absorbers and preservatives 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); C6-12 aminocarboxylic acids (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid and triethylenetetraminehexaacetic acid), polyvalent carboxylic acids [for example, maleic acid, polyacrylic acid (Mn1,000- 10,000) and isoamylene-maleic acid copolymers (Mn 1,000-10,000)], C3-10 hydroxycarboxylic acids (eg citric acid, gluconic acid, lactic acid and malic acid), condensed phosphoric acid (eg Repolyphosphoric acid and trimetaphosphoric acid) and their salts [e.g. alkali metal (e.g. sodium and potassium) salts, alkaline earth metal (e.g. calcium and magnesium) salts, ammonium salts, C1-20 alkylamines (e.g. methylamine, ethylamine and Octylamine) salts and C2-12 alkanolamine (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)] ;

  Examples of the surfactant include surfactants described in US Pat. No. 4,331,447, such as polyoxyethylene nonylphenol ether and sodium dioctylsulfosuccinate]; as an anti-blocking agent, polyether-modified silicone oil such as polyethylene oxide-modified silicone 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 (P) and / or the polymer flocculant (Q), or by mixing the organic coagulant (P) and the polymer flocculant (Q). The coagulation and aggregation treatment agent (Z) may be added after addition. 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 the weight of the organic coagulant (P) and / or (Q) when the additive is contained in the organic coagulant (P) and / or (Q) or (Z). Z) based on the weight of the monomer and when it is previously contained in the monomer aqueous solution, usually 30% or less based on the monomer weight, preferably 0 to 10% from the viewpoint of the effect of the present invention (condensation performance or aggregation performance) It is.
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%.

  The coagulation and flocculation treatment agent (Z) of the present invention may be in any known form such as powder (for example, crushed, true sphere and kitchen), film, aqueous solution, w / o emulsion and suspension. It's okay.

  Examples of the dehydration method (solid-liquid separation method) of floc sludge or wastewater formed by the above coagulation and coagulation treatment agent (Z) treatment method include gravity sedimentation, membrane filtration, column filtration, pressurized flotation, and concentration. Examples include a method using an apparatus (for example, thickener) and a dehydrating apparatus (for example, centrifugal dehydrator, belt press dehydrator, filter press dehydrator, screw press dehydrator, and capillary dehydrator). Among these, from the viewpoint of high floc strength which is the specific aggregating performance of the polymer flocculant of the present invention, a dehydrator, particularly a centrifugal dehydrator, a belt press dehydrator, a screw press dehydrator, and a filter press dehydrator is preferred. It is a method using.

  Other uses of the organic coagulant (P) or coagulation and flocculation treatment agent (Z) of the present invention include, for example, a flocculation agent for drilling and muddy water treatment, a papermaking agent (for example, formation agent for paper industry, drainage step) Retention improver, drainage improver and paper strength enhancer), crude oil production additive (crude oil secondary and tertiary recovery additive), dispersant, scale inhibitor, coagulant, decolorizer, thickener, electrification Examples thereof include an inhibitor and a treating agent for fibers, among which a flocculant for excavation and muddy water treatment, a chemical for papermaking, 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. 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). In the following, Examples 9, 21, and 35 are Reference Examples 1 to 3, respectively.

The composition, symbols, etc. of the raw materials used in the examples and comparative examples are as follows.
(1) Water-soluble cationic monomer (a1-1): 80% aqueous solution of aminoethyl methacrylate methanesulfonate (a1-2): 80% aqueous solution of aminoethyl methacrylate sulfate (a2-1): N, N- Methyl chloride salt of dimethylaminoethyl methacrylate
78.3% aqueous solution of (a2-2): methyl chloride salt of N, N-dimethylaminoethyl acrylate
80% aqueous solution

(2) Water-soluble monomers other than (a1) and (a2) (a3-1): 50% aqueous solution of acrylamide (a4-1): 80% aqueous solution of acrylic acid

(3) Divalent unsaturated monomer (b-1): 0.5% aqueous solution of methacryloylaminoethyl methacrylate (b-2): 0.6% aqueous solution of ethylene glycol dimethacrylate

(4) Radical polymerization initiator (d)
(D-1): Azobisamidinopropane hydrochloride [manufactured by Wako Pure Chemical Industries, Ltd.
10% aqueous solution of “V-50”, 10 hour half-life temperature: 56 ° C.] (d-2): 1% aqueous solution of hydrogen peroxide (d-3): 1% aqueous solution of ascorbic acid (d-4) : 1% aqueous solution of iron (II) sulfate

(5) Chain transfer agent (e)
(E-1): 10% aqueous solution of sodium hypophosphite

(6) Inorganic coagulant (C1-1): polyaluminum chloride (aluminum oxide 10-11% product) [trade name
"Poly aluminum chloride", manufactured by Taki Chemical Co., Ltd.]

  Evaluation of the organic coagulant (P), the coagulant and coagulant (Z) for sludge or waste water in the examples was performed according to the following method.

Evaluation [1] [Evaluation method of organic coagulant (P)]
(1) Supernatant liquid clarity (%)
Jar tester [model “JMD-6HS-A”, manufactured by Miyamoto Riken Kogyo Co., Ltd., and so on. Assembling a stirring device in which two plate-like stirring blades made of polyvinyl chloride (horizontal 5 cm, height 2 cm, thickness 0.2 cm) are continuously attached so as to form a cross (radius 2.5 cm). Next, 200 g of waste water is put into a 500 ml beaker and set in the stirring device. While stirring the jar tester at 300 rpm, a predetermined amount of 0.2% aqueous coagulant solution is added all at once and stirred for 30 seconds. After 10 minutes, the supernatant liquid was spectrophotometer [UV-1200, manufactured by Shimadzu Corporation, the same shall apply hereinafter. ] To measure the transmittance at wavelengths of 590 nm and 700 nm, and evaluate the filtrate clarity. The transmittance (%) indicates a value when the transmittance of ion-exchanged water is 100%.
(2) Coagulation (%)
After the evaluations [1] and (1) above, the measurement solution is returned to the beaker, and then the treated wastewater is centrifuged at 2,000 rpm for 10 minutes using a centrifuge [model LC06, manufactured by Tommy Seiko Co., Ltd.]. Measure the sedimentation sludge (lower layer) volume% with respect to the total wastewater volume and evaluate the setting. It shows that it is excellent in setting property, so that this volume% is small.
(3) Decolorization of supernatant after centrifugation (%)
About the supernatant liquid after centrifugation of said (2), the transmittance | permeability in wavelength 430nm and 700nm is measured with a spectrophotometer, and decoloring property is evaluated. In addition, the numerical value (%) of the transmittance indicates a value when the transmittance of ion-exchanged water is 100%.
(4) COD (mg / L) of supernatant after centrifugation
The supernatant liquid after centrifugation of (2) above is measured according to the COD _Mn analysis method described in JIS K-0102.

Evaluation [2] [Evaluation Method of Coagulation and Aggregation Treatment Agent (Z) for Sludge or Wastewater Treatment]
(1) Flock particle size (mm)
200 g of sludge or waste water is put into a 300 ml beaker and set in the same stirring device as the above evaluation [1] (1). The rotation speed of the jar tester is set to 300 rpm, and an aqueous solution of an organic coagulant with a predetermined concentration and an aqueous solution of a polymer flocculant with a predetermined concentration are added by a predetermined method while gradually stirring sludge or waste water, and stirred for 30 seconds. Then, stirring was stopped and the particle size (mm) of the formed floc was visually observed.

(2) Sludge volume ratio (%)
T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, 500 ml graduated cylinder was set, and all of the treated water after the above floc particle size test was added at once. Filter. The amount of sludge obtained by filtration is measured, and the volume ratio (%) with respect to the total wastewater volume is calculated to obtain the sludge volume ratio.

(3) Filtrate COD (mg / L)
About the filtrate after filtration of said (2), it measures with the analysis method of said evaluation [1] (4).
(4) Filtrate clarity (%)
About the filtrate after the filtration of said (2), it evaluates using the spectrophotometer of said evaluation [1] (1).
(5) Cake moisture content (%)
Part of the sludge obtained by filtration in the above (2) is taken out with a spatula and dehydrated using a press filter tester (pressure condition 2 kgf / cm ² , 60 seconds). About 3 g of the dehydrated cake was weighed in a petri dish (W3) and dried in a circulating air drier until the water was completely evaporated (for example, at 105 ± 5 ° C. for 8 hours), and then remained on the petri dish. Taking the weight of the dry cake as (W4), the moisture content of the cake is calculated from the following equation.

Cake moisture content (% by weight) = [(W3) − (W4)] × 100 / (W3)

Example 1 [Production of organic coagulant (P-1)] (solution dropping polymerization)
A reaction vessel was charged with 500 parts of ion-exchanged water [aqueous phase (2)] adjusted to pH = 1.9 with sulfamic acid in advance, and heated to 70 ° C. with stirring. In a separate container, according to Table 1, the monomer (a1-1), divalent unsaturated monomer (b1-1), chain transfer agent (e-1), radical polymerization initiator (d-1), and ion-exchanged water Were mixed and stirred until a homogeneous solution was obtained to prepare a monomer solution [drip solution]. Under stirring, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 1.9 using sulfamic acid while monitoring with a pH meter [ Aqueous phase (1)]. The monomer solution was transferred to a dropping funnel, and at a solution temperature of 20 ° C., nitrogen (purity 99.999% or more; the same applies hereinafter) was passed through the system to sufficiently replace it (gas phase oxygen concentration was about 2 L / min). 10 ppm).
Next, the monomer solution is removed from the dropping funnel while refluxing and stirring in a reaction vessel (gas phase oxygen concentration of about 10 ppm) adjusted to 67 to 73 ° C. with nitrogen flowing into the reaction vessel system (5 L / min). It was dripped over 2 hours. After dropping, the mixture is aged at the same temperature for 3 hours to complete the polymerization, and an aqueous solution (concentration 30.5%) 980 of the organic coagulant (P-1) containing the water-soluble (co) polymer (A-1). Got a part.

Examples 2 to 12, Comparative Example 1
[Production of organic coagulants (P-2) to (P-12) and (ratio P-1)] (solution dropping polymerization)
Each organic coagulant was obtained in the same manner as in Example 1 except that the monomer aqueous solution blending composition (parts) was changed based on Table 1 in Example 1. The results are shown in Table 1.

Production Example 1
[Production of polymer flocculant (Q-1)] (aqueous solution polymerization)
According to Table 1, an aqueous monomer solution containing the monomer (a1-1), buffer, chain transfer agent (e-1) and ion-exchanged water was mixed and stirred in the reaction vessel until the system became a homogeneous solution. Under stirring, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 2.0 using sulfuric acid while monitoring with a pH meter.
Next, the solution temperature in the reaction vessel was adjusted to 0 ° C. in a constant temperature water bath at 0 ° C., and the system was sufficiently substituted with nitrogen (gas phase oxygen concentration of about 10 ppm). Thereafter, radical polymerization initiators (d-1) to (d-4) are sequentially charged into the reaction vessel using a syringe, polymerization is started at a solution temperature of 0 ° C., and the solution temperature is increased by heat generated by the polymerization, When the temperature of the solution reached 80 ° C., the reaction vessel was placed in a constant temperature bath at 80 ° C. and kept warm for 10 hours to complete the polymerization. During the polymerization, the content became highly viscous and stirring became difficult, so stirring was stopped halfway.
Thereafter, the obtained hydrogel was taken out, mixed and kneaded by a meat chopper machine [model number “12VR-400K”, manufactured by ROYAL Co., Ltd., mesh opening 6 mm], and further minced into 80 ° C. After drying with hot air for 2 hours, the mixture was pulverized with a juicer mixer to obtain 990 parts of a polymer flocculant (Q-1) containing the water-soluble (co) polymer (B-1) (yield 99%). , Solid content 92%). The results are shown in Table 1.

Production Examples 2 and 3
[Production of polymer flocculants (Q-2) and (Q-3)] (aqueous solution polymerization)
In Production Example 1, each polymer flocculant was obtained in the same manner as in Production Example 1 except that the composition of the aqueous monomer solution and the monomer concentration in the aqueous monomer solution were changed based on Table 1. The results are shown in Table 1.

Examples 13 to 24, Comparative Example 2
[Performance evaluation of organic coagulant (P)]
Each of the obtained organic coagulants was dissolved in ion exchange water to obtain an aqueous solution having a solid content of 0.2%. Wastewater collected from M dyeing factory [pH 5.2, TS 0.09% COD _Mn 1,334 mg / L. same as below. Each 200 g was taken into a 500 mL beaker, 0.4 part of each aqueous solution of the above organic coagulant (solid content added at this time 0.50% / TS), and further each with an inorganic coagulant (C1-1). 0.08 parts (the solid addition amount at this time 50% / TS) was added, stirred at 300 rpm for 30 seconds, treated with waste water, and evaluated by the method of the evaluation [1]. The results are shown in Table 2.

  From Table 2, it can be seen that the organic coagulant (P) of the present invention is superior in all of the supernatant liquid clarity, coagulability, supernatant liquid decolorization and supernatant liquid COD compared to the comparative one.

Examples 25-38, Comparative Example 3
[Performance evaluation of coagulation and coagulation agent (Z) for sludge or waste water]
Organic coagulants (P-1) to (P-12), (ratio P-1), and polymer flocculants (Q-1) to (Q-3) are each dissolved in ion-exchanged water to obtain a solid content. A 0.2% aqueous solution was obtained.
Digested sludge [pH 7.5, TS 2.9%, SS 2.6%, organic content 65%, alkalinity 1,542 mg-CaCO ₃ / L] 200 g each from a digested A City treatment plant, 500 mL beakers Then, 1.75 parts of (C1-1) (solid addition amount 30% / TS at this time) was added and stirred at 300 rpm for 30 seconds.
Next, as shown in Table 3, 2.9 parts of each aqueous solution of the organic coagulant (solid content addition amount 0.1% / TS at this time) was added, and each was stirred at 300 rpm for 30 seconds.
Furthermore, in Examples 25-32, 35-38 and Comparative Example 3, an aqueous solution of a polymer flocculant (Q-1), an aqueous solution of a polymer flocculant (Q-2) in Example 33, and in Example 34, 29 parts of each of the polymer flocculants (Q-3) were added (solid content addition amount at this time: 1.00% / TS), and the performance was evaluated by the method of the evaluation [2]. The results are shown in Table 3.

Example 39
[Performance evaluation of coagulation and coagulation treatment agent (Z-11) for sludge or waste water]
50 parts of an aqueous solution of an organic coagulant (P-2) adjusted to a solid content concentration of 0.2% with ion-exchanged water, and a polymer flocculant (Q-1 adjusted to a solid content concentration of 0.2% with ion-exchanged water) ) Was measured in a beaker and mixed well for 10 minutes using a jar tester to obtain a coagulation and aggregation treatment agent (Z-11).
(C1-1) 31.9 parts of an aqueous solution of (Z-11) was added to the sludge after addition and stirring (C1-1) treated in the same manner as in Examples 25 to 38 and Comparative Example 3. (Solid content addition amount 1 at this time .1% / TS), and the performance was evaluated by the method of the evaluation [2]. The results are shown in Table 3.

  From Table 3, the coagulation and flocculation treatment agent (Z) for sludge or waste water of the present invention is excellent in floc particle diameter, filtrate COD and clarification, and has a small sludge volume fraction and cake water content, compared with the comparative one. Since the rate is low, it can be seen that the coagulation and aggregation performance is excellent.

  The organic coagulant (P), the coagulation and coagulation agent (Z) for sludge or wastewater treatment of the present invention is for sludge dewatering treatment, COD reduction treatment of wastewater such as paper mill wastewater, and for decolorizing colored components. In addition to being used, it can be used in a wide range of applications such as dye fixing agents, papermaking chemicals (for example, paper industry formation forming aids, drainage yield improvers, drainage improvers, and paper strength enhancers). Useful.

Claims (7)

An unsaturated monomer (a) containing a water-soluble cationic monomer (a1) represented by the following general formula (1) and a divalent unsaturated monomer (b) represented by the following general formula (2) Water-soluble (co) polymer (A), and based on the unsaturated monomer (a), the monomer (a1) is 50 mol% or more, and the monomer (b) is 0. Organic coagulant (P) which is 00001 to 0.5 mol%

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

[ Wherein R ¹ is CH ₃ ; R ^{2 to} R ⁴ are H; X ¹ is O ; Q is an ethylene group ; Z ⁻ is at least one proton selected from the group consisting of hydrochloric acid, sulfuric acid and methanesulfonic acid. It represents a residue excluding H ⁺ of the acid . ]

_{^{CH 2 = CR 5 -CO-OCH}} 2 CH 2 -X 2 -CO-CR 6 = CH 2 (2)

[Wherein R ⁵ and R ⁶ are methyl groups; X ² represents NH. ] The organic coagulant according to claim 1, wherein the water-soluble (co) polymer (A) satisfies the following relational expression.

10 ≦ Vw / [η] ≦ 50

[In the formula, Vw represents the viscosity (mPa · s, 25 ° C.) of a 1 wt% aqueous solution, and [η] represents the intrinsic viscosity. ] Coagulation and agglomeration for sludge or waste water comprising a combination of the organic coagulant (P) according to claim 1 or 2 and a polymer flocculant (Q) containing a water-soluble (co) polymer (B). Treatment agent (Z). Water-soluble (co) polymer (B) is a cationic (co) polymer (B1) and / or amphoteric (co) flocculation and aggregation treatment for the sludge or waste water of the polymer (B2) is a third aspect Agent. A method for treating sludge or wastewater, comprising mixing the sludge or wastewater with the organic coagulant (P) according to claim 1 or 2 . A method for treating sludge or wastewater, comprising mixing sludge or wastewater with the coagulation and agglomeration treatment agent (Z) according to claim 3 or 4 to form flocs and solid-liquid separation. The organic coagulant (P) according to claim 1 or 2 and sludge or waste water are mixed, and then the polymer flocculant (Q) is further mixed to form a floc and solid-liquid separation. To treat sludge or wastewater.