JP2005034839A - Polymer flocculant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer flocculant having superior functions to provide high floc strength, increase a floc particle size, reduce the water content of dewatering cake, and the like. <P>SOLUTION: The polymer flocculant comprises a (co)polymer (A1) having a monomer (a) represented by general formula (1) as an essential component and a water-soluble polymer (B1) other than (A1), which (B1) is prepared by polymerization of monomers (b) in the presence of (A1). General formula (1) is (CH<SB>2</SB>=CR<SP>1</SP>-CH<SB>2</SB>)<SB>2</SB>N<SP>+</SP>R<SP>2</SP>R<SP>3</SP>Z<SP>-</SP>, wherein R<SP>1</SP>is H or methyl group; R<SP>2</SP>and R<SP>3</SP>are independently H, (meth)allyl group, 1 to 16C alkyl group, or 2 to 4C hydroxyalkyl group; Z<SP>-</SP>is a counter anion. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer flocculant used for treating organic or inorganic sludge or wastewater such as sewage or factory wastewater, and a method for treating sludge or wastewater using the polymer flocculant.

  Conventionally, as a polymer flocculant used for the dehydration of organic sludge generated by the treatment of sewage or inorganic sludge generated by the treatment of factory wastewater, a tertiary salt or quaternized salt polymer of diallylamine ( For example, see Patent Document 1), a copolymer of a tertiary or quaternized salt of diallylamine and a tertiary or quaternized salt of dialkylaminoethyl (meth) acrylate (for example, Patent Documents 2 and 3). Are known).

JP 56-18611 (first page) JP 51-37986 (first page) JP 63-242309 A (first page)

  However, with these polymer flocculants, the floc particle size produced is small and the drainage is poor, the water content of the solid-liquid separated cake is high, and the filter cloth when a belt press dehydrator or filter press dehydrator is used. It was difficult to obtain a sufficient dehydration effect such as poor sludge removability.

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 is obtained by polymerizing the copolymer (A1) having the monomer (a1) represented by the general formula (1) as an essential constituent unit and the monomer (b) in the presence of (A1). A polymer flocculant comprising a water-soluble polymer (B1) other than (A1)

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

[Wherein, R ¹ is H or methyl group; R ² and R ³ are each independently H, (meth) allyl group, alkyl group having 1 to 16 carbon atoms or hydroxyalkyl group having 2 to 4 carbon atoms; Z ⁻ Represents a counter anion. A polymer flocculent comprising the combination of (a) and a copolymer (A2) having sulfur dioxide as an essential constituent unit and another water-soluble polymer (B2); In a sludge or wastewater treatment method comprising a step of solid-liquid separation by adding and mixing to sludge or wastewater to form a floc; and a method for treating sludge or wastewater characterized by using the polymer flocculant; And (A2) is added to and mixed with sludge or waste water, and then (B2) is further added and mixed to form a floc, followed by solid-liquid separation. is there.

The polymer flocculant of the present invention is extremely useful because of the following effects.
(1) By adding and mixing to sludge or wastewater, a strong and large particle size floc is formed.
(2) Since the flocs once formed are not easily broken or redispersed, there is no recontamination during agglomeration or dehydration, and the stability and processing speed of the agglomeration or dehydration can be significantly improved.
(3) Since the formed flocs are dense and the moisture content of the cake after dehydration is low, the amount of waste generated and the incineration costs can be greatly reduced.
(4) The COD of the filtrate generated during the dehydration step can be reduced and the colored components can be removed.

In the general formula (1), R ¹ represents H or a methyl group, and H is preferable from the viewpoint of aggregation performance described later. R ² and R ³ represent H, a (meth) allyl group, an alkyl group having 1 to 16 carbon atoms (hereinafter abbreviated as C) or a C2-4 hydroxyalkyl group [wherein the (meth) allyl group is allyl. Group and / or methallyl group, and the same description is used hereinafter]. When R ² or R ³ is an alkyl group, if C exceeds 16, the solubility in water becomes poor. When R ² or R ³ is a hydroxyalkyl group, it is not preferred that C is 1 or C exceeds 4 because it is difficult to obtain industrially.

Examples of the C1-16 alkyl group in R ² and R ³ include a methyl group, an ethyl group, an n- and i-propyl group, an n-, i-, sec- and t-butyl group, n-, i- , Sec- and t-amyl groups and lauryl groups. Examples of the C2-4 hydroxyalkyl group in R ² include CH ₂ CH ₂ OH, CH ₂ CH ₂ CH ₂ OH, and CH ₂ CH (CH ₂ OH) CH ₃ .
Preferred are hydroxyalkyl groups H and C2~4 of R ² and R ^3, more preferred H or CH ₂ CH ₂ CH ₂ OH, Particularly preferred are H and CH ₂ CH ₂ OH, most preferred are H.

Examples of Z ⁻ in the general formula (1) include the following anions.
Inorganic acids such as hydrohalic acids (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid sulfates 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 alcohols (C10-20) ethylene oxide (hereinafter abbreviated as EO) 1-60 mol adduct sulfate]

Sulfonic acids, eg C1-30 sulfonic acids [eg alkyl (C1-10) sulfonic acids (eg methylsulfonic acid and ethylsulfonic acid), alkylaryl (C7-30) sulfonic acids [alkylbenzenesulfonic acid, alkylphenolsulfonic acid and Alkyl naphthalenesulfonic 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) Alkyl sulfonic acids, alkyl diphenyl ether sulfonic acids and alkyl benzimidazole sulfonic acids]

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 (eg glucose-phosphate ester, glucoseamine phosphate ester, maltose-1-phosphate and sucrose phosphate) Esters) and glycerin phosphate (eg phosphatidic acid)

Phosphonic acids, eg 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 phosphonic acid) Higher alkyl (C10-30) phosphonic acids, phosphonic acids of higher fatty acid esters (C10-30), phosphonic acids of higher alcohol ethers (C10-30), alkylphosphonic acids of higher fatty acid amides (C10-30), alkyl diphenyl ethers Phosphonic acid and alkylbenzimidazolephosphonic acid]
Organic acids such as C1-30 carboxylic acids [eg formic acid, oxalic acid, acetic acid, propionic acid, maleic acid, fumaric acid and adipic acid]

Among these Z ⁻ , anion of sulfonic acid is preferable from the viewpoint of dehydration performance, and an anion of sulfuric acid, halogen (for example, Cl ⁻ and Br ⁻ ) and sulfuric acid ester (for example, alkyl and alkenyl sulfuric acid ester) is more preferable, particularly preferred are sulfuric, Cl ^-, anions of methyl sulphate and ethyl sulphate, and most preferred is Cl ^- is.

Examples of (a) include the following.
(A1) Primary or secondary amine salt containing two (meth) allyl groups (the counter anion is as exemplified above)
For example, a salt of a di (meth) allylamine and a di (meth) allylamine derivative [for example, N-methyldi (meth) allylamine, Nn-propyldi (meth) allylamine and N-β-hydroxyethyldi (meth) allylamine] (a2) A salt of a tertiary amine containing three (meth) allyl groups (the counter anion is as exemplified above)
For example, salt of tri (meth) allylamine (a3) quaternary ammonium salt containing two (meth) allyl groups (the counter anion is as exemplified above)
For example dialkyl [eg dimethyl, diethyl, di-n-propyl, methylethyl] diallylammonium salt

  Among these, di (meth) allylamine, N-methyldi (meth) allylamine, and trimethylamine are preferable from the viewpoint of agglomeration performance (improvement of floc strength, increase of floc particle size and reduction of moisture content of dehydrated cake, the same applies hereinafter). (Meth) allylamine hydrochloride and sulfate, and dimethyldiallylammonium salt, more preferred is di (meth) allylamine hydrochloride, and particularly preferred is diallylamine hydrochloride.

The lower limit of (a) based on the total amount of all monomers constituting (A1) or (A2) is preferably a lower limit of 50 mol% from the viewpoint of aggregation performance, more preferably 60 mol%, and an upper limit preferable from the viewpoint of aggregation performance. Is 99.9 mol%, more preferably 99 mol%, and when sulfur dioxide is introduced, the proportion is preferably 0.1 mol% from the viewpoint of increasing the molecular weight of (A2), The upper limit is preferably 1 mol%, and from the viewpoint of copolymerizability with (a), the upper limit is preferably 50 mol%, more preferably 45 mol%.
The proportions of (a) and sulfur dioxide can be calculated by measuring the nitrogen content and sulfur content by elemental analysis, respectively.

  Among the structural units consisting of (a) in (A1) and (A2), those containing 2 or 3 (meth) allyl groups have a structural unit in a 5-membered or 6-membered ring structure during polymerization. It is generally known that it is easy to cyclize. When each (meth) allyl unit is polymerized independently without being cyclized, it tends to be a crosslinked structure, which adversely affects the solubility in water. Further, by taking the ring structure, the polymer chain becomes more rigid and hardly forms a string in an aqueous solution, so that it easily acts effectively with sludge. The proportion of the structural unit having a 5-membered or 6-membered ring structure among the structural units consisting of (a) is preferably 90 mol% or more, more preferably 95-100 mol, from the viewpoints of solubility in water and aggregation performance. %.

  The production method of (A1) and (A2) is not particularly limited, and various radical polymerization methods such as aqueous solution polymerization, solution polymerization, reverse phase suspension polymerization, photopolymerization, precipitation polymerization and reverse phase emulsion polymerization can be employed. . Among these, aqueous solution polymerization and photopolymerization are preferable from an industrial viewpoint.

  As the aqueous solution polymerization, for example, (a) and, if necessary, sulfur dioxide is dissolved in water (monomer concentration: 5 to 80% by weight), and then a polymerization initiator {for example, a water-soluble azo initiator [for example, azobisamidinopropane ( Salt) [eg 2,2′-azobis (2-methylpropionamidine) dihydrochloride], azobiscyanovaleric acid (salt) and 2,2′-azobis [2- (5-methyl-2-imidazoline-2) -Yl) propane] (salt)] and a water-soluble peroxide (eg hydrogen peroxide, peracetic acid, t-butyl peroxide) from 0.01 to 30%, based on the total weight of (a) and sulfur dioxide, Preferably, a method of adding 0.1 to 10% and polymerizing at 0 to 100 ° C. (for example, a method described in JP-B-62-2163) can be used.

As photopolymerization, for example, (a) or a method in which sulfur dioxide is blown into (a) to form a viscous solution and polymerized by irradiating with light having a wavelength of 300 to 500 nm (for example, JP-B 45- 37033) can be used.
In the case of (A2), as a method for introducing sulfur dioxide, a method in which the gas is blown into the system as a gas, a method in which the gas is dissolved in a polar solvent such as water or acetone, and a method in which sodium bisulfite is polymerized in the system are used. ) And can be used for polymerization as sulfur dioxide.

The molecular weights of the copolymers (A1) and (A2) are generally 0.01 (incremental viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution from the viewpoint of aggregation performance (aggregation rate, floc strength). Above, preferably 0.05 or more, more preferably 0.1 or more, usually 5 or less, preferably 3 or less, more preferably 2 or less.

When the monomer (b) described below is polymerized in the presence of (A1), the form of (A1) is not particularly limited, but an aqueous solution is preferable because of ease of polymerization.
When (A2) and (B2) described later are combined and applied to sludge or wastewater, (A2) is in any form such as powder, flakes, oil, paste, aqueous solution, emulsion or suspension But you can.

In the water-soluble polymer (B1) or (B2) in the present invention, one or two kinds selected from the monomer (b1) represented by the following general formula (2) and other water-soluble unsaturated monomers (b2) Those obtained by (co) polymerizing the above monomers are included.

^{_{CH 2 = CR 3 -CO-X}} -Q-N + R 4 R 5 R 6 · 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 ³ is H or a methyl group; R ⁴ , R ⁵ and R ⁶ are independent of each other] And H, an alkyl group having 1 to 16 carbon atoms or an aralkyl group; Z ⁻ represents a counter anion. ]

The alkylene group having 1 to 4 carbon atoms of Q includes methylene, ethylene, n- and i-propylene, 1,2-, 1,3- and 2,3-tylene groups and a tetramethylene group; carbon The hydroxyalkylene groups of formulas 2 to 4 include hydroxyethylene, 1- and 2-hydroxypropylene, 1-hydroxy-i-propylene, 1- and 2-hydroxytetramethylene, 2-hydroxymethylpropylene and 2-methyl-2. -Hydroxypropylene groups are included.
Examples of the alkyl group for R ⁴ , R ^5, and R ⁶ include those exemplified above for R ² , and examples of the aralkyl group include benzyl and phenylethyl groups. Z is the same as described above.

Examples of (b1) include the following and mixtures thereof.
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, such as methylaminoethyl (meth) acrylate, methylaminopropyl (meth) acrylate and aminoethyl (meth) acrylate] and tertiary amino group-containing (meth) acrylate [C7-20, eg dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate], inorganic acids (eg hydrohalic acids (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid) Salts, organic acids (C1-30, such as formic acid, Acetic acid, oxalic acid, propionic acid, maleic acid, fumaric acid and adipic acid) salts and their amines (salts) are quaternized with a quaternizing agent (for example, methyl chloride, dimethyl sulfate and benzyl chloride) to form a quaternary Ammonium salt

Amine salt of (meth) acrylamide type [when X in formula (2) is N] Primary amino group-containing (meth) acrylamide [eg 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-based amine salt in which X is O is preferable from the viewpoint of easy industrial production, and more preferably, R ⁴ and R ⁵ are both CH ₃ and Z is Cl or Dimethylaminoethyl (meth) acrylate hydrochloride or dimethylaminoethyl (meth) acrylate sulfate which is 1 / 2SO ₄ , and these amines (salts) are quaternized with a quaternizing agent (as described above) 4 It is a quaternary ammonium salt.

Other water-soluble unsaturated monomers (b2) include the following (b21) to (b23), and mixtures thereof.
(B21) Nonionic monomer The following, and mixtures thereof (b211) (meth) acrylate derivatives Molecular weight 40 to number average molecular weight (hereinafter abbreviated as Mn) 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 (B212) (Meth) acrylamide derivatives C3-30, for example on (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-methylol (meth) acrylamide (b213) Nitrogen-containing vinyl monomers C3~30 other than, for example acrylonitrile, N- vinylformamide, N- vinyl-2-pyrrolidone, vinylimidazole, N- vinyl succinimide and N- vinylcarbazole

(B22) Cationic monomer The following, these salts (for example, the inorganic acid, organic acid salt and quaternary ammonium salt), and mixtures thereof (b221) vinyl compounds having an amino group C2-30, for example, vinylamine, Compounds having vinylaniline, (meth) allylamine, di (meth) allylamine, p-aminostyrene, 2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine and vinylmorpholine (b222) amineimide 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) acrylate Ruimido

(B23) 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

(B231) unsaturated carboxylic acids monocarboxylic acids [C3-30, such as (meth) acrylic acid, vinylbenzoic acid and allylacetic acid] and poly (2-4) carboxylic acids [C4-30, such as (anhydrous) maleic acid, Fumaric acid and itaconic acid]

(B232) 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) acrylo Oxypropanesulfonic 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- Dimethylethanesulfone Acid and p- (meth) acryloylaminomethylbenzenesulfonic acid] and alkyl (C1-20) (meth) allylsulfosuccinic acid ester [for example, methyl (meth) allylsulfosuccinic acid ester]
(B233) (Meth) acryloyl polyoxyalkylene (C1-6) sulfate, for example, (meth) acryloyl polyoxyethylene (degree of polymerization 2-50) sulfate

  Among (b2), from the viewpoint of increasing the molecular weight of (B1) or (B2), (b211) and (b222) are more preferable, and (b212), (b213), (b231) and (b232) are more preferable. ), Particularly preferred are (meth) acrylamide, acrylonitrile, N-vinylformamide, (meth) acrylic acid, (anhydrous) maleic acid, itaconic acid and alkali metal salts thereof, 2- (meth) acryloyloxyethanesulfonic acid, 2 -(Meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid and alkali metal salts thereof.

In addition to the above (b1) and (b2), the monomer constituting the water-soluble polymer (B1) or (B2) is further used in combination with a water-insoluble monomer (b3) as long as it does not inhibit the effects of the present invention. May be.
(B3) includes the following (b31) to (b36) and mixtures thereof.
(B31) C4-23 (cyclo) alkyl (meth) acrylate [C1-20 aliphatic and alicyclic alcohol (meth) acrylate [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)] Acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate and cyclohexyl (meth) acrylate]
(B32) C4-20 epoxy group-containing (meth) acrylate [for example, glycidyl (meth) acrylate]

(B33) Poly (polymerization degree 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]]

(B34) C2-30 unsaturated hydrocarbon monomers [eg ethylene, nonene, styrene and 1-methylstyrene]
(B35) 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)
(B36) Halogen-containing monomer (C2-8, such as vinyl chloride)

  Based on the number of moles of all monomers constituting (B1) or (B2), the proportion of (b1) is preferably at least 10 mol%, more preferably at least 20 mol%, particularly preferably 30 from the viewpoint of cohesiveness. The proportion of (b2) is preferably 90 mol% or less, more preferably 80 mol% or less, particularly preferably 30 to 70 mol% from the same viewpoint, and the proportion of (b3) is ( From the viewpoint of the solubility of B1) or (B2) in water, it is preferably 40 mol% or less, more preferably 20 mol% or less, particularly preferably 0 to 10 mol%.

  Of the above (B1) or (B2), a polymer having the monomer (b1) as an essential constituent unit is preferable from the viewpoint of cohesiveness, and more preferable is a polymer in all monomers constituting (B1) or (B2). The proportion of (b1) is 10 mol% or more, particularly preferably 20 mol% or more, and most preferably 30 to 70 mol%.

The production method of (B1) and (B2) is not particularly limited, and for example, radical polymerization methods such as aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization, 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, for example, an aqueous monomer solution is placed in a container in which heat does not enter and exit from the outside, and adiabatic polymerization is performed (for example, Japanese Examined Patent Publication No. Sho 59-40843). Among them, a method of performing constant temperature polymerization (for example, JP-A No. 3-189000) can be used.

As the reverse phase suspension polymerization, for example, an aqueous solution of a water-soluble vinyl monomer is dispersed in a water-in-oil type polymerization using an oil-soluble polymer substance or a nonionic surfactant as a dispersion stabilizer (for example, JP-A-56-56). -53111).
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 ester (C6-100, for example, glyceryl monostearate) is mentioned.
The amount of the oil-soluble polymer substance used is usually 0.1% by weight based on the weight of the organic solvent used, preferably 0.2% by weight, more preferably 0.5% by weight, and the upper limit is usually 10%. % By weight, preferably 5% by weight, more preferably 3% by weight.
Examples of the dispersion medium (organic solvent) used include aliphatic hydrocarbons (C6-30, such as hexane, heptane and n-decane), alicyclic hydrocarbons (C6-30, such as cyclohexane and decalin), aromatics, and the like. Group hydrocarbons (C6-12, such as benzene, toluene and xylene) and the like.

Further, as the reverse phase emulsion polymerization, 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 Japanese Patent Laid-Open No. 9-208802). Publication) can be used.
Examples of the dispersion medium to be used include hydrocarbons [C6-30, such as paraffin (for example, n-paraffin and isoparaffin), mineral oil (for example, kerosene, light oil and medium oil), and synthetic oil) and mixtures thereof.
As the surfactant used for emulsification, known ones described in, for example, Japanese Patent No. 2676483 and Japanese Patent Application Laid-Open No. 9-208802 can be used, and among these, preferred from the viewpoint of emulsion stability. Are nonionic surfactants and combinations of nonionic surfactants with other ionic surfactants.

Nonionic surfactants include, for example, 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 polyester). Oxyethylene ethers and polyoxyethylene nonylphenyl ethers) and long chain alkyl alkanolamides such as N, N-dihydroxyethyllaurylamide.
The amount of these surfactants used is usually 0.05%, preferably 0.1%, more preferably 0.12%, and the upper limit is usually 1%, preferably 0, based on the weight of the dispersion medium. 0.5%, more preferably 0.25%.
In addition, when the water-in-oil emulsion is diluted with water and used, a phase inversion agent may be added to the water-in-oil emulsion in advance so that the water-in-oil emulsion is poured into water and phase inversion is performed quickly. 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 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 amount of the radical polymerization initiator used is the total weight of the water-soluble unsaturated monomer (b2) and the water-insoluble unsaturated monomer (b3) used as necessary from the viewpoint of obtaining an optimum molecular weight as the water-soluble polymer of the present invention. Is preferably 0.001%, more preferably 0.005%, particularly preferably 0.01%, most preferably 0.02%, and the preferred upper limit is 1%, more preferably 0.5%. Particularly preferred is 0.1%, and most preferred is 0.05%.

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 Glycols (molecular weight 100-50,000) and polyethylene polypropylene glycol (molecular weight 100-50,000)], compounds having one or more amino groups in the molecule [eg ammonia and amines (C1-30, eg methyl Amine, dimethylamine, triethylamine and propanolamine)] and compounds having one or more thiol groups in the molecule (described later).
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, mixtures thereof and salts thereof [alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts, Amine (C1-20) salts and inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts].
Monovalent thiol aliphatic mercaptan [C1-20, such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, hexadecyl mercaptan, n-octadecyl mercaptan, 2-mercaptoethanol, mercaptoacetic acid, 3 -Mercaptopropionic acid, thioacetic acid, 1-thioglycerol, monoethanolamine thioglycolate, thiomaleic acid, cysteine and 2-mercaptoethylamine], cycloaliphatic mercaptans (C5-20, eg cyclopentyl mercaptan and cyclohexyl mercaptan) and aromatics Mercaptans (C6-12, such as thiophenol, benzyl mercaptan, thiobenzoic acid and thiosalicylic acid).

Polyvalent thiols dithiols [aliphatic dithiols (C2-40, eg ethylenedithiol, diethylenedithiol, triethylenedithiol, propylenedithiol, 1,3- and 1,4-butanedithiol, 1,6-hexanedithiol and neopentyldithiol ), Alicyclic dithiols (C5-20, such as cyclopentanedithiol and cyclohexanedithiol) and aromatic dithiols (C6-16, such as benzenedithiol and biphenyldithiol), trithiols (C3-20, such as thioglycerin).

  From the viewpoint of obtaining an optimal molecular weight as the water-soluble polymer of the present invention, the amount used when using a chain transfer agent for radical polymerization is preferably 0.0001%, more preferably based on the total weight of monomers. 0.0005%, particularly preferably 0.001%, most preferably 0.005%, and a preferable upper limit is 10%, more preferably 5%, particularly preferably 3%, and most preferably 1%.

The lower limit of the monomer concentration in the aqueous monomer solution in radical polymerization is usually 20%, preferably 25%, more preferably 30%, particularly preferably 40%, most preferably 50, based on the total weight of the aqueous monomer solution in aqueous solution polymerization. %, The upper limit is usually 80%, preferably 75%, more preferably 70%, particularly preferably 65%, and most preferably 60%.
In reverse 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%, preferably 85%, more preferably. 80%, particularly preferably 78%, most preferably 75%.
In the inverse emulsion polymerization, the lower limit is usually 10%, preferably 20%, more preferably 30%, particularly preferably 40%, most preferably 55% or more, and the upper limit is usually 90%, preferably 80%, more preferably 75%, particularly preferably 70%, most preferably 65%.

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

  In aqueous solution polymerization, the lower limit is usually −10 ° C., preferably 0 ° C., more preferably 5 ° C., particularly preferably 10 ° C., most preferably 15 ° C., and the upper limit is usually 50 ° C., preferably 40 ° C. Preferably it is 30 ° C., particularly preferably 25 ° C., 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 lower limit of the polymerization temperature in the reverse phase suspension polymerization is usually 10 ° C or higher, preferably 20 ° C, more preferably 30 ° C, particularly preferably 40 ° C, most preferably 50 ° C, and the upper limit is usually 95 ° C, preferably 90 ° C. More preferably, it is 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 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., and the upper limit is usually 95 ° C., preferably 90 ° C. Preferably it is 80 degreeC, Especially preferably, it is 70 degreeC, Most preferably, it is 55 degreeC.
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 time can be confirmed to end when the exotherm is eliminated by polymerization, but from the viewpoint of completing the polymerization from 1 to 24 hours from the point of confirming the start of polymerization by normal exotherm, and reducing the residual monomer. , 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 referred to as 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 from the viewpoint of easy temperature control 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 during polymerization is not particularly limited, but is preferably 1 to 8, more preferably 2 to 7, particularly preferably 3 to 6. from the viewpoint of the polymerization rate and the solubility of the resulting water-soluble polymer. 5.
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 at room temperature (20 ° C.) for a stock solution of the monomer aqueous solution used in the polymerization.

  The water-soluble polymers (B1) and (B2) may be polymerized in advance by the above-described method and then polymer-modified. As the polymer modification reaction, for example, when a water-soluble unsaturated monomer (b2) 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 (b2) (the hydrolysis rate is about 1 to 60 mol% based on the total number of 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) ) (Eg methyl chloride and ethyl chloride) And a method of forming an amidine ring in the molecule by a ring-closing reaction between a nitrile group such as acrylonitrile and an amino group obtained by hydrolysis of vinylformamide (for example, JP-A-5-192513). Gazette).

  Moreover, when using 2 or more types of water-soluble polymer among (B1) or (B2), you may mix after superposing | polymerizing each beforehand, and superpose | polymerize one beforehand and add at the time of superposition | polymerization of the other. May be polymerized.

When the molecular weight of the water-soluble polymers (B1) and (B2) is expressed in terms of the intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N-NaNO ₃ aqueous solution, from the viewpoint of aggregation performance, From the viewpoint of increase in diameter), the lower limit is usually 1, preferably 1.5, more preferably 2, particularly preferably 4, most preferably 6, and from the viewpoint of agglomeration performance (especially improvement in floc strength), the upper limit is usually 40, preferably 30, more preferably 20, particularly preferably 15, and most preferably 12.

The polymer flocculant of the present invention includes those composed of (A1) and (B1), and those obtained by combining (A2) and (B2).
In the polymer flocculant comprising (A1) and (B1), the ratio of (A1) based on the total weight of (A1) and (B1), or the polymer flocculant obtained by combining (A2) and the above (B2) The ratio of (A2) based on the total weight of (A2) and (B2) is preferably 0.5 from the viewpoint of the flocculant performance and the effect of improving the clarity of the filtrate (for example, COD reduction and decolorization). %, Preferably 1%, more preferably 2%, particularly preferably 3%, most preferably 5%, from the viewpoint of flocculant performance, the preferred upper limit is 70% or less, preferably 60% or less, more preferably 50% Particularly preferably, it is 30%, most preferably 20%.

  (B1) in the present invention includes those obtained by polymerizing (b) in the presence of (A1), and (A1) partly or entirely grafted with (b). That is, (B1) includes the polymer (homopolymer) of (b) in addition to the graft polymer obtained by grafting (b) to (A1). Hereinafter, a mixture of (A1) and (B1) obtained by polymerizing (b) in the presence of (A1) is abbreviated as (AB1).

  In the method of polymerizing (b) in the presence of (A1), for example, (1) a method in which an aqueous solution of (A1) or (A1) and an aqueous solution of (b) are mixed in advance and then polymerized (2) ( A method in which the aqueous solution of (b) is dropped into the aqueous solution of A1) or (A1) and polymerized, and a method of polymerizing by dropping the aqueous solution of (A1) or (A1) in the aqueous solution of (3) and (b). included. Of these, the method (1) is preferable from the viewpoint of introducing a uniform graft structure into (A1) and exhibiting excellent coagulation performance, and more preferable is the aqueous solution (A1) and (b). This is a method in which an aqueous solution of is mixed in advance and polymerized.

Moreover, among the polymer flocculants formed by combining (A2) and (B2), the mixing method when mixing (A2) and (B2) is not particularly limited as long as (A2) and (B2) can be mixed. After (A2) and (B2) are obtained by polymerization, for example, a method of mixing using a stirrer such as a blender, and before (A2) or (B2) is produced, during production or after production (B2 ) Or (A2) is included.
Hereinafter, the products obtained by adding (B2) or (A2) before or during the production of (A2) or (B2) are abbreviated as (BA2) or (AB2), respectively.

  The polymer flocculant in the present invention is an antifoaming agent, a chelating agent, a pH adjuster, a surfactant, an antiblocking agent, an antioxidant, an ultraviolet absorber, and an antifoaming agent as necessary, as long as the effects of the present invention are not impaired. An additive selected from the group consisting of preservatives can be included.

Antifoaming agents include silicones (eg 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 carbonic acid) , And salts of these metals (eg, alkali metals and alkaline earth metals) (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, dioctylsulfosuccinate, etc.];
Anti-blocking agents include polyether-modified silicone oils such as polyethylene oxide-modified silicone and polyethylene oxide / polypropylene oxide-modified silicone;

  Antioxidants include phenols [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 , Sodium hypophosphite, triphenyl phosphite (TPP) and triisodecyl phosphite (TDP)] and nitrogenous compounds [amine systems such as octylated diphenylamine, Nn-butyl-p-aminophenol and N , N-diisopropyl-p-phenylenediamine), urea and guanidine (and the inorganic acid salt)];

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 any of (A1), (A2), (B1) and / or (B2), or (A2) and (B2) are mixed to form a polymer flocculant (C ) And may be added and contained. In addition, additives other than the anti-blocking agent are previously contained in the monomer aqueous solution before polymerization of (A1), (A2), (B1) and / or (B2) unless the effects of the present invention are impaired. You may let them.
When the additive is contained in (A1), (A2), (B1) and / or (B2) or (C), the amount of the additive used is (A1), (A2), (B1) and / Or based on the total weight of (B2) or the weight of (C), and when previously contained in the monomer aqueous solution, the antifoaming agent is usually 5% or less, preferably 1 to 3%, based on the monomer weight. The chelating agent is usually 30% or less, preferably 2 to 10%, the pH adjuster is usually 10% or less, preferably 1 to 5%, and the surfactant and the antiblocking agent are each usually 5% or less, preferably 1 Each of ˜3%, antioxidant, ultraviolet absorber and preservative is usually 5% or less, preferably 0.1 to 2%.

Since the polymer flocculant of the present invention exhibits an unprecedented specific flocculation effect and an effect of improving the clarity of the filtrate (for example, COD reduction and decolorization), sewage or human waste (hereinafter abbreviated as sewage) or factory wastewater. It can be used as a polymer flocculant for dehydration treatment of organic sludge or inorganic sludge generated by the above treatment, and is particularly suitably used for dehydration 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 cationic colloid equivalent of the cationic polymer flocculant based on the total weight of (A1) and (B1) or the total weight of (A2) and (B2) (meq / g) Is preferably 0.1 from the viewpoint of aggregation performance, more preferably 0.5, particularly preferably 1, most preferably 1.5, and from the same viewpoint, the preferable upper limit is 20, more preferably 12, especially. Preferably 8 and most preferably 6.
In addition, the cation colloid equivalent value (meq / g) in the amphoteric polymer flocculant of the present invention is preferably 1, preferably 1.5, particularly preferably 2, and a preferred upper limit from the same viewpoint as described above. 6, more preferably 5, particularly preferably 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 (1000 rpm), and melt | dissolves completely, and prepares a 0.2 weight% polymer flocculant solution. 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 method for treating organic sludge such as sewage or inorganic sludge such as factory wastewater or wastewater using the polymer flocculant of the present invention is (AB1) and / or copolymer (A2) and a water-soluble polymer. Any combination of (B2) may be added to sludge or wastewater and mixed to form a floc and solid-liquid separation is not particularly limited.
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 (AB1) and / or (AB2) is added to and mixed with sewage sludge or wastewater to form a floc, and solid-liquid separation is performed. (2) After (A2) is added to and mixed with sludge or wastewater. Further, (B2) is added and mixed to form a floc to perform solid-liquid separation, and (3) (A2) and (B2) are mixed in advance to obtain a polymer flocculant (C). (C) is added to and mixed with sewage sludge or wastewater to form flocs, and solid-liquid separation is performed. More preferable is the method (1) and (2), and particularly preferable is the method (1). is there.

In the method (2), as a method for adding (A2) to wastewater, from the viewpoint of uniform mixing, it is preferable to add (A2) to an aqueous solution and then add it to sewage sludge or wastewater and sufficiently stir ( A2) may be added to the waste water as it is and stirred and mixed. When (A2) is used as an aqueous solution, the concentration of (A2) is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight.
Although the dissolution method of (A2) and the dilution method after dissolution are not particularly limited, for example, a predetermined amount of (A2) is added while stirring water using a stirring device such as a jar tester for several hours. A method of stirring and dissolving (about 1 to 4 hours) can be employed.

  The amount of (A2) used in the method (2) varies depending on the type of sewage sludge or wastewater, the content of suspended particles, the molecular weight of (A2), etc., and is not particularly limited, but evaporation in wastewater Based on the weight of the residue (hereinafter abbreviated as TS), from the viewpoint of the effect of improving the clarity of the filtrate, the preferable lower limit is 0.01%, more preferably 0.05%, particularly preferably 0.1%, most preferably The upper limit is preferably 0.2%, and from the viewpoint of aggregation performance, the upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 2%.

  Moreover, when using (A2) for sludge or wastewater, you may use together 1 or more types of well-known inorganic coagulants and organic coagulants. When these are used in combination, either the method of previously adding to (A2) or the method of adding (A2) and the inorganic coagulant and / or organic coagulant separately to the sludge or waste water in random order is adopted. May be.

Examples of the inorganic coagulant include sulfate band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime.
Examples of organic coagulants include polycondensates of epihalohydrin and amine (or its hydrochloride, hereinafter abbreviated as hydrochloride), polycondensates of epihalohydrin and alkylenediamine (hydrochloride), polyethyleneimine (hydrochloride), alkyl, and the like. Range halide-alkylene polyamine polycondensate (hydrochloride), aniline-formaldehyde polycondensate (hydrochloride), polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine (hydrochloride), (di) methyldi (meth) allylammonium chloride and polyvinylimidazoline (Hydrochloride).
These inorganic coagulants and organic coagulants may be used singly or in combination, or both may be used in combination.

  When the coagulant is added to (A2) in advance, the amount of inorganic coagulant is usually 100% or less, preferably 5 to 50%, more preferably 10 to 30 based on the weight of (A2). %, The organic coagulant is usually 20 or less, preferably 1 to 10%, more preferably 2 to 5%.

  When inorganic coagulant and / or organic coagulant is added to waste water separately from (A2), the amount of inorganic coagulant and / or organic coagulant used is the type of sludge or waste water, the size of suspended particles Depending on the TS in the wastewater and the like, based on the TS in the wastewater, the inorganic coagulant preferably has a lower limit of 0.5%, more preferably 1%, particularly preferably 2% from the viewpoint of cohesiveness. From the viewpoint of the above, the preferable upper limit is 10%, more preferably 8%, particularly preferably 5%. For the organic coagulant, the preferable lower limit is 0.01%, more preferably 0.05%, particularly from the viewpoint of cohesiveness. The upper limit is preferably 0.1%, and from the same viewpoint, the upper limit is preferably 5% or less, more preferably 3% or less, and particularly preferably 1%.

In the method (2), (B2) is not particularly limited as a method for adding to the sludge or wastewater treated in (A2), and (B2) may be added to the sludge or wastewater as it is. From the viewpoint of uniform mixing, a method of adding (B2) to the sludge or waste water after making it into an aqueous solution is preferable. When (B2) is used as an aqueous solution, the concentration of (B2) 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 (A2). In particular, when powdered (B2) is dissolved in water, adding (B2) all at once is not preferable because it causes dents and makes it difficult to dissolve in water.

  In the method (2), the amount of (B2) 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 (B2), etc. and is not particularly limited. However, from the viewpoint of flocculation performance based on TS in sludge or wastewater, the preferable lower limit is 0.01%, more preferably 0.1%, particularly preferably 1%, most preferably 1.5%, the same viewpoint. Therefore, 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) and (B1) of the present invention to the sludge or waste water in the methods (1) and (3) is not particularly limited, and (C) or (B1) Although it may be added to the wastewater as it is, the method of adding (C) or (B1) to the sludge or wastewater after making (C) or (B1) into an aqueous solution is preferable. When (C) or (B1) 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 (A2) and (B2) above.

  The amount of (C) and (B1) used when adding to sludge or wastewater in the methods (1) and (3) is the kind of sludge or wastewater, the content of suspended particles and the polymer flocculant The lower limit is preferably 0.01%, more preferably 0.1%, particularly preferably 1%, most preferably from the viewpoint of agglomeration performance based on TS in sludge or wastewater. The upper limit is preferably 1.5%, and from the same 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), (2) or (3) above, for example, gravity sedimentation, membrane filtration, column filtration, pressurized flotation, And a method using a concentrator (eg, thickener) and a dehydrator (eg, centrifugal dehydrator, belt press dehydrator, filter press dehydrator and capillary dehydrator). 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, 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, decolorizers, thickeners, antistatic agents and fiber treatment agents, Of these, a flocculant for excavation and muddy water treatment, a papermaking chemical, and an additive for increasing crude oil production are preferred.

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,% in an Example shows weight% and a copolymerization ratio represents molar ratio.
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) 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).
The floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarification in this example were carried out according to the following methods.

<Flock particle size>
Jar tester [Miyamoto Riken Kogyo Co., Ltd., Model JMD-6HS-A] and two plate-like PVC stirring blades (diameter 5 cm, height 2 cm, thickness 0.2 cm) up and down to form a cross Continuously attached to a stirring bar, 200 ml of sludge or waste water [or sludge or waste water mixed with (A) previously added and mixed] was placed in 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 number of revolutions was set to 300 rpm, and further stirred for 30 seconds. Then, the stirring was stopped and the size of the aggregate was visually observed again (the floc particle size at the number of revolutions 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 And the amount of filtrate 60 seconds after immediately after injection | throwing-in was measured using the stopwatch.
<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: did.
A: Very easy to peel off (almost no filter cloth deposits)
○: Easy to peel off (slightly filter cloth deposits)
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). Thereafter, the weight of the dry cake remaining on the petri dish was defined as (W4), and the moisture content of the cake was calculated from the following formula.

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

<COD>
Using the filtrate after measuring the filtrate amount, COD was measured according to the COD _Mn analysis method described in JIS K-0102 (1998 version).
<Filtrate clarity>
Using the filtrate after the filtrate amount measurement, absorbance at wavelengths of 590 nm and 700 nm was measured with an absorptiometer [manufactured by Shimadzu Corporation, UV-1200]. The numerical value (%) of absorbance indicates a value when the absorbance of ion-exchanged water is 100%.

Production Example 1
In an autoclave equipped with a stirrer, a temperature sensor, and a temperature controller, 230 parts of water and 76 parts of 35% hydrochloric acid were charged, and 72 parts of diallylamine was gradually added dropwise while cooling to obtain a diallyl ammonium chloride aqueous solution. Next, after sufficiently replacing the system with nitrogen (purity 99.999% or more), 18 parts of anhydrous sodium bisulfite and 18 parts of 35% hydrochloric acid were charged to generate sulfur dioxide in the system. -29.2 parts of a 10% aqueous solution of azobis (2-methylpropionamidine) dihydrochloride 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. 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. 108 parts of a copolymer [A1] was obtained (yield 93%, solid content 95%). According to elemental analysis, the ratio of diallylammonium chloride based on the total amount of all monomers constituting [A1] was 80 mol%, and the ratio of sulfur dioxide was 20 mol%.

Production Example 2
In a Kolben equipped with a stirrer, a temperature sensor and a temperature control device, 970 parts of methyldiallylammonium chloride crystals are placed, and 163 parts of sulfur dioxide is added thereto while cooling from the outside so that the inside of the system becomes 20 to 80 ° C. I gradually blown in. With the exotherm, sulfur dioxide was absorbed by methyldiallylammonium chloride to obtain a liquid mixture. Next, 100 parts of this mixture was placed in a transparent polyethylene bag having a thickness of 0.1 mm and spread on a flat plate having a thickness of about 3 mm and a length and width of 5 cm each. This was placed at a position 10 cm immediately below the center of a fluorescent lamp (40 W, length 120 cm) having a wavelength distribution of 300 to 450 nm and irradiated for 3 hours. Immediately after irradiation, polymerization started with exotherm and the whole solidified. After the polymerization, the content was taken out and thereafter treated in the same manner as in Production Example 1 to obtain 97 parts of a powdery copolymer [A2] (yield 97%, solid content 99%). According to elemental analysis, the proportion of methyldiallylammonium chloride based on the total amount of all monomers constituting [A2] was 72 mol%, and the proportion of sulfur dioxide was 28 mol%.

Production Example 3
200 parts of a 60% aqueous solution of dimethyldiallylammonium chloride was placed in an autoclave equipped with a stirrer, a temperature sensor, and a temperature controller. Next, after sufficiently replacing the system with nitrogen (purity 99.999% or more), 29.2 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride as an initiator was stirred. Added while. The inside of the system was gradually heated from the outside, polymerization started at 50 ° C., and heat generation was observed. 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. 121 parts of a copolymer [A3] was obtained (yield 96%, solid content 95%).

Production Example 4
After adding 115 parts (100 mol%) of an 80% aqueous solution of quaternary ammonium salt obtained by reacting N, N-dimethylaminoethyl methacrylate with methyl chloride to 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 thereafter treated in the same manner as in Production Example 1 to obtain 95 parts of a powdered water-soluble polymer [B1] (yield 98%, solid content 95%).

Production Example 5
In Production Example 4, instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 74 parts (40 mol) of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate %) And 65 parts (60 mol%) of a 50% aqueous solution of acrylamide in the same manner as in Production Example 3 to obtain 97 parts of a powdery water-soluble polymer [B2] (yield 98%, solid 93% content).

Production Example 6
In Production Example 4, 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 aqueous solution was mixed with methyl of N, N-dimethylaminoethyl acrylate. Powder in the same manner as in Production Example 3, 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%).

Comparative production 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 Production Example 1 was performed to obtain 23 parts of a powdery polycondensate [A4] (yield 93%).

Example 1
9 parts of the water-soluble polymer [B1] and 1.3 parts of the copolymer [A1] were placed in a glass bottle that could be sealed and shaken well until uniform to obtain 10.3 parts of a polymer flocculant [C1]. .

Example 2
Example 1 was used except that 9 parts of the water-soluble polymer [B2] was used instead of the water-soluble polymer [B1] and 0.42 part of the copolymer [A2] was used instead of the copolymer [A1]. As a result, 9.42 parts of a polymer flocculant [C2] were obtained.

Example 3
Example 1 was used except that 9 parts of the water-soluble polymer [B3] was used instead of the water-soluble polymer [B1], and 0.84 part of the copolymer [A2] was used instead of the copolymer [A1]. As a result, 9.84 parts of a polymer flocculant [C3] was obtained.

Example 4
In Production Example 4, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 113 parts (100 mol%) of the aqueous solution and 33 parts of a 30% aqueous solution of [A1] were used. Except for the use, in the same manner as in Production Example 4, 105 parts of a powdery water-soluble polymer [C4] was obtained (yield 99%, solid content 95%).

Example 5
In Production Example 4, instead of 115 parts of an 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 113 parts (100 mol%) of the aqueous solution and 33 parts of a 30% aqueous solution of [A3] were used. Except for the use, in the same manner as in Production Example 4, 105 parts of a powdery water-soluble polymer [C5] was obtained (yield 99%, solid content 95%).

Example 6
In Production Example 4, instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 73 parts (40 moles) of 80% aqueous solution of methyl chloride salt of N, N-dimethylaminoethyl acrylate %), 64 parts (60 mol%) of a 50% aqueous solution of acrylamide and 33 parts of a 30% aqueous solution of [A2], in the same manner as in Production Example 4, a powdered water-soluble polymer [C6] 106 (Yield 98%, solid content 93%).

Example 7
In Production Example 4, 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 aqueous solution was mixed with methyl of N, N-dimethylaminoethyl acrylate. Other than using 57 parts (30 mol%) of 80% aqueous solution of chloride salt, 50 parts (45 mol%) of 50% aqueous solution of acrylamide and 11 parts (20 mol%) of acrylic acid and 33 parts of 30% aqueous solution of [A2] Produced 103 parts of a powdery water-soluble polymer [C7] in the same manner as in Production Example 4 (yield 96%, solid content 93%).

Comparative Example 1
Instead of 115 parts of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate, 56 parts (30 mol%) of 80% aqueous solution of methyl chloride quaternary ammonium salt of N, N-dimethylaminoethyl acrylate And powdered polymer flocculant [C8] in the same manner as in Production Example 4, except that 65 parts (60 mol%) of a 50% aqueous solution of acrylamide and 17 parts (10 mol%) of a 60% aqueous solution of diallylammonium chloride were used. ] 92 parts were obtained (yield 98%, solid content 93%).

Comparative Example 2
Instead of the water-soluble polymer (B1), 9 parts of the water-soluble polymer [B3] and 0.84 parts of the polycondensate [A4] obtained in Comparative Production Example 1 were used instead of the copolymer [A1]. Otherwise in the same manner as in Example 1, 9.84 parts of the polymer flocculant [C9] was obtained.

  (Co) polymer [A1 to A3] obtained in Production Examples 1 to 3, water-soluble polymer [B1 to B3] obtained in Production Examples 4 to 6, and polycondensation obtained in Comparative Production Example 1 The body [A4] is shown in Table 1. Table 2 shows the polymer flocculants [C1 to C7] obtained in Examples 1 to 7 and the polymer flocculants [C8 and C9] obtained in Comparative Examples 1 and 2.

AAM: Acrylamide DAAQ: Methyl chloride of N, N-dimethylaminoethyl acrylate
Quaternary ammonium salt DAMQ: methyl chloride of N, N-dimethylaminoethyl methacrylate
Quaternary ammonium salt AAc: Acrylic acid

Examples 8-9, Comparative Example 3
Copolymers [A1, A2], polycondensate [A4] and water-soluble polymer [B3] were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. Digested sludge collected from G sewage treatment plant [pH 7.2, TS 1.8%, organic content 60%, and so on. ] Into three separate beakers of 500 parts, and add 25 parts of each of the aqueous solutions of [A1], [A2] and [A4] (the solid content addition amount at this time is 0.56% / TS). The mixture was sufficiently stirred and mixed with a mixer. Each 200 parts of the sludge is further mixed with 40 parts of the above [B3] aqueous solution by the addition and mixing methods described in the above <Flock particle size> measurement method. The cloth peelability, cake moisture content, COD and filtrate clarity were measured (the solid content of [B3] at this time was 2.3% / TS). The test results are shown in Table 3.
From the results of Table 3, Examples 8 to 9 formed flocs having a large particle diameter as compared with Comparative Example 3, and the flocs once formed were not easily broken even under high agitation (300 rpm) (high flock strength). In other words, it has been found that it has good filter cloth peelability, high dewaterability (low cake water content), COD reduction effect and filtrate clarifying effect.

Examples 10-11, Comparative Examples 4-5
The polymer flocculant [C3, C7] of the present invention and the polymer flocculant [C9] and the water-soluble polymer [B3] as comparative examples are each dissolved in ion-exchanged water to have a solid content of 0.2%. It was. G digested sludge collected from the sewage treatment plant is taken into four separate beakers of 200 parts each, and 45 parts of each aqueous solution is mixed by the apparatus, addition and mixing method described in the above <Flock particle size> measurement method. The floc particle size, filtrate amount, filter cloth peelability, cake water content, COD and filtrate clarity were measured by the above-mentioned methods [[C3], [C7], [C9] and [B3] at this time. The solid content is 2.5% / TS]. The test results are shown in Table 4.
From the result of Table 4, Examples 10-11 form the floc of a large particle size compared with Comparative Examples 4-5, and the floc once formed is hard to break even under high agitation (300 rpm) (floc strength is It has been found that it has the effect of enhancing the filter cloth releasability, high dewaterability (low cake water content), COD reduction effect and filtrate clarification.

Examples 12-14, Comparative Example 6
The polymer flocculant [C1, C4, C5] of the present invention and the water-soluble polymer [B1] as a comparative example were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. J Surplus sludge [pH 6.2, TS 2.4%, organic content 75%] collected from the sewage treatment plant was taken in four separate beakers of 200 parts each, and 50 parts of each aqueous solution was measured in the <Flock particle size> measurement. The mixture was processed by the apparatus and addition described in the method, and the mixing method, and the floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarification were measured by the above method [at this time [C1], [C4], [C5] and [B1] have a solid content addition of 2.1% / TS]. The test results are shown in Table 5.
From the result of Table 5, Examples 12-14 form the floc of a large particle diameter compared with the comparative example 6, and even if it is under high stirring (300 rpm), the floc once formed is hard to be broken (a floc intensity | strength is strong). In other words, it has been found that it has good filter cloth peelability, high dewaterability (low cake water content), COD reduction effect and filtrate clarifying effect.

Examples 15-16, Comparative Examples 7-8
The polymer flocculant [C2, C6] of the present invention and, as a comparative example, the water-soluble polymer [B2] and the polymer flocculant [C8] are each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. did. M surplus sludge [pH 7.2, TS 1.5%, organic content 55%] collected from M Food Factory was taken in 4 separate beakers of 200 parts each, and 30 parts of each aqueous solution was measured in the <Flock particle size> measurement method. The floc particle size, filtrate amount, filter cloth peelability, cake moisture content, COD and filtrate clarification were measured by the above-mentioned methods. The solid content of C2], [C6], [B2] and [C8] was 2.0% / TS]. The test results are shown in Table 6.
From the result of Table 6, Examples 15-16 formed the floc of a large particle size compared with Comparative Examples 7-8, and the floc once formed was hard to break even under high agitation (300 rpm) (floc strength is It has been found that it has the effect of enhancing the filter cloth releasability, high dewaterability (low cake water content), COD reduction effect and filtrate clarification.

  Since the polymer flocculant of the present invention exhibits an unprecedented low addition amount and a high coagulation rate and a high dehydration rate (that is, low cake moisture content), organic sludge produced by treatment of sewage or factory wastewater or the like It can be used as a polymer flocculant for dewatering treatment of inorganic sludge, and particularly preferably used for dewatering treatment of organic sludge. Other uses include, for example, flocculants for drilling and muddy water treatment, papermaking chemicals (for example, paper industry formation forming aids, drainage yield improvers, drainage improvers and paper strength enhancers), and crude oil production increases. Additives (additives for secondary and tertiary recovery of crude oil), dispersants, scale inhibitors, coagulants, decolorizers, thickeners, antistatic agents and textile treatment agents, among which drilling and muddy water It is suitably used as a processing flocculant, a papermaking chemical and an additive for increasing crude oil production.

Claims (11)

The (co) polymer (A1) having the monomer (a) represented by the general formula (1) as an essential structural unit and the monomer (b) in the presence of (A1), other than (A1) A polymer flocculant comprising the water-soluble polymer (B1).

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

[Wherein, R ¹ is H or methyl group; R ² and R ³ are each independently H, (meth) allyl group, alkyl group having 1 to 16 carbon atoms or hydroxyalkyl group having 2 to 4 carbon atoms; Z ⁻ Represents a counter anion. ] Polymer aggregation characterized by combining monomer (a) represented by general formula (1) and copolymer (A2) having sulfur dioxide as an essential constituent unit with other water-soluble polymer (B2) Agent.

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

[Wherein, R ¹ is H or methyl group; R ² and R ³ are each independently H, (meth) allyl group, alkyl group having 1 to 16 carbon atoms or hydroxyalkyl group having 2 to 4 carbon atoms; Z ⁻ Represents a counter anion. ] The polymer flocculant according to claim 1 or 2, wherein R ³ is H. The polymer flocculant according to claim 2 or 3, wherein the ratio of sulfur dioxide based on the total amount of all monomers constituting (A2) is 0.1 to 50 mol%. The polymer flocculant according to any one of claims 1 to 3, wherein the ratio of (a) based on the total amount of all monomers constituting (A1) or (A2) is 50 to 99.9 mol%. The polymer flocculant according to any one of claims 1 to 5, wherein R ¹ and R ² are H and Z is Cl. The ratio of the structural unit which has a 5-membered ring structure or a 6-membered ring structure among the structural units which consist of (a) in (A1) or (A2) is 90 mol% or more. Polymer flocculants. The ratio of (A1) based on the total weight of (A1) and (B1) or the ratio of (A2) based on the total weight of (A2) and (B2) is 0.5 to 70%. The polymer flocculant as described in any one of. The polymer flocculant according to any one of claims 1 to 8, wherein (B1) or (B2) is a polymer having the monomer (b1) represented by the general formula (2) as an essential constituent unit.

^{_{CH 2 = CR 4 -CO-X}} -Q-N + R 5 R 6 R 7 · 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 ⁴ is H or a methyl group; R ⁵ , R ⁶ and R ⁷ are each independently And H, an alkyl group having 1 to 16 carbon atoms or an aralkyl group; Z ⁻ represents a counter anion. ] The polymer flocculant according to any one of claims 1 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. The high content according to any one of claims 2 to 9, wherein (A2) is added to and mixed with sludge or wastewater, and then (B2) is further added and mixed to form a floc for solid-liquid separation. How to use molecular flocculants.