JP4786558B2 - Polymer flocculant - Google Patents

Description

  The present invention relates to a novel polymer flocculant used for dehydration of organic sludge generated by microbial treatment such as sewage or human waste (hereinafter abbreviated as sewage), and a method for treating sludge using the polymer flocculant.

Conventionally, cationic polymer flocculants have been widely used in the dehydration of organic sludge (hereinafter sometimes simply referred to as sludge) generated by microbial treatment of sewage or the like. However, in recent years, while sludge consolidation for the purpose of improving the efficiency of sludge treatment has progressed, it takes a long time for sludge to be dewatered due to sludge transport and storage, etc., and sludge decay causes difficulty in dewatering. Therefore, in order to improve dewaterability, a method of using an inorganic flocculant and an amphoteric polymer flocculant in combination (for example, see Patent Documents 1 and 2) has been proposed and widely used. However, this method has a higher drug cost than the method using a cationic polymer flocculant, and there are problems such as an increase in sludge cake generated by the use of an inorganic flocculant and an increase in ash after incineration. Reduction of inorganic flocculants is required. However, if the amount of the inorganic flocculant is reduced, the strength of the sludge flocculation floc (hereinafter abbreviated as “floc”) is lowered and easily broken, resulting in an increase in water content.
In order to solve these problems, amphoteric polymer flocculants obtained by copolymerizing hydrophobic monomers have been proposed (see, for example, Patent Document 2). However, the copolymerization of anionic, cationic and hydrophobic monomers is difficult to uniformly polymerize hydrophobic monomers due to the difference in solubility, and the amount of hydrophobic monomers introduced is limited. Was insufficient.
On the other hand, in recent years, the dehydrator is changing from a belt press dehydrator to a screw press dehydrator in terms of odor control and downsizing. Since the screw press dehydrator has a greater shearing force on the sludge coagulation floc, the conventional cationic polymer flocculant mainly used in the belt press dehydrator has a low water content because it has a weak floc strength and is easily broken. There are problems such as worsening.

Japanese Patent Laid-Open No. 2-180700 JP 11-156400 A

As described above, a polymer flocculant used for sludge treatment in recent years is required to have a capability of forming a stronger floc with a low addition amount and reducing the moisture content of the cake after dehydration.
An object of the present invention is to provide a polymer flocculant capable of forming sluggish flocs with a low addition amount and enhancing the treatment efficiency of sludge.

［式中、ＸはＯまたはＮＨ；Ｑは炭素数２〜４のアルキレン基または炭素数２〜４のヒドロキシアルキレン基；Ｒ¹はＨまたはメチル基；Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立にＨ、炭素数１〜１６のアルキル、アリールアルキルまたはアルキルアリール基；Ｚ^-は対アニオンを表す。］
；並びに、該高分子凝集剤を有機性汚泥に添加してフロックを形成させ、固液分離させることを特徴とする汚泥の処理方法である。 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 provides 50 to 85 mol% of a repeating unit represented by the following general formula (1), 15 to 50 mol% of a compound having one (meth) acryloyl group and one vinyl group. A polymer flocculant comprising a copolymer (A) having a repeating unit composed of one or more hydrophobic monomers (b) selected from the group consisting of aromatic ring-containing vinyl compounds having

[Wherein X is O or NH; Q is an alkylene group having 2 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ¹ is H or a methyl group; R ² , R ³ and R ⁴ are each independently selected. And H, an alkyl, arylalkyl or alkylaryl group having 1 to 16 carbon atoms; Z ⁻ represents a counter anion. ]
And a sludge treatment method characterized in that the polymer flocculant is added to organic sludge to form a floc and solid-liquid separation is performed.

  The polymer flocculant of the present invention has the effect of adding a small amount to organic sludge and mixing it to form a strong floc and greatly reduce the moisture content of the cake after sludge dewatering treatment.

該（Ａ）は、下記一般式（２）で表されるカチオン性モノマー（ａ）と、疎水性モノマー（ｂ）からなるモノマーを有機溶媒中で共重合させてなる共重合体（Ａ０）を、酸で中和もしくは４級化剤で４級化することにより形成される。

式（１）、（２）中、ＸはＯまたはＮＨ、また、Ｑは炭素数（以下Ｃと略記）２〜４（好ましくは２〜３）のアルキレン基またはＣ２〜４（好ましくは２〜３）のヒドロキシアルキレン基を表す。ＱのＣが４を超えると（Ａ）の水への溶解性が悪くなる。 The copolymer (A) in the present invention is a compound having 50 to 85 mol% of a repeating unit represented by the following general formula (1) and 15 to 50 mol% of a (meth) acryloyl group and It has a repeating unit composed of one or more hydrophobic monomers (b) selected from the group consisting of an aromatic ring-containing vinyl compound having one vinyl group.

The (A) is a copolymer (A0) obtained by copolymerizing a cationic monomer (a) represented by the following general formula (2) and a monomer comprising a hydrophobic monomer (b) in an organic solvent. It is formed by neutralization with an acid or quaternization with a quaternizing agent.

In the formulas (1) and (2), X is O or NH, and Q is an alkylene group having 2 to 4 (preferably 2-3) carbon atoms (hereinafter abbreviated as C) or C2-4 (preferably 2 to 2). 3) a hydroxyalkylene group. When C of Q exceeds 4, the solubility of (A) in water becomes poor.

  C2-4 alkylene groups include ethylene, n- and i-propylene, 1,2-, 1,3- and 2,3-butylene and tetramethylene groups; C2-4 hydroxyalkylene groups , Hydroxyethylene, 1- and 2-hydroxypropylene, 1-hydroxy-i-propylene, 2-hydroxymethylpropylene and 2-methyl-2-hydroxypropylene, and 1- and 2-hydroxytetramethylene groups.

In the formulas (1) and (2), R ¹ represents H or a methyl group, and a methyl group is preferred from the viewpoint of floc strength. R ² , R ³ and R ⁴ each independently represent H, C 1-16 (preferably C 1-10) alkyl, arylalkyl or alkylaryl groups.
When C exceeds 16, the solubility of (A) in water becomes poor. Examples of the alkyl group include methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, n-, i-, sec- and t-amyl and lauryl groups; arylalkyl groups Examples include benzyl and phenylethyl groups; examples of alkylaryl groups include toluyl, ethylphenyl, and cumyl groups.
It is preferable that one of R ² , R ³ and R ⁴ is H from the viewpoint of flock strength.

In formula (1), examples of Z ⁻ include the following anions.
(1) inorganic acids such as hydrohalic acids (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid (2) sulfate esters such as C1-30 sulfate esters [eg alkyl or alkenyl sulfates (eg methyl Sulfuric acid, 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) 1-10 mol adduct Of sulfate]

(3) Sulfonic acids such as C1-30 sulfonic acids [eg alkyl (C1-10) sulfonic acids (eg methylsulfonic acid and ethylsulfonic acid), alkylaryl (C7-30) sulfonic acids [alkylbenzenesulfonic acid, alkylphenolsulfone Acid and alkyl naphthalene sulfonic acid], higher alkyl (C10-30) sulfonic acid, higher fatty acid ester (C10-30) sulfonic acid, higher alcohol ether (C10-30) sulfonic acid, sulfosuccinic acid ester, higher fatty acid amide (C10 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 these Z ⁻ , the anion of sulfonic acid is preferable from the viewpoint of the water solubility of (A), and more preferable are sulfuric acid, halogen (for example, Cl ⁻ and Br ⁻ ) and sulfuric acid esters (for example, alkyl and alkenyl sulfuric acid esters). ), Particularly preferred are sulfuric acid, Cl ⁻ , methylsulfuric acid and ethylsulfuric acid anions, and most preferred are sulfuric acid and Cl ⁻ .

Examples of the cationic monomer (a) include the following, and mixtures thereof.
(A1) (Meth) acrylate [when X in the general formula (1) 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) ) Acrylates, methylaminopropyl (meth) acrylates and aminoethyl (meth) acrylates] and tertiary amino group-containing (meth) acrylates [C7-20, such as dimethylaminoethyl (meth)
Acrylate and dimethylaminopropyl (meth) acrylate].

(A2) (Meth) acrylamide compound [when X in the general formula (1) is N]
Primary amino group-containing (meth) acrylamide [C5-20, such as aminoethyl (meth) acrylamide and aminopropyl (meth) acrylamide] Secondary amino group-containing (meth) acrylamide [C6-20, such as methylaminoethyl (meth) ) Acrylamide and methylaminopropyl (meth) acrylamide] and tertiary amino group-containing (meth) acrylamide [C7-20, such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide].

  Among these, (a1) is preferable from an industrial viewpoint, tertiary amino group-containing (meth) acrylate is more preferable, and dimethylaminoethyl (meth) acrylate is particularly preferable.

The hydrophobic monomer (b) is one or two selected from the group consisting of a compound (b1) having one (meth) acryloyl group and an aromatic ring-containing vinyl compound (b2) having one vinyl group These monomers. Here, hydrophobic means that the solubility in water at 20 ° C. is 1 g / 100 g or less of water, and the same applies hereinafter.
When the solubility of (b) in water exceeds 1 g / 100 g of water and becomes non-hydrophobic, a strong floc is not formed even when the obtained polymer flocculant is added to organic sludge.

Examples of (b1) include the following and mixtures thereof.
(B11) (Meth) acrylic acid ester C8 or more and number average molecular weight [hereinafter abbreviated as Mn, measurement is by gel permeation chromatography (GPC) method. ] 1,000 or less, for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkenyl ester, and (meth) acrylic acid polyoxypropylene ester: for example, butyl methacrylate, (meth) acrylic acid 2-ethylhexyl, ( (Meth) acrylic acid octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid lauryl, (meth) acrylic acid cetyl, (meth) acrylic acid stearyl, (meth) acrylic acid oleyl, polypropylene glycol (Mn100-800) (Meth) acrylic acid ester.

(B12) C8-24 N-substituted (meth) acrylamides N-alkyl substituted (meth) acrylamides, N-alkenyl substituted (meth) acrylamides, and N- (poly) oxypropyl substituted (meth) acrylamides; for example, N, N −
Diethyl (meth) acrylamide, N-2 ethylhexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N-lauryl (meth) acrylamide, N-cetyl (meth) acrylamide, N-stearyl (Meth) acrylamide, N-oleyl (meth) acrylamide, N, N-di (poly) oxypropyl [(poly) oxypropyl group added with 1 to 3 moles of PO] (meth) acrylamide and the like.

  Among these (b1), from the viewpoint of hydrophobicity, industrially and copolymerization with (a), (b11) is preferable, and more preferable are C8-24 alkyl (meth) acrylates and alkenyl esters, Particularly preferred are lauryl (meth) acrylate, -cetyl, -stearyl and -oleyl.

Examples of (b2) include the following and mixtures thereof.
(B21) Monocyclic compounds C8 to C13, such as styrene, α-methylstyrene, β-methylstyrene, methylstyrene, dimethylstyrene, trimethylstyrene, hydroxystyrene, methoxystyrene, acetoxystyrene, allylbenzene, and allylphenol.
(B22) Polycyclic compounds C12 to C15, such as vinylnaphthalene, naphthylacrylic acid, and vinylnaphthol.
Of these (b2), styrene, α-methylstyrene, hydroxystyrene, and acetoxystyrene are preferable from the industrial viewpoint, and styrene, α-methylstyrene, and acetoxystyrene are more preferable, and styrene is particularly preferable.

If necessary, the copolymer (A0) may contain other ethylenically unsaturated group-containing monomer (c) as a constituent unit other than (a) and (b) as long as the effects of the present invention are not impaired. Can do. (C) includes the following monomers and mixtures thereof.
(C1) Water-soluble compound having one unsaturated group Water-soluble herein means that the solubility in water at 20 ° C. exceeds 1 g / 100 g of water.
(C11) (Meth) acrylate C5 or more and Mn 3,000 or less, for example, hydroxyl group-containing (meth) acrylate [for example, hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol (degree of polymerization 3 to 50) mono (meta ) Acrylate and (poly) glycerol (degree of polymerization 1 to 10) mono (meth) acrylate], 2-cyanoethyl (meth) acrylate, methyl (meth) acrylate, glycidyl (meth) acrylate

(C12) Unsaturated carboxylic acids Monocarboxylic acids [C3-30, such as (meth) acrylic acid, vinylbenzoic acid and allylic acetic acid] and poly (divalent to tetravalent or higher) carboxylic acids [C4-30, such as ( Anhydrous) maleic acid, fumaric acid and (anhydrous) itaconic acid]
(C13) Unsaturated sulfonic acid Aliphatic sulfonic acid [C2-20, such as vinylsulfonic acid, (meth) allylsulfonic acid]; Aromatic sulfonic acid [C6-20, such as styrenesulfonic acid, α-methylstyrenesulfonic acid] Alkenyl and alkyl (C1-18) alkenyl esters of sulfocarboxylic acids (eg α-sulfoalkanoic acids and sulfosuccinic acids) [C7-30, eg methylvinyl, propyl (meth) allyl and stearyl (meth) allylsulfosuccinate, (Meth) allylsulfolaurate]; sulfo group-containing (meth) acrylate [C4-30, for example, (meth) acryloyloxyalkane (C in alkane is 2-20) sulfonic acid [
For example, 2- (meth) acryloyloxyethanesulfonic acid, 2- and 3- (meth) acryloyloxypropanesulfonic acid, 2- and 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2, 2-dimethylethanesulfonic acid], p- (meth) acryloyloxymethylbenzenesulfonic acid]; sulfo group-containing (meth) acrylamide [C5-30, such as 2- (meth) acryloylaminoethane-, propane- and butane-sulfone Acid, 3- (meth) acryloylaminopropanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzene Sulfonic acid]; alkyl (C1- 0) (meth) allyl sulfosuccinate [C8~28, such as methyl (meth) allyl sulfosuccinate], etc.

(C14) C3-7 (meth) acrylamide compound (meth) acrylamide, N-alkyl (C1-3) (meth) acrylamide [N-methyl, -ethyl, -n- and -i-propyl (meth) acrylamide, etc. And N-methylol (meth) acrylamide etc. (c15) Compound having amine imide group 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide, 1,1- Dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth) acrylimide and 1,1,1-trimethylamine (meth) acrylimide, etc. (c16) Other nitrogen atom-containing unsaturated group-containing compounds C3-20, such as acrylonitrile, N-vinylformamide, N-vinyl-2- Pyrrolidone, vinyl imidazole, N- vinyl succinimide, N- vinyl carbazole, vinyl aniline, (meth) allylamine, di (meth) allylamine, 2-vinylpyridine, 3-vinyl piperidine, vinyl pyrazine and vinyl morpholine

(C2) Hydrophobic compound having one unsaturated group C2-7, for example, unsaturated hydrocarbon [ethylene, propylene and other α-olefins (1-butene, 1-hexene, 1-heptane, etc.), etc.] Can be mentioned.
(C3) Compound containing two unsaturated groups C10-54, for example, unsaturated hydrocarbon (divinylbenzene, etc.), di (meth) acrylate [1,6-hexanediol di (meth) acrylate, (poly) ethylene Glycol (C2 or more and Mn 1,200 or less) di (meth) acrylate, (poly) propylene glycol (C3 or more and Mn 900 or less) di (meth) acrylate, etc.]

(C4) Amine salt of (meth) acrylate [when X in the general formula (1) is O] An inorganic acid (above) salt of an amino group-containing (meth) acrylate exemplified as the above (a1), organic Acid salts (sulfuric acid ester, sulfonic acid, phosphoric acid ester, phosphonic acid, carboxylic acid, etc.), and amino group-containing (meth) acrylates or salts thereof are converted into quaternizing agents [C1-6 alkyl, C7- A quaternary ammonium salt (c5) (meth) acrylamide compound [general formula (4) quaternized with 16 arylalkyls or C7-16 alkylaryl halides such as methyl chloride, ethyl chloride, benzyl chloride, phenethyl chloride] Amine salt in the case where X in 1) is N] Amino group-containing (meta) exemplified as (a2) above Inorganic acid (above) salts of acrylamide, organic acid (above) salts, and amino group-containing (meth) acrylamides or salts thereof are quaternized with a quaternizing agent (above). Quaternary ammonium salt

  Of these (c), (meth) acrylamide, polyethylene glycol (polymerization degree: 3 to 50) mono are preferable from the viewpoint of solubility in an organic solvent during polymerization, water solubility of (A0) and industrial viewpoint. (Meth) acrylate; quaternary ammonium salt formed by quaternization with methyl chloride or benzyl chloride of dimethylamiethyl (meth) acrylate is preferred from the viewpoint of improving cationicity; and a cationic group in (A) From the viewpoint of improving floc strength by ionic crosslinking with an anionic group, (meth) acrylic acid is preferred; from the viewpoint of improving charge density by making (A) a crosslinked or branched structure, two unsaturated groups are preferred. It is a compound that has. As will be described later, glycidyl methacrylate is preferable from the viewpoint of grafting a water-soluble monomer to (A).

  The proportion of (a) in the total monomers constituting (A0) is preferably from 50 to 85 mol%, preferably from 53 to 83 mol%, more preferably from the viewpoint of charge neutralization and hydrophobicity on the sludge particle surface. -80 mol%, particularly preferably 60-78 mol%; the proportion of (b) is 15-50 mol%, preferably 17-47 mol%, more preferably 20-, from the viewpoint of the balance between hydrophobicity and hydrophilicity The proportion of 45 mol%, particularly preferably 22 to 40 mol%; (c) is preferably 40 mol% or less, more preferably 30 mol% or less, particularly preferably 20 mol% or less.

In (A), (a) and (b) are first copolymerized in an organic solvent or a mixed solvent of an organic solvent and water to give (A0), and then neutralized with an acid, or 4 with a quaternizing agent. It can manufacture by classifying into a quaternary ammonium salt.
The proportions and preferred proportions of the structural units comprising (A), (b) and optionally (c) constituting (A) are the same as those proportions in (A0).
The production method of (A0) includes a radical polymerization method, and solution dropping polymerization is preferable from the viewpoint of industrial viewpoint and molecular weight control.
The solution dropping polymerization can be produced, for example, by a method of dropping a monomer, a solvent and a radical polymerization initiator solution at the boiling point of the solvent (for example, JP-A-6-211942).

Examples of the solvent used include alcohols (C1-6, such as methanol, ethanol, n- and i-propyl alcohol), ketones (C3-6, such as acetone, methyl ethyl ketone), tetrahydrofuran (THF), dimethylformamide (DMF), A polar solvent such as a mixture of these and a mixture of these with water, or a nonpolar solvent such as toluene or xylene can be used.
Of these, i-propyl alcohol, methyl ethyl ketone, and a mixed solvent thereof with water are preferable from the viewpoints of solubility of the monomer and initiator and ease of solvent removal after polymerization. More preferred are i-propyl alcohol and methyl ethyl ketone.

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

  The use amount of the radical polymerization initiator is preferably 0.001%, more preferably 0.005%, particularly preferably from the viewpoint of obtaining an optimal molecular weight as (A0) based on the total weight of the monomers. 0.01%, most preferably 0.05%, and a preferable upper limit is 20%, more preferably 10%, particularly preferably 5%, and most preferably 3%.

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 of 32 or more and Mn of 50,000 or less, such as methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene Glycol, polyethylene glycol (molecular weight 106 or more and Mn 50,000 or less) and (poly) ethylene (poly) propylene glycol (molecular weight 120 or more and Mn 50,000 or less)], having one or two or more amino groups in the molecule Examples include compounds [for example, ammonia and amines (C1-30, for example, methylamine, 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, salts thereof [alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metal (for example, magnesium and calcium) salts, ammonium salts, amines (C1- 20) salts and inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts], and mixtures thereof.
(1) Monovalent thiol Aliphatic thiol [C1-20, such as methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, 1-thioglycerol, thioglycolic acid monoethanolamine), 1-thioglycerol, thioglycolic acid monoethanolamine, thiomaleic acid, cysteine and 2-mercaptoethylamine], alicyclic thiols (C5-20) For example, cyclopentanethiol and cyclohexanethiol) and aromatic (aliphatic) thiols (C6-12, such as benzenethiol and benzyl mercaptan and thiosalicylic acid).

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

  In the case of using a chain transfer agent for radical polymerization, the preferred lower limit is 0.001% based on the total weight of monomers, more preferably 0.001%, from the viewpoint of obtaining an optimal molecular weight as (A0). 005%, particularly preferably 0.01%, most preferably 0.05%, and a preferred upper limit is 10%, more preferably 5%, particularly preferably 3%, most preferably 1%.

  The monomer concentration in the monomer solution in the solution dropping polymerization is, based on the total weight of the monomer solution, the lower limit is usually 5%, preferably 10% from the viewpoint of reducing the residual monomer, more preferably 15%, particularly preferably 25%, Most preferably, it is 25%, the upper limit is usually 90%, preferably 85%, more preferably 80%, particularly preferably 75%, most preferably 70% from the viewpoint of temperature control during polymerization.

  The polymerization temperature in the solution dropping polymerization is preferably controlled from the viewpoint of molecular weight control so as to keep the predetermined temperature constant (for example, predetermined temperature ± 5 ° C.). Although the temperature can be controlled by appropriately heating and cooling the reaction vessel, it is preferable to perform drop polymerization at the boiling point of the solvent from the viewpoint that it is easy to keep the predetermined temperature constant. The boiling point of the solvent can be adjusted by the type and pressure of the solvent. The polymerization temperature is usually from 40 to 190 ° C., preferably from 50 to 180 ° C., more preferably from 60 to 170 ° C., particularly preferably from 70 to 160 ° C., and most preferably from 80 to 150 ° C. from the viewpoint of ease of temperature control and safety. It is.

The end point of the reaction can be confirmed when the heat generation due to the polymerization disappears, but the polymerization time is usually 1 to 24 hours from the time when the start of the polymerization is confirmed by the heat generation. From a specific viewpoint, it is preferably 2 to 12 hours.
The monomer concentration, polymerization temperature, and polymerization time can be appropriately adjusted depending on the monomer composition, polymerization method, initiator type, and the like.

Mn of (A0) is preferably 1,000, more preferably 3,000, particularly preferably 5,000 from the viewpoint of flock strength, and 1,000,000, more preferably 1,000,000 from the viewpoint of the solubility of the polymer flocculant. Preferably it is 500,000, particularly preferably 200,000.
The GPC measurement conditions for Mn of (A0) will be described later.

As a method for producing (A) by neutralizing (A0) with an acid, after producing (A0), neutralization is carried out by adding an acid and water as required, followed by desolvation (and water if necessary. The same applies hereinafter). ), After removing (A0), removing the solvent, and then neutralizing by adding an acid and water if necessary, and by adding (A0) to the acid aqueous solution to neutralize and then removing the solvent, etc. Can be mentioned. Preferred from the viewpoint of industrial and uniform neutralization is a method in which (A0) is produced, neutralized by adding acid and water as necessary, and then desolvated. Examples of the acid include the aforementioned acids having Z ⁻ as an anion.
As a method of producing (A) by quaternizing (A0) with a quaternizing agent, after removing (A0) and then removing the solvent, quaternization is performed by adding a quaternizing agent and water as required. Examples thereof include a method of adding quaternization by adding (A0) to an aqueous solution of a quaternizing agent. From the viewpoint of industrialization and uniform quaternization, the method of quaternization by preparing (A0), removing the solvent, and then adding a quaternizing agent and water as necessary is preferable. Examples of the quaternizing agent include those described above.
(A) may be an aqueous solution, or may be dehydrated and dried to be taken out in a solid state, cooled and pulverized into granules or pellets.

The polymer flocculant of the present invention is characterized by containing the above (A), but if necessary, it may contain a water-soluble (co) polymer (B) other than (A).
Examples of the monomer constituting (B) include water-soluble monomers having an ethylenically unsaturated group, such as the cationic monomers (a), (c4) and (c5), and the unsaturated group-containing monomers (c1) to (c1) to ( c3) and mixtures thereof. In addition, the hydrophobic monomer (b) can be used in combination with the above monomer as long as it does not inhibit the effects of the present invention.

Of the above cationic monomers (a), (c4), (c5) and mixtures thereof constituting (B), (meth) acrylate amine (salt) is more preferable from an industrial viewpoint, and more preferable. It is a quaternary ammonium salt formed by quaternizing dimethylaminoethyl (meth) acrylate hydrochloride or sulfate, and these amines (salts) with a quaternizing agent (as described above).
Of the unsaturated group-containing monomers (c1) to (c3), (meth) acrylamide and polyethylene glycol (polymerization degree 3 to 50) mono (meth) acrylate are preferable from an industrial viewpoint, which will be described later. From the viewpoint of increasing the floc strength due to the ionic crosslinking effect with the inorganic flocculant, unsaturated carboxylic acid is preferable, and (meth) acrylic acid is more preferable from the industrial viewpoint.

When the molecular weight of the water-soluble (co) polymer (B) is expressed in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, the lower limit is usually 1, and the aggregation performance (particularly the floc particle size) From the viewpoint of (increased), preferably 1.5, more preferably 2, particularly preferably 4, most preferably 6, the upper limit is usually 40, preferably 30 from the viewpoint of agglomeration performance (especially improvement in floc strength), more preferably 25, particularly preferably 20, and most preferably 16.

The production method of (B) is not particularly limited, and various radical polymerization methods such as aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization, precipitation polymerization and reverse phase emulsion polymerization can be employed. Among these, aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization and reverse phase emulsion polymerization are preferable from an industrial viewpoint, and aqueous solution polymerization and reverse phase suspension polymerization are more preferable.
As aqueous solution polymerization, for example, an aqueous monomer solution is placed in a container that does not allow heat to enter and exit from the outside, and adiabatic polymerization is performed (for example, Japanese Patent Publication No. 59-40843). And a method of performing constant temperature polymerization (for example, JP-A-3-1899000) can be used.

As the photopolymerization, for example, a method in which a photosensitizer is further added to the monomer as necessary, and polymerization is performed by irradiating light with a wavelength of 300 to 500 nm (for example, a method described in JP-B-45-37033) is used. it can.
Photosensitizers include peroxides (benzoyl peroxide, etc.), azo compounds (azobisisobutyronitrile, etc.), carbonyl compounds (diacetyl, dibenzyl, etc.), sulfur compounds (diphenyl mono- and disulfides, dibenzoyl mono). -And disulfides), halogen compounds (carbon tetrachloride, etc.), and metal salts (iron trichloride, etc.).

The reverse phase suspension polymerization is, for example, a method in which an aqueous monomer solution is dispersed in a water-in-oil type polymer using an oil-soluble polymer substance or a nonionic surfactant as a dispersion stabilizer (for example, JP-A-56-53111). Publication) can be used.
Examples of the oil-soluble polymer substance include cellulose ether (Mn 100 to 100,000, such as ethyl cellulose and ethyl hydroxyethyl cellulose), a copolymer of alkene and α, β-unsaturated polyvalent carboxylic acid (anhydride), or a derivative thereof. [Mn 100-100,000, for example, C20-40 1-olefin and (anhydrous) maleic acid copolymer].
Nonionic surfactants include, for example, sucrose fatty acid esters (C13-100, such as sucrose distearate and sucrose tristearate), sorbitan fatty acid esters (C7-100, such as sorbitan monostearate and sorbitan monooleate) and ( Poly) glycerin fatty acid esters (C6-100, such as glycerin monostearate).
The amount of the oil-soluble polymer substance to be used is based on the weight of the below-mentioned dispersion medium (organic solvent) to be used, the lower limit is usually 0.1%, preferably 0.2% from the viewpoint of stabilizing the dispersed particle diameter, Preferably, it is 0.5%, the upper limit is usually 10%, preferably 5%, more preferably 3% from the viewpoint of reducing the viscosity of the reaction system.
The use amount of the nonionic surfactant is usually 0.1% based on the weight of the below-mentioned dispersion medium (organic solvent) to be used, preferably 0.2% from the viewpoint of stabilizing the dispersed particle diameter, Preferably, it is 0.5%, the upper limit is usually 5%, preferably 3%, more preferably 1% from the viewpoint of reducing the viscosity of the reaction system.
Examples of the dispersion medium (organic solvent) to be used include aliphatic hydrocarbons [C6-30, such as hexane, heptane, n-decane, paraffin (for example, n- and i-paraffin), mineral oil (for example, kerosene, light oil, and medium oil). And alicyclic hydrocarbons (C6-30, such as cyclohexane and decalin) and aromatic hydrocarbons (C6-12, such as benzene, toluene, and xylene) and mixtures thereof.
The amount of the dispersion medium used is preferably 25%, more preferably 40%, particularly preferably 65%, from the viewpoint of the viscosity of the dispersion, based on the total weight of the aqueous monomer solution from the viewpoint of the stability of the dispersion. The upper limit is 1,000%, more preferably 400%, particularly preferably 200%.

Further, as the inverse emulsion polymerization, for example, a method of polymerizing an aqueous monomer solution 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). The described method) can be used.
Examples of the dispersion medium to be used include the same ones as in the reverse phase suspension polymerization. The use amount of the dispersion medium is preferably 20%, more preferably 30%, particularly preferably 40% based on the total weight of the monomer aqueous solution from the viewpoint of emulsion stability, and the preferred upper limit from the viewpoint of the viscosity of the emulsion. 80%, more preferably 70%, particularly preferably 60%.
As the surfactant used for emulsification, for example, those described in Japanese Patent No. 2676483 and Japanese Patent Application Laid-Open No. 9-208802 can be used. Of these, nonionic properties are preferable from the viewpoint of emulsion stability. It is a surfactant.

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

  In the radical polymerization method, the radical polymerization initiator, the type of radical polymerization chain transfer agent used as required, the amount used, and the like are the same as described above.

  The 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%, more preferably 10%, particularly preferably 10% based on the viewpoint of reducing residual monomer. Preferably 15%, most preferably 20%, upper limit is usually 80%, preferably 75% based on temperature control during polymerization, more preferably 70%, particularly preferably 65%, most preferably 60%; In the 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% based on the viewpoint of reducing the residual monomer. From the viewpoint of temperature control during polymerization, preferably 85%, more preferably 80%, particularly preferably 78%, most preferably Preferably 75%; in reverse phase emulsion polymerization, the lower limit is usually 10%, preferably 20%, more preferably 30%, particularly preferably 40%, most preferably 55%, the upper limit based on the viewpoint of reducing residual monomers. Is usually 90%, preferably 80% based on temperature control during polymerization, more preferably 75%, particularly preferably 70%, and most preferably 65%.

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

  In aqueous solution polymerization, the lower limit 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 130 ° C. (under pressure), preferably 100 ° C., more preferably 95 ° C., particularly preferably 90 ° C., most preferably 85 ° C. from the same viewpoint as described above. Further, during polymerization, the temperature may be adjusted by appropriately heating and cooling so as to keep a predetermined temperature constant (for example, a predetermined polymerization temperature ± 5 ° C.), or adiabatic polymerization may be performed in a glass heat insulating container or the like. .

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

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

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

  The pressure at the time of polymerization (unit: kPa, hereinafter indicates absolute pressure) is not particularly limited, but is usually carried out under normal pressure. In the case of aqueous solution polymerization, when the boiling point is exceeded, it is preferably carried out under pressure. Specifically, the preferred lower limit is normal pressure (101 kPa), more preferably 150 kPa, particularly preferably 200 kPa, and the preferred upper limit is 1,000 kPa, more preferably 500 kPa, and particularly preferably 300 kPa. In the case of reverse phase suspension polymerization, the pressure at which the dispersion medium boils or the pressure at which the hydrophobic dispersion medium and water azeotrope is preferably used at the polymerization temperature because the temperature can be easily adjusted during the polymerization. . Specifically, the preferred lower limit is 5 kPa, more preferably 12 kPa, particularly preferably 25 kPa, and the preferred upper limit is 95 kPa, more preferably 80 kPa, and particularly preferably 65 kPa.

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

(B) may be prepared in advance by the above method and then polymer-modified. As the polymer modification reaction, for example, when a water-soluble unsaturated monomer having a hydrolyzable functional group in the molecule such as acrylamide is used, a caustic alkali (for example, sodium hydroxide and potassium hydroxide) or carbonic acid is used during or after the polymerization. Alkali (for example, sodium carbonate and potassium carbonate) is added to partially hydrolyze the amide group of the monomer (the hydrolysis rate is about 1 to 60 mol% based on the total number of moles of all monomers) to convert the carboxyl group. Methods of introduction (for example, JP-A-56-16505), for example, formaldehyde, dialkyl (C1-12) amine and halogenated (for example, chloride, bromide and iodide) alkyl (C1-12) (for example, methyl chloride and Ethyl chloride) and partially cationic groups by Mannich reaction 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). .
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.

The polymer flocculant containing (A) of the present invention includes (A) alone and a polymer flocculant obtained by combining (A) and (B). The polymer flocculant used in combination of (A) and (B) includes a method of containing (A) in advance in (B), and (B) and (A) during sludge treatment. A method of adding to sludge separately, simultaneously or sequentially is included. Among these, the method of using (A) in advance in (B) is preferable from the viewpoint of floc strength.
As a method of previously containing (A) in (B), [1] a method of mixing and containing (B) and (A) produced by the above method, and [2] cutting after producing (B) A method of adding to and mixing with the polymerized gel and drying, and a method of producing (B) by polymerizing the water-soluble monomer having an ethylenically unsaturated group in the presence of [3] (A), etc. Is mentioned. Among these, the homogeneity of (A) in the polymer flocculant and at least a part of (A) are grafted to (B), and the hydrophobicity of (B) is increased, so that the flocs during sludge treatment are increased. From the viewpoint that the strength can be improved, the method [3] is preferable.

  In order to graft (A) to (B) in the method [3] above, it is preferable to introduce a (meth) acryloyl group, a vinyl group or the like into (A). As the introduction method, for example, when (a) is a primary or secondary amine monomer, there is a method of reacting glycidyl (meth) acrylate or maleic anhydride with an amine after the polymerization is completed and the solvent is removed. When (a) is a tertiary amine monomer, it can be introduced by reacting glycidyl (meth) acrylate after the polymerization is completed and after removing the solvent, after adding an organic acid (as described above). And Japanese Patent No. 2629120).

From the viewpoint of easy handling, the polymer flocculant is preferably in the form of powder (in the case of aqueous solution polymerization, photopolymerization and reverse phase suspension polymerization), emulsion (in the case of reverse phase emulsion polymerization) or aqueous solution.
As a pulverization method in the case of aqueous solution polymerization and photopolymerization, the hydrogel after polymerization is shredded and heated using a known dryer (such as a band dryer or a far-infrared dryer) (temperature 80 to 120 ° C). And then dried and pulverized using a known pulverizer [Nara type pulverizer [manufactured by Nara Machinery Co., Ltd.], roll type pulverizer, etc.] to obtain a powder with a volume average particle size of 100 to 2,000 μm. Etc.
As a pulverization method in the case of reverse phase suspension polymerization, a water-containing gel after polymerization (usually volume average particle size of 100 to 2,000 μm) is subjected to solid-liquid separation by filtration or centrifugation, and then a known dryer ( Examples thereof include a method of heating (temperature 30 to 120 ° C.) and drying using a vacuum dryer, screw conveyor, drum dryer or the like.

  The content of (A) in the polymer flocculant of the present invention is preferably 5%, more preferably 6%, particularly preferably 8% based on the weight of the polymer flocculant from the viewpoint of floc strength. From the viewpoint of water solubility of the polymer flocculant, the upper limit is preferably 100%, more preferably 80%, particularly preferably 60%, and most preferably 40%.

When the molecular weight of the polymer flocculant of the present invention is expressed in terms of intrinsic viscosity (dl / g) measured at 30 ° C. in a 1N—NaNO ₃ aqueous solution, the lower limit is usually 1, and the aggregation performance (particularly, increase in floc particle size) From the viewpoint, it is preferably 1.5, more preferably 2, particularly preferably 4, most preferably 6, the upper limit is usually 40, preferably 30 from the viewpoint of agglomeration performance (particularly improvement of floc strength), more preferably 25, especially Preferably 20 and most preferably 16.

Among the polymer flocculants, the cationic colloid equivalent of the cationic polymer flocculant (meq / g) is preferably 0.1, more preferably 0.5, particularly preferably 1 from the viewpoint of aggregation performance. The upper limit is preferably 1.5, and from the same viewpoint, the upper limit is preferably 20, more preferably 12, particularly preferably 8, and most preferably 6. In addition, the cation colloid equivalent value (meq / g) in the amphoteric polymer flocculant is preferably the lower limit of 1, more preferably 1.5, particularly preferably 2, and the preferable upper limit of 6, from the same viewpoint as described above. Further preferred is 5, particularly preferred is 4.5.
The lower limit of the anionic colloid equivalent value (meq / g) is preferably -5, more preferably -4, particularly preferably -3 from the viewpoint of the solubility of the polymer flocculant in water, and the upper limit preferable from the viewpoint of aggregation. Is -0.1, more preferably -0.3, particularly preferably -0.5.
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, and an amphoteric polymer flocculant and Is 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, in water. It is a polymer flocculant that exhibits cationic and anionic properties when dissolved. An anionic polymer flocculant is a polymer flocculant having an anionic group in the molecule, that is, an anionic property when dissolved in water. The polymer flocculant shown.

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

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

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

  The polymer flocculant of 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 long as the effects of the present invention are not impaired An additive selected from the group consisting of 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);
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 acids (eg tripolyphosphoric acid and trimetaphosphoric acid) and their salts [eg alkali metal (eg sodium and potassium) salts, alkaline earth metals (eg calcium and magnesium)
Salts, ammonium salts, C1-20 alkylamine (eg methylamine, ethylamine and octylamine) salts and C2-12 alkanolamine (eg mono-, di- and triethanolamine) salts];

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

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

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

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

These additives may be contained in either (A) and / or (B). Further, additives other than the anti-blocking agent may be preliminarily contained in the monomer aqueous solution before the production of (A) and / or (B) within a range that does not impair the effects of the present invention.
When the additive is contained in (A) and / or (B), the total amount of the additive is preliminarily contained in the monomer aqueous solution based on the weight of (A) and / or (B). In the case, it is usually 30% or less based on the monomer weight, and preferably 0 to 10% from the viewpoint of the effect (floc strength) of the present invention.
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 polymer flocculant of the present invention has an unprecedented floc strength and exhibits a specific flocculation effect and a clarification improvement effect of filtrate (for example, reduction of filtrate SS). It can be used as a polymer flocculant for dehydration treatment of organic or inorganic sludge generated in the above, and is particularly suitably used for dehydration treatment of organic sludge.

  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 to add and mix the polymer flocculant to sludge or wastewater to form a floc. The method is not particularly limited as long as it is a method for performing solid-liquid separation.

  Moreover, when using the polymer flocculent of this invention for sludge or wastewater, you may use together 1 or more types of well-known inorganic and organic coagulants. When these are used in combination, the organic coagulant and / or inorganic coagulant is added to the sludge, and then the polymer coagulant of the present invention is added. The organic coagulant and / or inorganic coagulant and polymer coagulant are added simultaneously. Method. Any method of adding an organic coagulant and / or an inorganic coagulant to the cake after adding the polymer flocculant of the present invention and dehydrating may be employed.

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

  When a known inorganic and / or organic coagulant is added to sludge or wastewater, the amount used is the type of sludge or wastewater, the size of suspended particles, and the weight of evaporation residue in wastewater (hereinafter abbreviated as TS). ), Etc., but based on the TS in the sludge or wastewater, in the known inorganic coagulant, the preferable lower limit from the viewpoint of cohesiveness is 0.5%, more preferably 1%, particularly preferably 2%, the same From the viewpoint, the preferable upper limit is 40%, more preferably 30%, particularly preferably 20%. In the known organic coagulants, the preferable lower limit is 0.01%, more preferably 0.05%, from the viewpoint of aggregation. The upper limit is preferably 0.1%, and from the same viewpoint, the upper limit is preferably 10% or less, more preferably 8% or less, and particularly preferably 5%.

The method for adding the polymer flocculant of the present invention to sludge or wastewater is not particularly limited, and it may be added to the sludge or wastewater as it is, but from the viewpoint of uniform mixing, the polymer flocculant is preferred. This is a method of adding an aqueous solution to the sludge or waste water. The concentration when the polymer flocculant is used as an aqueous solution 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. However, when the powdery polymer flocculant is dissolved in water, if it is added at once, it becomes undesirably generated and difficult to dissolve in water.
Moreover, in order to improve the solubility of the polymer flocculant of the present invention, it is preferable to add and adjust the aforementioned pH adjuster so that the pH of the dissolved aqueous solution is in the range of 2.0 to 5.0. More preferably, the pH is 2.5 to 4.0, and particularly preferably 2.7 to 3.5.

  The amount of the polymer flocculant used when added to the sludge or wastewater varies depending on the type of sludge or wastewater, the content of suspended particles and the molecular weight of the polymer flocculant, and is not particularly limited. From the viewpoint of flocculation performance based on TS in wastewater, the preferred lower limit is 0.01%, more preferably 0.05%, particularly preferably 0.1%, most preferably 0.5%, from the same viewpoint, The upper limit is preferably 10%, more preferably 8%, particularly preferably 5%, and most preferably 3%.

  In addition, as a dehydration method (solid-liquid separation method) of floc sludge formed by the above-described treatment method, for example, gravity sedimentation, membrane filtration, column filtration, pressurized flotation, and a concentration device (for example, thickener) and a dehydration device ( Examples thereof include a method using a centrifugal dehydrator, a screw press dehydrator, a belt press dehydrator, a filter press dehydrator, and a capillary dehydrator. Among these, the method using a dehydrator, particularly a centrifugal dehydrator and a screw press dehydrator is preferable from the viewpoint of high floc strength, which is a specific aggregating performance of the polymer flocculant of the present invention.

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 a manufacture example and an Example represents a weight part, and% represents weight%. Mn of (A0) was measured under the following GPC conditions.
(GPC measurement conditions)
Measuring machine: HLC-8220GPC, manufactured by Tosoh Corporation Column: Guardcolumn α, TSKgel α-M
Eluent: DMF LiBr 0.01M
Flow rate: 1 ml / min
Sample concentration: 0.125%
Injection volume: 100 μl
Column temperature: 40 ° C
Calibration curve standard material: polystyrene The intrinsic viscosity [η] (dl / g) of the polymer flocculant 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 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, 1997 edition).
The floc particle size, filtrate amount, filter cloth peelability, cake moisture content, and filtrate clarity in this example were evaluated according to the following methods.

<Flock particle size>
Jar tester [Miyamoto Riken Kogyo Co., Ltd., model JMD-6HS-A, and so on. ] Two plate-shaped PVC stirring blades (diameter: 5 cm, height: 2 cm, thickness: 0.2 cm) are attached to the stirring bar continuously in a vertical shape to form a cross, and 200 parts of sludge or waste water is placed in a 500 ml beaker. And set it on the jar tester. While rotating the jar tester at 120 rpm and slowly stirring the sludge, add a predetermined amount of 0.2% by weight of the polymer flocculant aqueous solution at once, and after stirring for 30 seconds, stop stirring and reduce the size of the aggregate. Observe visually (the floc particle diameter at 120 rpm is shown in the table).
Subsequently, the rotational speed is set to 300 rpm, and after stirring for 30 seconds, the stirring is stopped and the size of the aggregate is visually observed again (the floc particle size at the rotational speed of 300 rpm is shown in the table).

<Amount of filtrate>
T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, graduated cylinder that can measure 300 ml, set sludge after the above floc particle size test and filter at once Then, using a stopwatch, measure the filtrate amount 60 seconds after immediately after the addition.
<Filter cloth peelability>
Part of the filtered sludge is removed with a spatula and subjected to a dehydration test (2 kg / cm ² , 60 seconds) using a press filter tester, and the peelability of the dewatered cake from the filter cloth after the test is evaluated according to the following criteria: To do.

A: Very easy to peel off (almost no filter cloth deposits)
○: Easy to peel off (slightly attached filter cloth)
Δ: Slightly difficult to peel off (there is a filter cloth deposit, slightly sticking to the inside of the filter cloth)
×: Hard to peel off (attaches to the inside of the filter cloth)

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

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

<Filtrate clarity>
Using the filtrate after measuring the above filtrate amount, an absorbance meter [manufactured by Shimadzu Corporation, UV-1200, the same shall apply hereinafter. ], The absorbance at wavelengths of 590 nm and 700 nm is measured, and the filtrate clarity is evaluated. The numerical value (%) of absorbance indicates a value when the absorbance of ion-exchanged water is 100%.

[Production of Copolymer (A)]
Production Example 1
In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, a dropping funnel, and a mantle heater, 200 parts of i-propyl alcohol (hereinafter abbreviated as IPA) was charged and heated to reflux with stirring. From the dropping funnel, 96 parts of N, N-dimethylaminoethyl methacrylate (hereinafter abbreviated as DAM) as a cationic monomer, 104 parts of lauryl methacrylate as a hydrophobic monomer, and azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator. 1.6 parts of the homogeneous mixed solution was dropped into the reaction vessel in 4 hours with stirring in the reaction vessel at 80 to 85 ° C. After the dropwise addition, the mixture was aged at the same temperature for 2 hours to complete the polymerization. Further, a solution of 50 parts of IPA and 0.4 part of AIBN was added dropwise over 1 hour and aged at the same temperature for 3 hours to obtain a copolymer (A01) A solution was obtained. The Mn of (A01) was 20,000.
Thereafter, 64 parts of hydrochloric acid (containing 35% hydrogen chloride, the same shall apply hereinafter) was added dropwise over 1 hour, and then 200 parts of water was added dropwise over 30 minutes and cooled. The polymer solution was transferred to a metal tray, and IPA and water were removed at 80 ° C. in a vacuum dryer. The polymer was cooled and pulverized with a juicer mixer to obtain a granular copolymer (A1).
Production Example 2
To the above (A01) solution, 5 parts of acetic acid and 1.2 parts of glycidyl methacrylate were added and reacted at 80 ° C. for 2 hours to obtain a copolymer (A02) solution. The Mn of (A02) was 22,000. Thereafter, a granular copolymer (A2) was obtained in the same manner as in Production Example 1.
Production Example 3
A copolymer (A03) [Mn25,000] solution was prepared in the same manner as in Production Example 1 except that the monomer was replaced with 172 parts of DAM, 6 parts of lauryl methacrylate, 20 parts of styrene, and 2 parts of methacrylic acid. After that, a granular copolymer (A3) was obtained in the same manner as in Production Example 1 except that 64 parts of hydrochloric acid was replaced with 114 parts.
Production Example 4
In Production Example 2, a copolymer (A04) [Mn27,000] solution was obtained in the same manner as in Production Example 2 except that the (A01) solution was replaced with the (A03) solution, and then 64 parts of hydrochloric acid was added. A granular copolymer (A4) was obtained in the same manner as in Production Example 2, except that the amount was changed to 114 parts.
Production Example 5
In Production Example 1, a copolymer (A05) [Mn 15,000] solution was obtained in the same manner as in Production Example 1 except that the monomer was replaced with 120 parts of DAM, 60 parts of lauryl methacrylate, and 20 parts of methacrylic acid. In the same manner as in Example 1, except that 80 parts of hydrochloric acid was used, a granular copolymer (A5) was obtained in the same manner as in Production Example 1.
Production Example 6
In Production Example 1, a copolymer (A06) [Mn25,000] solution was obtained in the same manner as in Production Example 1 except that the monomer was replaced with 123 parts of DAM, 10 parts of lauryl methacrylate, and 67 parts of styrene. A granular copolymer (A6) was obtained in the same manner as in Production Example 1 except that 64 parts were replaced with 82 parts.
Comparative production example 1
In Production Example 1, a copolymer (ratio A01) [Mn 25,000] solution was obtained in the same manner as in Production Example 1 except that the monomer was replaced with 178 parts of DAM and 22 parts of lauryl methacrylate, and then, 64 parts of hydrochloric acid was added to 118 parts. A granular copolymer (Ratio A1) was obtained in the same manner as in Production Example 1 except that the part was changed to the part.
Comparative production example 2
In Production Example 1, a copolymer (ratio A02) [Mn 20,000] solution was obtained in the same manner as in Production Example 1 except that the monomer was replaced with 180 parts of DAM and 20 parts of methacrylic acid. A granular copolymer (Ratio A2) was obtained in the same manner as in Production Example 1 except that the part was changed to the part.
Comparative production example 3
In Production Example 1, a copolymer (ratio A03) [Mn 27,000] solution was obtained in the same manner as in Production Example 1 except that the monomer was replaced with 200 parts of DAM, and then 64 parts of hydrochloric acid was replaced with 133 parts. Except that, in the same manner as in Production Example 1, a granular copolymer (ratio A3) was obtained.

[Production of polymer flocculant (X)]
Example 1
In a 100 ml beaker, 45 parts of a 60% aqueous solution of DAM methyl chloride quaternary salt and 3 parts of (A1) were added and stirred to obtain a uniform aqueous solution. The entire amount of the aqueous solution was transferred to a test tube having an inner diameter of 25 mm and a height of 200 mm, and after nitrogen substitution was performed by bubbling nitrogen through the solution for 5 minutes, a 2% aqueous solution of 2,2′-azobis- (amidinopropane) dihydrochloride was added. 2.5 parts was added, and polymerization was carried out at 50 ° C. for 20 hours in a sealed state. Thereafter, the gel in the test tube is taken out, chopped, dried at 80 ° C. for 2 hours with a circulating drier, and further pulverized with a juicer mixer (volume average particle diameter of 0.1 to 1.7 mm, the same applies hereinafter). A flocculant (X1) was obtained. The intrinsic viscosity of (X1) was 6.1 dl / g (hereinafter expressed only by numerical values), and the cation colloid equivalent value was 4.6 meq / g (hereinafter expressed only by numerical values).
Example 2
A polymer flocculant (X2) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (A2) in Example 1. The intrinsic viscosity of (X2) was 7.1, and the cation colloid equivalent value was 4.6.
Example 3
A polymer flocculant (X3) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (A3) in Example 1. The intrinsic viscosity of (X3) was 7.5, and the cation colloid equivalent value was 4.8.
Example 4
In Example 1, a polymer flocculant (X4) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (A4). The intrinsic viscosity of (X4) was 8.0, and the cation colloid equivalent value was 4.8.
Example 5
In Example 1, a polymer flocculant (X5) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (A5). The intrinsic viscosity of (X5) was 8.1, and the cation colloid equivalent value was 4.7.
Example 6
In Example 1, a polymer flocculant (X6) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (A6). The intrinsic viscosity of (X6) was 7.1, and the cation colloid equivalent value was 4.7.
Example 7
In Example 1, 45 parts of a 60% aqueous solution of DAM methyl chloride quaternary salt is 47 parts, (A1) 3 parts is 1.8 parts, and 2,2′-azobis- (amidinopropane) dihydrochloride 2 A polymer flocculant (X7) was obtained in the same manner as in Example 1 except that 2.5 parts of the% aqueous solution was replaced with 2.6 parts. The intrinsic viscosity of (X7) was 8.2, and the cation colloid equivalent value was 4.7.
Example 8
In Example 1, 45 parts of 60% aqueous solution of DAM methyl chloride quaternary salt is 25 parts, 3 parts of (A1) is 15 parts, and 2% aqueous solution of 2,2′-azobis- (amidinopropane) dihydrochloride. The polymer flocculant (X8) was obtained in the same manner as in Example 1 except that 2.5 parts were replaced with 1.4 parts. The intrinsic viscosity of (X8) was 4.4, and the cation colloid equivalent value was 3.8.
Comparative Example 1
In Example 1, a polymer flocculant (ratio X1) was obtained in the same manner as in Example 1 except that (A1) was not used. (Ratio X1) had an intrinsic viscosity of 6.0 and a cation colloid equivalent value of 4.8.
Comparative Example 2
In Example 1, a polymer flocculant (Ratio X2) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A1). (Ratio X2) had an intrinsic viscosity of 7.1 and a cation colloid equivalent value of 4.8.
Comparative Example 3
In Example 1, a polymer flocculant (Ratio X3) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A2). (Ratio X3) had an intrinsic viscosity of 7.2 and a cation colloid equivalent value of 4.8.
Comparative Example 4
In Example 1, a polymer flocculant (Ratio X4) was obtained in the same manner as in Example 1 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A3). (Ratio X4) had an intrinsic viscosity of 7.0 and a cation colloid equivalent value of 4.9.
Example 9
In Example 1, 45 parts of a 60% aqueous solution of DAM methyl chloride quaternary salt, 21 parts of a 60% aqueous solution of DAM methyl chloride quaternary salt, 3.8 parts of a 60% aqueous solution of dimethylaminoethyl acrylate methyl chloride quaternary salt, A polymer flocculant (X9) was obtained in the same manner as in Example 1 except that 20.6 parts of 50% aqueous solution of acrylamide and 1.7 parts of acrylic acid were used. The intrinsic viscosity of (X9) was 8.0, the cation colloid equivalent value was 2.7, and the anion colloid equivalent value was −0.8 meq / g (hereinafter, only represented by numerical values).
Example 10
In Example 9, a polymer flocculant (X10) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (A2). The intrinsic viscosity of (X10) was 9.1, the cation colloid equivalent value was 2.7, and the anion colloid equivalent value was -0.8.
Example 11
In Example 9, a polymer flocculant (X11) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (A3). The intrinsic viscosity of (X11) was 10.0, the cation colloid equivalent value was 2.9, and the anion colloid equivalent value was -0.8.
Example 12
In Example 9, a polymer flocculant (X12) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (A4). The intrinsic viscosity of (X12) was 10.1, the cation colloid equivalent value was 2.9, and the anion colloid equivalent value was -0.8.
Example 13
In Example 9, a polymer flocculant (X13) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (A5). The intrinsic viscosity of (X13) was 10.2, the cation colloid equivalent value was 2.8, and the anion colloid equivalent value was -0.9.
Example 14
In Example 9, a polymer flocculant (X14) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (A6). The intrinsic viscosity of (X14) was 10.1, the cation colloid equivalent value was 2.8, and the anion colloid equivalent value was -0.8.
Example 15
In Example 9, 21 parts of a 60% aqueous solution of DMA methyl chloride quaternary salt was added to 21.9 parts, 3.8 parts of a 60% aqueous solution of dimethylaminoethyl acrylate methyl chloride quaternary salt was added to 4.0 parts, and acrylamide 20.6 parts of a 50% aqueous solution of the above, 21.5 parts, 1.7 parts of acrylic acid, 1.8 parts, (A1) 3 parts, 1.8 parts, 2,2′-azobis- (amidinopropane) ) A polymer flocculant (X15) was obtained in the same manner as in Example 9 except that 2.5 parts of a 2% aqueous solution of dihydrochloride was replaced with 2.6 parts. The intrinsic viscosity of (X15) was 11.0, the cation colloid equivalent value was 2.7, and the anion colloid equivalent value was -0.8.
Example 16
In Example 9, 21 parts of a 60% aqueous solution of DMA methyl chloride quaternary salt was added to 11.7 parts, 3.8 parts of a 60% aqueous solution of dimethylaminoethyl acrylate methyl chloride quaternary salt was added to 2.1 parts, acrylamide 21.4 parts of a 50% aqueous solution, 11.4 parts, 1.7 parts of acrylic acid, 0.9 parts, (A1) 3 parts, 15 parts of 2,2′-azobis- (amidinopropane) di A polymer flocculant (X16) was obtained in the same manner as in Example 9 except that 2.5 parts of a 2% aqueous solution of hydrochloride was replaced with 1.4 parts. The intrinsic viscosity of (X16) was 5.3, the cation colloid equivalent value was 2.7, and the anion colloid equivalent value was -0.4.
Comparative Example 5
In Example 9, a polymer flocculant (ratio X5) was obtained in the same manner as in Example 9 except that (A1) was not used. (Ratio X5) had an intrinsic viscosity of 8.2, a cation colloid equivalent value of 2.7, and an anion colloid equivalent value of -0.9.
Comparative Example 6
In Example 9, a polymer flocculant (Ratio X6) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A1). (Ratio X6) had an intrinsic viscosity of 8.3, a cation colloid equivalent value of 2.9, and an anion colloid equivalent value of -0.8.
Comparative Example 7
In Example 9, a polymer flocculant (Ratio X7) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A2). (Ratio X7) had an intrinsic viscosity of 8.0, a cation colloid equivalent value of 2.9, and an anion colloid equivalent value of -0.9.
Comparative Example 8
In Example 9, a polymer flocculant (Ratio X8) was obtained in the same manner as in Example 9 except that 3 parts of (A1) was replaced with 3 parts of (Ratio A3). (Ratio X8) had an intrinsic viscosity of 8.1, a cation colloid equivalent value of 2.9, and an anion colloid equivalent value of -0.8.

  Table 1 shows the compositions, colloid equivalent values, and intrinsic viscosities of the polymer flocculants (X1) to (X16) and (Ratio X1) to (Ratio X8) obtained above.

ＤＡＭ ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレート
ＬＭＡ ：ラウリルメタクリレート
Ｓｔ ：スチレン
ＭＡｃ ：メタクリル酸
ＧＭＡ ：グリシジルメタクリレート
ＡＡＭ ：アクリルアミド
ＤＡＡＱ：Ｎ，Ｎ−ジメチルアミノエチルアクリレートのメチルクロライド４級アンモ
ニウム塩
ＤＡＭＱ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレートのメチルクロライド４級アン
モニウム塩
ＡＡｃ ：アクリル酸

DAM: N, N-dimethylaminoethyl methacrylate LMA: Lauryl methacrylate St: Styrene MAc: Methacrylic acid GMA: Glycidyl methacrylate AAM: Acrylamide DAAQ: Methyl chloride quaternary ammonia of N, N-dimethylaminoethyl acrylate
Nium salt DAMQ: N, N-dimethylaminoethyl methacrylate methyl chloride quaternary amine
Monium salt AAc: Acrylic acid

[Performance evaluation of polymer flocculants]
Examples 1-8, Comparative Examples 1-4
(X1) to (X8) and (Ratio X1) to (Ratio X4) were used as polymer flocculants, and performance evaluation was performed on each.
Each polymer flocculant was dissolved in ion exchange water to obtain an aqueous solution having a solid content of 0.2%. Take 200 parts of digested sludge [pH 6.0, TS 1.9%, organic content 63%] collected from the sewage treatment plant A in a required number of 500 ml beakers, and add 17 parts of each aqueous solution previously prepared (solid content) The amount of addition was 0.9% / TS), and the mixture was stirred and mixed, and the performance was evaluated with respect to the floc particle size, the filtrate amount, the filter cloth peelability, the cake moisture content, and the filtrate clarity by the above-described evaluation methods. The results are shown in Table 2.
From Table 2, in Examples 1-8, compared with Comparative Examples 1-4, a floc with a large particle diameter is formed, and the flocs once formed are not easily broken even under high agitation (300 rpm) (the floc is strong). ), A high filtration rate, and excellent effects in filter cloth peelability, cake moisture content (dehydration) and filtrate clarification.

Examples 9-17, Comparative Examples 5-8
(X9) to (X16), (A1) / (Ratio X5), and (Ratio X5) to (Ratio X8) were used as polymer flocculants, and performance evaluation was performed on each.
Each polymer flocculant was dissolved in ion exchange water to obtain an aqueous solution having a solid content of 0.2%.
About Example 17, it was set as the 0.2% aqueous solution whose ratio of (A1) and (ratio X5) is 1/9 (weight ratio).
200 parts of mixed sludge collected from T sewage treatment plant [excess sludge / digested sludge = 1/1 (weight ratio), pH 5.8, TS 2.7%, organic content 72%] in 200 ml beakers of the required number. Polytetsu [manufactured by Nittetsu Mining Co., Ltd., and so on. ] After adding 0.27 parts and stirring and mixing with a hand mixer for 30 seconds, 19 parts of each previously prepared aqueous solution was added (solid content addition amount 0.7% / TS), and the above Examples 1 to 8, The performance was evaluated in the same manner as in Comparative Examples 1 to 4. The results are shown in Table 3.
From Table 3, in Examples 9-17, compared with Comparative Examples 5-8, flocs having a large particle diameter were formed, and the flocs once formed were not easily broken even under high agitation (300 rpm) (the flocs are strong). ), A high filtration rate, and excellent effects in filter cloth peelability, cake moisture content (dehydration) and filtrate clarification.

実施例１８〜２１、比較例９〜１１
（Ａ１）、（Ａ３）、（Ａ５）、（Ａ６）、（比Ａ１）、（比Ａ２）、（比Ａ３）を高分子凝集剤として用い、それぞれについて性能評価を行った。
高分子凝集剤をそれぞれイオン交換水に溶解して固形分含量０．２％の水溶液とした。Ｈ食品工場から採取した廃水［ｐＨ６．６、ＴＳ０．８％、有機分７２％］を必要な個数の５００ｍｌビーカーに２００部ずつ採り、それぞれポリテツ０．８部を添加しハンドミキサーで３０秒間撹拌混合し、１０％の水酸化ナトリウム水溶液を添加してｐＨを７．０とした後、先に調製した各水溶液１０部を添加（固形分添加量１．２５％／ＴＳ）して、上記実施例１〜８、比較例１〜４と同様に性能評価した。結果を表４に示す。
表４から、実施例１８〜２１では、比較例９〜１１に比べて、大粒径のフロックが形成され、高撹拌下（３００ｒｐｍ）でも一旦形成されたフロックが壊れにくい（フロックが強固である）こと、ろ過速度が速いこと、およびろ布剥離性、ケーキ含水率（脱水性）およびろ液清澄性において優れた効果を示すことがわかる。

Examples 18-21, Comparative Examples 9-11
(A1), (A3), (A5), (A6), (Ratio A1), (Ratio A2), and (Ratio A3) were used as polymer flocculants, and performance evaluation was performed on each.
Each polymer flocculant was dissolved in ion exchange water to obtain an aqueous solution having a solid content of 0.2%. H Take 200 parts of waste water [pH 6.6, TS 0.8%, organic content 72%] collected from a food factory in a required number of 500 ml beakers, add 0.8 parts of polytetsu and stir with a hand mixer for 30 seconds. After mixing and adding 10% aqueous sodium hydroxide solution to adjust the pH to 7.0, 10 parts of each previously prepared aqueous solution was added (solid content addition amount 1.25% / TS). The performance was evaluated in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4. The results are shown in Table 4.
From Table 4, in Examples 18-21, compared to Comparative Examples 9-11, flocs having a large particle size were formed, and the flocs once formed were not easily broken even under high agitation (300 rpm) (the flocs are strong) ), A high filtration rate, and excellent effects in filter cloth peelability, cake moisture content (dehydration) and filtrate clarification.

  The polymer flocculant of the present invention is suitably used for the dehydration treatment of organic sludge or inorganic sludge generated by the treatment of sewage or the like or factory wastewater, particularly for the dehydration treatment of organic sludge, a dispersant, Wide range of uses such as scale inhibitors, coagulants, decolorizers, thickeners, antistatic agents, textile treatment agents, and especially flocculants for drilling and muddy water treatment, papermaking chemicals (for example, formation forming aids for the paper industry, It is also suitably used for drainage yield improvers, drainage improvers and paper strength enhancers.

Claims (4)

50 to 85 mol% of a repeating unit represented by the following general formula (1), 15 to 50 mol% of a compound having one (meth) acryloyl group and an aromatic ring having one vinyl group Containing a copolymer (A) having a repeating unit consisting of one or more hydrophobic monomers (b) selected from the group consisting of vinyl compounds, and in the presence of (A), an ethylenically unsaturated group A polymer flocculant obtained by polymerizing a water-soluble monomer containing

[Wherein X is O or NH; Q is an alkylene group having 2 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ¹ is H or a methyl group; R ² , R ³ and R ⁴ are each independently selected. And H, an alkyl, arylalkyl or alkylaryl group having 1 to 16 carbon atoms; Z ⁻ represents a counter anion. ] The polymer flocculant according to claim 1, wherein the content of (A) is 5 to 80 % by weight. 50 to 85 mol% of a cationic monomer (a) represented by the following general formula (2), 15 to 50 mol% of a compound having one (meth) acryloyl group and one vinyl group A copolymer (A0) obtained by copolymerizing a monomer consisting of one or more hydrophobic monomers (b) selected from the group consisting of aromatic ring-containing vinyl compounds in an organic solvent is neutralized with an acid or The method for producing a polymer flocculant comprising the copolymer (A) according to claim 1 or 2 , wherein the polymer is quaternized with a quaternizing agent.

[Wherein, X is O or NH; Q is an alkylene group having 2 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R ¹ is H or a methyl group; R ² and R ³ are each independently H, An alkyl, arylalkyl or alkylaryl group having 1 to 16 carbon atoms is represented. ] 3. A method for treating organic sludge, comprising adding the polymer flocculant according to claim 1 or 2 to organic sludge to form a floc for solid-liquid separation.