JP2005144346A - Coagulating agent and its usage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coagulating agent comprising two kinds of cross-linking water-soluble ionic polymers and its usage, especially a coagulating agent solving the problem of reducing the loadings while retaining the advantages of the cross-linking polymers. <P>SOLUTION: The agent comprises a vinyl polymer type cross-linking water-soluble ionic polymer of a charge inclusion rate of ≥35% and a vinyl polymer type cross-linking water-soluble ionic polymer of a charge inclusion rate of 5-35%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aggregating treatment agent comprising two kinds of crosslinkable water-soluble ionic polymers and a method for using the same, and more specifically, an ionic monomer and a polyfunctional monomer and / or a crosslinkable monomer. A vinyl-polymerizable cross-linkable ionic water-soluble polymer (A) having a charge inclusion rate of 35% or more produced by copolymerization of a monomer mixture containing an ionic monomer as an essential component, an ionic monomer and a plurality of vinyl groups A vinyl-polymerizable crosslinkable ionic water-soluble polymer having a charge inclusion ratio of 5% or more and less than 35%, which is obtained by copolymerizing a monomer mixture containing a polyfunctional monomer and / or a crosslinkable monomer as an essential component The present invention relates to an aggregating agent combined with (B) and a method for using the same.

  Conventionally, a cationic polymer flocculant has been used for dewatering various sludges. Due to the recent increase in sludge generation and deterioration of sludge properties, conventional cationic polymer flocculants have limited sludge throughput, dehydrated cake moisture content, SS recovery rate, from cake filter cloth The treatment state is not always satisfactory in terms of peelability and the like, and improvement is demanded.

  On the other hand, for the purpose of lowering the moisture content of the dehydrated cake and improving the peelability from the filter cloth, Patent Document 1), Patent Document 2, and the like disclose crosslinkable ionic polymer flocculants. As described above, the crosslinkable water-soluble polymer has various characteristics and functions. However, when the polymer is applied to a sludge dehydrating agent, the molecular spread in the aqueous solution is relatively small. There is a problem that the amount of addition increases compared to the above. In order to improve such disadvantages of the crosslinkable water-soluble polymer, Patent Document 3 or Patent Document 4 contains a quaternary ammonium base, a methacrylate monomer, an acrylate monomer and an anion. An amphoteric polymer dehydrating agent obtained by copolymerizing an ionic monomer at a certain ratio is disclosed. However, these also did not fully satisfy the purpose.

Japanese Patent Laid-Open No. 2-219887 Japanese Patent Publication No. 8-164 JP 7-256299 A JP 7-256300 A

  When a crosslinkable water-soluble ionic polymer is used as a sludge dewatering agent, excellent points such as a decrease in the moisture content of the dehydrated cake are manifested, but on the other hand, the amount of addition is inevitably increased until the effect is manifested. As a result, there arises a problem of an increase in cost. An object of the present invention is to provide an aggregating agent that leaves the advantages of a crosslinkable water-soluble ionic polymer and solves the problem of reducing the amount of addition.

  As a result of intensive studies to solve the above problems, the present inventor has reached the following invention. That is, the invention of claim 1 includes a vinyl polymerization-type crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and a vinyl polymerization-type crosslinkable water-soluble ionicity having a charge inclusion rate of 5 to less than 35%. The present invention relates to an aggregating agent combined with a polymer (B).

一般式（１）
Ｒ_１は水素又はメチル基、Ｒ_２、Ｒ_３は炭素数１〜３のアルキルあるいはアルコキシル基、Ｒ_４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基を表わす、Ｘ_１ ⁻は陰イオンをそれぞれ表わす。

一般式（２）
Ｒ_５は水素又はメチル基、Ｒ_６、Ｒ_７は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｘ_２ ⁻は陰イオンをそれぞれ表わす。

一般式（３）
Ｒ_８は水素、メチル基またはカルボキシメチル基、ＱはＳＯ_３ ⁻、Ｃ_６Ｈ_４ＳＯ_３ ⁻、ＣＯＮＨＣ（ＣＨ_３）_２ＣＨ_２ＳＯ_３ ⁻、Ｃ_６Ｈ_４ＣＯＯ⁻あるいはＣＯＯ⁻、Ｒ_９は水素またはＣＯＯ⁻Ｙ_１ ^＋、Ｙ^＋およびＹ_１ ^＋は水素イオンまたは陽イオン In the invention of claim 2, the vinyl polymerized crosslinkable water-soluble ionic polymer (A) and (B) is a monomer represented by the following general formula (1) and / or (2): 100 mol%, a monomer mixture consisting of 0 to 50 mol% of the monomer represented by the following general formula (3) and 0 to 95 mol% of a nonionic monomer and a polyfunctional monomer and / or An aqueous solution of a crosslinkable monomer was emulsified and polymerized by a surfactant so that the water-immiscible organic liquid was a continuous phase and the aqueous monomer mixture solution was a dispersed phase. The aggregating agent according to claim 1, wherein the agent is an aggregating agent.

General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are alkyl or alkoxyl groups having 1 to ₃ carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group, or a benzyl group. A may be oxygen or NH, B may represent an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, and X ₁ ⁻ may represent an anion.

General formula (2)
R ₅ represents hydrogen or a methyl group, R ₆ and R ₇ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.

General formula (3)
R ₈ is hydrogen, methyl group or carboxymethyl group, Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , R ₉ Is hydrogen or COO ⁻ Y ₁ ⁺ , Y ⁺ and Y ₁ ⁺ are hydrogen ions or cations

According to the invention of claim 3, the vinyl polymerized crosslinkable water soluble ionic polymer (A) or the vinyl polymerized crosslinkable water soluble ionic polymer (B) is a single monomer of (A1) or (B1), respectively. It is manufactured by emulsifying and polymerizing an aqueous body mixture solution with a surfactant so that the water-immiscible organic liquid becomes a continuous phase and an aqueous monomer mixture solution as a dispersed phase, and then appropriately adding a phase inversion agent. The aggregating agent according to claim 1, wherein:
Monomer composition (A1): 5-100 mol% of the monomer represented by the general formula (1) and / or (2), and 0-50 mol of the monomer represented by the general formula (3) % And non-ionic monomer 0-95 mol%. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.
Monomer composition (B1): The crosslinkable water-soluble ionic polymer (B) contains 5 to 100 mol% of the monomer represented by the general formula (3) and nonionic monomers 0 to 95. Mol%.
Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.

According to the invention of claim 4, the vinyl polymerization crosslinkable water-soluble ionic polymer (A) or the vinyl polymerization crosslinkable water soluble ionic polymer (B) is a single amount of (A2) or (B2), respectively. It is manufactured by emulsifying and polymerizing an aqueous body mixture solution with a surfactant so that the water-immiscible organic liquid becomes a continuous phase and an aqueous monomer mixture solution as a dispersed phase, and then appropriately adding a phase inversion agent. The aggregating agent according to claim 1, wherein:
Monomer composition (A2): 5-100 mol% of the monomer represented by the general formula (3) and 0-95 mol% of a nonionic monomer. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.
Monomer composition (B2): 5-100 mol% of the monomer represented by the general formula (1) and / or (2), and 0-50 mol of the monomer represented by the general formula (3) % And non-ionic monomer 0-95 mol%. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.

The invention of claim 5 is characterized in that an aggregating agent combining the crosslinkable water-soluble ionic polymers (A) and (B) according to claims 1 to 4 is added to sludge and dehydrated by a dehydrator. This is a sludge dewatering method.

  A crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and a crosslinkable water-soluble ionic polymer (B) having a charge inclusion rate of 5 or more and less than 35%, comprising the W / O type emulsion of the present invention. ) In combination, it suppresses the increase in processing cost, which is a disadvantage of the crosslinkable water-soluble ionic polymer, and reduces the amount of addition while retaining the advantages such as the reduced moisture content of the dehydrated cake. Can be solved.

In the present invention, a cationic crosslinkable water-soluble ionic polymer and a crosslinkable water-soluble ionic polymer that is amphoteric and has a positive molar concentration difference between a cationic monomer and an anionic monomer, The charge inclusion rate is calculated as follows.
Charge inclusion rate [%] = (1−α / β) × 100
α is a 0.01% aqueous solution of a crosslinkable water-soluble ionic polymer adjusted to pH 4.0 with acetic acid by a PCD titration apparatus (M &uuml; tek PCD 03, M &uuml; tek PCD-Two Titortor Version 2) manufactured by Mutec. Dropping solution: 1/1000 N aqueous polyvinyl sulfonate solution, dropping rate: 0.05 ml / 10 sec, end point determination: 0 mV. Titration determined by titration. β is added to a 0.01% aqueous solution of a crosslinkable water-soluble ionic polymer adjusted to pH 4.0 with acetic acid in an amount sufficient to neutralize the charge with a 1 / 400N aqueous potassium polyvinyl sulfonate solution, and sufficiently stirred. Similarly, titrate with a PCD titrator at a drop solution: 1 / 1000N diallyldimethylammonium chloride aqueous solution, drop rate: 0.05 ml / 10 sec, end point determination: 0 mV, and subtract this titration value from the blank value. . The blank value is the same as the sample adjusted to pH 4.0 with acetic acid, and the same concentration of potassium polyvinyl sulfonate aqueous solution is similarly added by a PCD titration apparatus. Dropping solution: 1 / 1000N diallyldimethylammonium chloride aqueous solution, dropping rate: 0.05 ml / 10 sec, end point determination: titration obtained by titration at 0 mv.

In the present invention, an anionic crosslinkable water-soluble ionic polymer and a crosslinkable water-soluble ionic polymer that is amphoteric and has a negative difference in molar concentration between the cationic monomer and the anionic monomer, The charge inclusion rate is calculated as follows.
Charge inclusion rate [%] = (1−α / β) × 100
α is a 0.01% aqueous solution of a cross-linkable water-soluble ionic polymer adjusted to pH 10.0 with ammonia using a PCD titration apparatus (M &uuml; tek PCD 03, M &uuml; tek PCD-Two Titortor Version 2) manufactured by Mutec. Dropping solution: 1 / 1000N diallyldimethylammonium chloride aqueous solution, dropping rate: 0.05 ml / 10 sec, end point determination: 0 mV. Titration determined by titration. β is added to a 0.01% aqueous solution of a crosslinkable water-soluble ionic polymer adjusted to pH 10.0 with ammonia by adding a sufficient amount of 1 / 400N diallyldimethylammonium chloride aqueous solution to neutralize the charge, and sufficiently agitated. In the same manner, titrate with a PCD titrator at a drop solution: 1 / 1000N potassium polyvinylsulfonate aqueous solution, drop rate: 0.05 ml / 10 sec, end point determination: 0 mV, and subtract this titration value from the blank value. . The blank value is a diallyldimethylammonium chloride aqueous solution having the same concentration as that of the above sample adjusted to pH 10.0 with ammonia in the same manner by using a PCD titration apparatus. Dropping solution: 1/1000 N aqueous potassium polyvinylsulfonate solution, dropping rate: 0.05 ml / 10 sec, end point determination: titration obtained by titration at 0 mv.

Examples of combinations of the crosslinkable water-soluble ionic polymer used in the present invention include the following. That is, a cationic or amphoteric crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and a cationic or amphoteric crosslinkable water-soluble ionic polymer (B) having a charge inclusion rate of 5 or more and less than 35% Combination. A combination of a cationic or amphoteric crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and an anionic crosslinkable water-soluble ionic polymer (B) having a charge inclusion rate of 5 or more and less than 35%. Further, a combination of an anionic crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and a cationic or amphoteric crosslinkable water-soluble ionic polymer (B) having a charge inclusion rate of 5 or more and less than 35% It is.

The cationic or amphoteric crosslinkable water-soluble polymer (A) or (B) is a monomer represented by the general formula (1) and / or (2) in an amount of 5 to 100 mol%,
Preferably 20 to 100 mol%, 0 to 49 mol%, preferably 0 to 35 mol% of a monomer represented by the following general formula (3) and 0 to 95 mol% of nonionic monomer, preferably 0 It can be produced by copolymerizing a monomer mixture comprising ˜80 mol% with a polyfunctional monomer and / or a crosslinkable monomer.

In the anionic crosslinkable water-soluble polymer (A) or (B), the monomer represented by the general formula (3) is 5 to 100 mol%, preferably 10 to 70 mol%, and a nonionic monomer. It can be produced by copolymerizing a monomer mixture consisting of 0 to 95 mol%, preferably 30 to 90 mol% of a body, a polyfunctional monomer and / or a crosslinkable monomer.

Among the ionic monomers used in producing the cationic or amphoteric crosslinkable water-soluble polymers (A) and (B) used in the present invention, examples of the cationic monomers are as follows. That is, polymers and copolymers such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and methyldiallylamine are raised, and examples of quaternary ammonium group-containing polymers include the above-mentioned tertiary amino-containing monomer (Meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (Meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium Arm chloride, diallyl dimethyl ammonium chloride, and the like.

  In addition, as the anionic monomer used when producing the amphoteric crosslinkable water-soluble polymers (A) and (B) or the anionic crosslinkable water-soluble ionic polymers (A) and (B), sulfone may be used. Either a group-containing monomer or a carboxyl group-containing monomer may be used, and both may be used in combination. Examples of the sulfone group-containing monomer are vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, and the like. Examples of the carboxyl group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, maleic acid, and p-carboxystyrene.

Examples of nonionic monomers used when producing cationic or amphoteric crosslinkable water-soluble polymers (A) and (B), or anionic crosslinkable water-soluble polymers (A) and (B) , (Meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide Examples include acryloyl morpholine and acryloyl piperazine.

  Examples of the polyfunctional monomer having a plurality of vinyl groups used in the present invention include methylene bisacrylamide and ethylene glycol di (meth) acrylate. Examples of the crosslinkable monomer include thermally crosslinkable monomers such as N, N-dimethylacrylamide.

The addition amount of the polyfunctional monomer having a plurality of vinyl groups and / or the crosslinkable monomer with respect to the ionic monomer or the ionic monomer and the nonionic monomer is usually the above-mentioned single monomer. It is in the range of 0.005 to 0.1% by weight, preferably 0.01 to 0.1% by weight, based on the monomer mixture. In order to adjust the degree of polymerization, it is effective to use 0.01 to 3% by weight of isopropyl alcohol as a chain transfer agent in combination with the monomer.

The crosslinkable water-soluble ionic polymer of the present invention is an ionic monomer, or a polyfunctional monomer having a plurality of vinyl groups and / or an ionic monomer and a nonionic monomer and / or a crosslinkable property. It can manufacture by copolymerizing the monomer mixture which consists of a monomer. The polymerization can be carried out by an ordinary polymerization method after preparing an aqueous solution in which these monomers are mixed.

  As the polymerization method, after polymerization by aqueous solution polymerization, water-in-oil emulsion polymerization, water-in-oil dispersion polymerization, salt water dispersion polymerization, etc., it can be made into any product form such as aqueous solution, dispersion, emulsion or powder. . A preferred form is a water-in-oil emulsion polymerized product having a high concentration and a short dissolution time.

  As a method for producing a water-in-oil polymer emulsion, a monomer mixture comprising an ionic monomer or an ionic monomer and a copolymerizable monomer is water, at least water-immiscible. An oily substance composed of a hydrocarbon, an amount effective for forming a water-in-oil emulsion, and at least one surfactant having HLB are mixed and stirred vigorously to form a water-in-oil emulsion, followed by polymerization. This is a method of synthesis.

  Examples of oily substances composed of hydrocarbons used as dispersion media include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon-based synthetics having characteristics such as boiling point and viscosity substantially in the same range as these. An oil or a mixture thereof may be mentioned. As content, it is the range of 20 weight%-50 weight% with respect to the total amount of water-in-oil emulsion, Preferably it is the range of 20 weight%-35 weight%.

  Examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB are HLB 3-11 nonionic surfactants, specific examples of which include sorbitan monooleate Sorbitan monostearate, sorbitan monopalmitate and the like. The addition amount of these surfactants is 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the water-in-oil emulsion.

  After the polymerization, a hydrophilic interfacial modifier called a phase inversion agent is added to make the emulsion particles covered with the oil film easy to become familiar with water, and to dissolve the water-soluble polymer therein. Dilute with and use for each application. Examples of hydrophilic surfactants are cationic surfactants and nonionic surfactants of HLB 9-15, such as polyoxyethylene polyoxypropylene alkyl ether systems and polyoxyethylene alcohol ether systems. is there.

  The polymerization conditions are usually appropriately determined according to the monomer used and the copolymerization mol%, and the temperature is in the range of 0 to 100 ° C. In particular, when the water-in-oil emulsion polymerization method is applied, it is carried out in the range of 20 to 80 ° C, preferably 20 to 60 ° C. For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile and the like.

Examples of water-soluble azo initiators include 2,2′-azobis (amidinopropane) dichloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of redox systems include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine, and the like. Examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate, etc. I can give you.

The polymerization concentration of the monomer is in the range of 20 to 50% by weight, preferably in the range of 25 to 40% by weight. The concentration and temperature of the polymerization are appropriately determined depending on the monomer composition, the polymerization method, and the selection of the initiator. Set. The molecular weight of the water-soluble polymer obtained by polymerizing these monomers is preferably in the range of 3 million to 20 million.

  The mixing ratio of the crosslinkable water-soluble ionic polymer (A) having a charge inclusion ratio of 35% or more and the crosslinkable water-soluble ionic polymer (B) having a charge inclusion ratio of 5 to 35% is 10: It is the range of 90-90: 10, Preferably it is the range of 20: 80-80: 20. If either component is greater than this range, one of the properties will appear too strong and the features will be lost. When a crosslinkable water-soluble anionic polymer and a crosslinkable water-soluble cationic or amphoteric polymer are combined, the ratio of the ion equivalent value to the unit weight of the polymer (the total of the crosslinkable water-soluble cationic or amphoteric polymer). The cation equivalent value) / (total anion equivalent value of the crosslinkable water-soluble anionic polymer) is preferably larger than 0.8, more preferably 1.0 or more. The addition method can be arbitrary, such as simultaneous, sequential, or mixing two kinds.

  An aggregating agent combining the crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and the crosslinkable water-soluble ionic polymer (B) having a charge inclusion rate of 5 to 35% according to the present invention, For the dewatering of surplus sludge generated when biological treatment such as paper wastewater, chemical industrial wastewater, food industrial wastewater, etc., or organic sludge such as raw sludge, mixed raw sludge, surplus sludge, digested sludge, etc. Can be used.

An aggregation treatment agent comprising the crosslinkable water-soluble ionic polymer having a charge inclusion ratio of 35% or more according to the present invention and (A) and the crosslinkable water-soluble ionic polymer (B) having a charge inclusion ratio of 5 to 35%. The addition amount is usually in the range of 0.1 to 3% by weight with respect to the sludge solid content, and preferably in the range of 0.2 to 2%.

(Synthesis Example 1) In a reaction vessel equipped with a stirrer and a temperature controller, 5.0 g of sorbitan monooleate was charged and dissolved in 130 g of isoparaffin having a boiling point of 190 ° C to 230 ° C. Separately, acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DMQ) 80% aqueous solution 211.8 g, acrylamide (abbreviated as AAM) 50% aqueous solution 31.1 g, methylenebisacrylamide 0.2% aqueous solution 2.78 g, isopropyl alcohol 0.7. 19 g (0.1% by weight of monomer) and 119.1 g of ion-exchanged water were each collected, mixed and completely dissolved. Thereafter, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 15 minutes. The monomer composition at this time is DMQ / AAM = 80/20 (mol%).

  The obtained emulsion was maintained at a temperature of the monomer solution at 40 to 43 ° C., and after nitrogen substitution for 30 minutes, dimethyl-2,2-azobisisobutyrate (V-601 manufactured by Wako Pure Chemical Industries) 7 g (0.038% by weight of monomer) was added to initiate the polymerization reaction. The reaction was completed at a reaction temperature of 42 ± 2 ° C. for 12 hours to complete the reaction. After the polymerization, 5.0 g of polyoxyethylene polyoxypropylene alkyl ether (1% by weight with respect to the liquid) was added to and mixed with the resulting water-in-oil emulsion as a phase inversion agent. Then, when the product viscosity was measured with a B-type viscometer, it was 330 mPa · s. The charge inclusion rate determined by the colloid titration method and the above formula was 65.3%. This is used as a sample for a dehydration test and is referred to as Sample-1. Furthermore, DMQ / AAM = 80/20 (mol%) charge inclusion rate 48.7% (sample-2), DMQ / AAM = 80/20 (mol%) charge inclusion rate 29.1 in the same manner as in Synthesis Example 1. % (Sample-3), DMQ / AAM = 80/20 (mol%) charge inclusion rate 11.3% (sample-4) DMQ / AAM / AAC = 80/10/10 (mol%) charge inclusion rate 42. 0% (sample-5), DMQ / AAM / AAC = 80/20/10 (mol%) charge inclusion rate 17.5% (sample-6), DMQ / AAC = 80/20 (mol%) charge inclusion rate A crosslinkable water-soluble polymer having 40.5.0% (sample-7), DMQ / AAC = 80/20 (mol%), and charge inclusion rate of 21.6% (sample-8) was synthesized. The results are shown in Table-1.

(Comparative Synthesis Example 1) 5.0 g of sorbitan monooleate was charged and dissolved in 130 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. in a reaction vessel equipped with a stirrer and a temperature controller. Separately, acryloyloxyethyltrimethylammonium chloride (abbreviated as DMQ) 80% aqueous solution 211.8 g, acrylamide (abbreviated as AAM) 50% aqueous solution 31.1 g, isopropyl alcohol 0.19 g (0.1% by weight monomer) , 121.9 g of ion-exchanged water was collected, mixed and completely dissolved. Thereafter, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 15 minutes. The monomer composition at this time is DMQ / AAM = 80/20 (mol%).

ＤＭＱ：アクリロイルオキシエチルトリメチルアンモニウムクロリド、ＡＡＭ：アクリルアミド、ＡＡＣ：アクリル酸、エマルジョン粘度；ｍＰａ・ｓ、架橋性単量体添加量；対単量体重量％、電荷内包率；％
（表２）

配合比；重量比

（表３）

配合比；重量比 The obtained emulsion was maintained at a temperature of the monomer solution at 40 to 43 ° C., and after nitrogen substitution for 30 minutes, dimethyl-2,2-azobisisobutyrate (V-601 manufactured by Wako Pure Chemical Industries) 7 g (0.038% by weight of monomer) was added to initiate the polymerization reaction. The reaction was completed at a reaction temperature of 42 ± 2 ° C. for 12 hours to complete the reaction. After the polymerization, 5.0 g of polyoxyethylene polyoxypropylene alkyl ether (1% by weight with respect to the liquid) was added to and mixed with the resulting water-in-oil emulsion as a phase inversion agent. Then, when the product viscosity was measured with a B-type viscometer, it was 290 mPa · s. The charge inclusion rate determined from the above calculation formula was 2.3%. This is used as a sample for dehydration test and is referred to as Comparative-1. The results are shown in Table 1. Thereafter, sludge dewatering samples M-1 to M-10 and comparative samples CM-1 to CM-13 were prepared by mixing the samples as shown in Tables 2 and 3, respectively.











(Table 1)

DMQ: acryloyloxyethyltrimethylammonium chloride, AAM: acrylamide, AAC: acrylic acid, emulsion viscosity; mPa · s, addition amount of crosslinkable monomer; monomer weight%, charge inclusion rate:%
(Table 2)

Mixing ratio; weight ratio

(Table 3)

Mixing ratio; weight ratio

200 ml of excess human waste sludge was collected in a 300 ml beaker, and the water-in-oil emulsion consisting of a mixture of the two cross-linkable water-soluble polymers shown in Table 2, M-1 to M-4 was treated with 0.2% aqueous solution. After adding the liquid weight of 100 to 300 ppm, the beaker was transferred 20 times to produce sludge aggregation floc by stirring, and the floc particle size was measured. Then, using a 40 mesh filter cloth as a filter, the dispersion liquid in which the sludge aggregation floc was generated was gravity filtered. The amount of each filtrate was measured after 5 and 20 seconds. Moreover, the external appearance of the obtained filtrate was visually evaluated in the following five stages.

(Evaluation criteria for the appearance of the filtrate)
○: Clearness of the filtrate is good, SS (suspension particles) is not found in the filtrate ○-: Good clarity of the filtrate, SS is seen in the filtrate Δ: The filtrate is turbid, SS is seen in the filtrate △ −: The filtrate is turbid, and SS is observed in the filtrate. ×: The filtrate is extremely turbid, and SS is observed in the filtrate.

フロック径；ｍｍ、濾液量；ｍＬ、
濾液状態；試験条件に記載、含水率；重量％











（表５）

フロック径；ｍｍ、濾液量；ｍＬ、
濾液状態；試験条件に記載、含水率；重量％ The obtained sludge cake was squeezed and dehydrated with a sludge dewatering test apparatus using nylon # 202 as a filter cloth under the conditions of 3.0 Kg / cm ² and 30 seconds, and the moisture content of the sludge cake was measured. The results are shown in Table 4. The properties of the test sludge are as follows. TS: 22,000 mg / l, VTS: 69.3% / TS, SS: 22,500 mg / l (200 mesh filtration) pH 6.68. In addition, comparative samples CM-1 to CM-9 shown in Table 3 were used as comparative tests, and the same test operation as in Example 1 was performed. The results are shown in Table 5.
(Table 4)

Flock diameter: mm, filtrate amount: mL,
Filtrate state; described in test conditions, moisture content: wt%











(Table 5)

Flock diameter: mm, filtrate amount: mL,
Filtrate state; described in test conditions, moisture content: wt%

フロック径；ｍｍ、濾液量；ｍＬ、
濾液状態；試験条件に記載、含水率；重量％ In the same manner as in Example 1, M-5 to M-10 were tested. The results are shown in Table 6. As a comparative test, CM-5 to CM-8 were tested in the same manner as in Example 2. The results are shown in Table 6.









(Table 6)

Flock diameter: mm, filtrate amount: mL,
Filtrate state; described in test conditions, moisture content: wt%

As described above, the present invention leaves the advantages of the crosslinkable water-soluble ionic polymer and solves the problem of reducing the addition amount.

Claims (5)

A vinyl polymerized crosslinkable water-soluble ionic polymer (A) having a charge inclusion rate of 35% or more and a vinyl polymerized crosslinkable water soluble ionic polymer (B) having a charge encapsulation rate of 5 or more and less than 35% were combined. Aggregation treatment agent. The vinyl-polymerizable cross-linkable water-soluble ionic polymer (A) and (B) is a monomer represented by the following general formula (1) and / or (2): A monomer mixture comprising 0 to 50 mol% of the monomer represented by (3) and 0 to 95 mol% of a nonionic monomer and an aqueous solution of a polyfunctional monomer and / or a crosslinkable monomer It is produced by emulsifying and polymerizing a water-immiscible organic liquid in a continuous phase and a monomer mixture aqueous solution in a dispersed phase with a surfactant, and then adding a phase inversion agent as appropriate. The aggregation treatment agent according to claim 1.

General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are alkyl or alkoxyl groups having 1 to ₃ carbon atoms, R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group, or a benzyl group. A may be oxygen or NH, B may represent an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, and X ₁ ⁻ may represent an anion.

General formula (2)
R ₅ represents hydrogen or a methyl group, R ₆ and R ₇ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.

General formula (3)
R ₈ is hydrogen, methyl group or carboxymethyl group, Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , R ₉ Is hydrogen or COO ⁻ Y ₁ ⁺ , Y ⁺ and Y ₁ ⁺ are hydrogen ions or cations The vinyl-polymerizable crosslinkable water-soluble ionic polymer (A) or vinyl-polymerizable crosslinkable water-soluble ionic polymer (B) is used as a surfactant in the aqueous solution of the monomer mixture (A1) or (B1), respectively. The emulsion is prepared by emulsifying and polymerizing an immiscible organic liquid in water to form a continuous phase and an aqueous monomer mixture in a dispersed phase, and then adding a phase inversion agent as appropriate. The aggregating agent described in 1.
Monomer composition (A1): 5-100 mol% of the monomer represented by the general formula (1) and / or (2), and 0-50 mol of the monomer represented by the general formula (3) % And non-ionic monomer 0-95 mol%. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.
Monomer composition (B1): The crosslinkable water-soluble ionic polymer (B) contains 5 to 100 mol% of the monomer represented by the general formula (3) and nonionic monomers 0 to 95. Mol%.
Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum. The vinyl-polymerizable crosslinkable water-soluble ionic polymer (A) or the vinyl-polymerizable crosslinkable water-soluble ionic polymer (B) is used as a surfactant in an aqueous monomer mixture of (A2) or (B2), respectively. The emulsion is prepared by emulsifying and polymerizing an immiscible organic liquid in water to form a continuous phase and an aqueous monomer mixture in a dispersed phase, and then adding a phase inversion agent as appropriate. The aggregating agent described in 1.
Monomer composition (A2): 5-100 mol% of the monomer represented by the general formula (3) and 0-95 mol% of a nonionic monomer. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum.
Monomer composition (B2): 5-100 mol% of the monomer represented by the general formula (1) and / or (2), and 0-50 mol of the monomer represented by the general formula (3) % And non-ionic monomer 0-95 mol%. Furthermore, the polymer in which the polyfunctional monomer and / or the crosslinkable monomer is added is added in a molar ratio that maintains water solubility with respect to the monomer sum. A sludge dewatering method comprising adding a coagulation treatment agent combining the crosslinkable water-soluble ionic polymers (A) and (B) according to claim 1 to sludge and dewatering with a dehydrator.