WO2000011052A1 - Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water - Google Patents

Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water Download PDF

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WO2000011052A1
WO2000011052A1 PCT/KR1999/000462 KR9900462W WO0011052A1 WO 2000011052 A1 WO2000011052 A1 WO 2000011052A1 KR 9900462 W KR9900462 W KR 9900462W WO 0011052 A1 WO0011052 A1 WO 0011052A1
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formula
mixture
compound
anionic
group
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PCT/KR1999/000462
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French (fr)
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Sung Wook Han
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Green Technology Inc.
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Priority to JP2000566320A priority Critical patent/JP2002523533A/en
Priority to US09/762,507 priority patent/US6531531B1/en
Priority to EP99938641A priority patent/EP1161468A1/en
Priority to AU53080/99A priority patent/AU5308099A/en
Publication of WO2000011052A1 publication Critical patent/WO2000011052A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water. More particularly, it relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant, which has the properties of declining and reducing the water content of flock as well as water content of sludge cake obtained after treating the waste water.
  • the method of flocculation using a flocculant can be explained by following mechanism. Firstly, colloidal particles are enhanced to be coagulated by the addition of inorganic flocculant in the waste water ; secondly, the coagulated particles become larged by the influence of flocculant ; lastly, the flocculated particles are separated by the difference of sedimental velocity or floating velocity in the waste water.
  • the anionic flocculant is desirable, whereas the cationic flocculant is desirable in the waste water having sulfur compound or clay. Further, the anionic flocculant is effective for treating the water in the neutral waste water.
  • the polymer flocculant used for the treatment of colloidal materials in waste water is high molecular weight compound, and it neutralizes and collects the suspended particles. Further, the polymer flocculant is classified into following groups : i ) anionic polymer flocculant, such as, sodium alginate, sodium polyacrylate, salt of maleic acid copolymer, partly hydrolyzed salt of polyacrylamide, ii ) cationic polymer flocculant, such as, aery late, methacrylate, hydrophilic aniline resin hydrochloride salt, polythiourea hydrochloride salt, polyethylene amino triazole, polyvinyl benzyl trimethyl ammonium fluoride, chitosan, polyethylene amine, vinylpyridine copolymer, and iii) nonionic polymer flocculant, such as, starch, hydrophilic urea resin, polyacrylamide, polyoxyethylene.
  • anionic polymer flocculant such as, sodium alginate, sodium polyacryl
  • the polymer flocculant forms the flock induced by bridging between colloid particle and polymer flocculant according to the force between them.
  • the commercially marketed polymer flocculant has molecular weight in the range of 10,000 ⁇ - 10,000,000.
  • the commercially marketed product contains the polymer or copolymer of quaternary acrylate, dimethyl diallyl ammonium chloride, tertiary acrylate and acrylamide.
  • the flocculation by the polymer flocculant depends upon the degree of linear polymerization of the polymer flocculant, that is, molecular weight and ionic density. Further, the degree of polymerization is controlled by condition of polymerization, whereas the ionic density is controlled by molar ratio of cationic monomer.
  • the polymer flocculant having high degree of polymerization makes a large flock, and the polymer flocculant having strong ionic density raises a strength of flock. Also, there is a correlation between degree of polymerization and ionic density, so that the higher molecular weight of polymer flocculant becomes, and the lower ionic density of polymer flocculant becomes.
  • the flock formed by single injection of the polymer flocculant contains a large amount of water. Therefore, it requires additional steps for lowering water content of the flock. However, it has some limitation for fully drying the flock, because the flock has hygroscopic property in itself.
  • the water content of the flock can influence the water content of dehydrated sludge cake, which is removed and reclaimed.
  • the smaller water content of the sludge cake induces the smaller amount of cake, which causes the efficient treatment of the sludge. Further, such smaller cake sludge saves the cost for removing and reclaiming it.
  • aqueous dispersions of water-soluble nonionic and anionically charged vinyl and allyl addition polymers were disclosed in WO 97/34933. Also, they can be obtained by polymerizing in the presence of an anionically charged water-soluble polymer stabilizer in a saturated salt solution.
  • dialkylaminoalkyl (meth)acrylamide polymer dispersions For forming dialkylaminoalkyl (meth)acrylamide polymer dispersions, a novel dispersant system was disclosed in U. S. Pat. No. 5,597,859. Further, European Pat. 0 839,767 A2 suggested a method for clarifying ink-laden water obtained from the recycling of paper stocks by treating said water with a conventional coagulant followed by treatment with a hydrophilic dispersion polymer. In this method, the hydrophilic dispersion flocculant is a copolymer of DMAEA • MCQ [dimethylaminoethyl (meth)acrylate methyl chloride quaternary] and (meth)acrylamide.
  • the present invention relates to a hydrophilic polymer dispersion composition containing an inorganic flocculant and a method for preparing such composition which comprises the following steps of : i ) mixing acrylamide, cationic monomer, anionic monomer, polymer of cationic monomer, anionic salt and inorganic flocculant, ⁇ ) lst-polymerizing the mixture obtained in previous step, iii) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely, and iv) adding and mixing anionic salt to obtained polymers.
  • hydrophilic polymer dispersion containing an inorganic flocculant of the present invention is prepared by following steps of : i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 — 10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40-75 wt % of water ; ii ) lst
  • Ri is hydrogen atom or methyl ;
  • R 2 and R 3 are each independently alkyl group having 1 to 3 carbon atoms ;
  • Ai is oxygen atom or NH ;
  • Bi is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ;
  • Xi is anionic counter ion.
  • R is hydrogen atom or methyl
  • R5 and R 6 are each independently alkyl group having 1 to 2 carbon atoms ;
  • R 7 is hydrogen atom or alkyl group having 1 to 2 carbon atoms ;
  • a 2 is oxygen atom or NH ;
  • B 2 is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and X 2 is anionic counter ion.
  • the conventional hydrophilic polymer flocculant contains a dispersion of polymer of mixture of cationic monomers and anionic monomers, whereas the hydrophilic polymer dispersion of the present invention contains further inorganic flocculant. Further, the present invention enhances the degree of polymerization of the polymer dispersion by adding and mixing nonionic surfactant to the mixture of cationic monomers.
  • Acrylamide can be used as monomer, and acrylic acid, methacrylic acid or itaconic acid can be used as anionic monomer.
  • the cationic monomer of formula I and cationic monomer of formula TJ can be mixed in a ratio of 10 : 0 to 2 : 8.
  • the reacting materials for the polymer are a cationic monomer of formula I , cationic monomer of formula TJ, and homopolymer of cationic monomer of formula I , homopolymer of cationic monomer of formula LT, or copolymer of cationic monomer of formula I and formula ⁇ as polymer in the present invention.
  • the higher content of the cationic monomer induces the higher ionic density, which causes the improved strength of flock.
  • the quantity of monomers and polymers can be determined experimentally in consideration of size and strength of flock in flocculation.
  • the anionic salt has the function for preparing dispersion by dispersing polymer materials to fine particles.
  • Said anionic salt is selected from the group consisting of ammonium sulfate, ammonium chloride, sodium sulfate, magnesium sulfate, aluminium sulfate, ammonium hydrogenphosphate, sodium hydrogenphosphate, and potassium hydrogenphosphate. Further, half or more of said anionic salt can be added before polymerization reaction, and the remaining said anionic salt has to be added after polymerization reaction. It is proved as the desirable preparation method for the stable polymer dispersion experimentally.
  • the inorganic flocculant firstly introduced in the present invention has the functions of improving the strength of flock and reducing the water content of sludge cake.
  • the dehydrating function of inorganic flocculant promotes the patch flocculation of flock, which raises density of flock and reduces the water content of flock.
  • Said inorganic flocculant is selected from the group consisting of polyaluminium chloride, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, aluminium chlorohydrate, and aluminasol.
  • the content of inorganic flocculant is less than 1 wt %, the reducing effect of water content shall not be sufficient.
  • the stability of dispersion shall be declined by inhibiting the dispersed state of polymer flocculant.
  • Said polymer flocculant and inorganic flocculant can be stabilized by stabilizer, such as, nonionic surfactant and glycerin.
  • the particles of dispersed polymer material is stabilized by following mechanisms of : i ) steric hindrance of said nonionic surfactant and ii ) repulsion caused by high charge of the polymer material.
  • the content of nonionic surfactant is less than 0.01 wt %, stability of dispersion obtained is lowered. Further, in case that the content of nonionic surfactant is more than 1 wt %, wasted surfactant remains.
  • 0—2 wt % of glycerin can be used as subsidiary dispersant.
  • the nonionic surfactant of the present invention activates the nuclei formation, which results in the reduction of in-production viscosity and the stabilization of polymer particles caused by the steric hindrance of the surfactant. Therefore, the nonionic surfactant has a role to enhance the mobility of the final product.
  • the azobis initiator which is a kind of radical initiator, can be used for polymerizing said cationic monomer of formula I and formula TJ and said anionic monomer. 0.001 —0.1 wt % of said polymerization initiator can be used. In case that the content of initiator is less than 0.001 wt %, there are some drawbacks of : i ) not maintaining polymerization reaction and ii ) obtaining insoluble polymer material having high degree of polymerization.
  • the viscosity and pH of said hydrophilic polymer dispersion containing an inorganic flocculant can be controlled less than 1,000 cps and more than pH 3.0. It is desirous that the viscosity and ionic density of 1% aqueous solution of the hydrophilic polymer dispersion is more than 40 cps and more than 1.0 meq. In case that the product is centrifuged to 1,800 rpm for 10 minutes, the precipitation has to be less than 5% of total weight in order to keep the product for a long time.
  • hydrophilic polymer dispersion containing an inorganic flocculant of the present invention is prepared by following steps of : [mixing step] i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 —10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40 — 75 wt % of water in the reactor, ii ) nitrogen purging in the reactor, and agitating said mixture more than 30
  • initiiator adding step] i heating said mixture at 30—50X3, ii ) adding 0.00 1 —0.1 wt % of initiator to said mixture ;
  • [lst-polymerizing step] lst-polymerizing said mixture at 30— 50 °C for 3—6 hours ;
  • [2nd-polymerizing step] 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.001—0.1 wt % of initiator to said mixture for 3—15 hours ;
  • the mixing step the inside of a reactor is purged with nitrogen, and the raw materials are mixed and agitated homogeneously. Particularly, a part of anionic salt is added in this step, and the remaining part of anionic salt is added after the polymerization.
  • This mixing step is important for raising stability of the dispersion.
  • the initiator for example, azobis initiator or redox initiator, such as, ammonium persulfate and sodium bisulfite is added for polymerizing anionic monomer, cationic monomer of formula I and TJ .
  • Said mixture has to be heated at 30— 50 °C where the polymerization is initiated.
  • the reactor has to be cooled to achieve the maintenance of temperature at 30— 50 °C. This step has to be maintained for 3—6 hours until polymerization is finished.
  • the final product is obtained by the finishing step.
  • the pH of polymer dispersion is more than 4.0, the stability of dispersion is lowered and the efficiency of dispersion is declined.
  • the polymer dispersion is prepared by following steps of : i ) mixing 138.941g of 50% acrylamide aqueous solution, 126.761g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 36.401g of dimethylaminoethyl acrylate methyl chloride quaternary monomer (80%), 20.0g of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 5.0g of dimethyldiallyl ammonium chloride polymer (40%), 131.707g of ammonium sulfate, 2.0g of aromatic ethoxylate, 6.0g of glycerin, 160.0g of polyaluminium chloride (10%) and 304.897g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 46 "C,
  • the polymer dispersion is prepared by following steps of : i ) mixing 190.211g of 50% acrylamide aqueous solution, 102.270g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 38.463g of dimethyldiallyl ammonium chloride monomer (60%), lO.Og of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 10.0g of dimethyldiallyl ammonium chloride polymer (40%), 122.201g of ammonium sulfate, 2.0g of aromatic ethoxylate, lO.Og of glycerin, lOO.Og of ferric sulfate (8%) and 337.055g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 37°C, iv) adding 0.05g
  • the polymer dispersion is prepared by following steps of : i ) mixing 34.305g of 50% acrylamide aqueous solution, 203.432g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 87.627g of dimethylaminoethyl acrylate methyl chloride quaternary monomer (80%), 18.75g of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 15.625g of dimethyldiallyl ammonium chloride polymer (40%), 116.747g of ammonium sulfate, 2.0g of aromatic ethoxylate, 125.0g of aluminium chlorohydrate (10%) and 332.261g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 35 °C, iv) adding 0.05g of azobis initiator (VA-044) to
  • the polymer dispersions prepared in Example 1 —3 have less than 2% of water content of flock as compared with conventional polymer dispersions in dry test.
  • hydrophilic polymer dispersion containing an inorganic flocculant of the present invention and the commercially marketed polymer dispersions not containing an inorganic flocculant, such as, i ) powder flocculant (A), ii ) emulsion flocculant (B), and iii) dispersion flocculant (C) are selected as tested flocculants.
  • the flocculation effect is measured by using the surplus sludge of manure waste water having pH 6.8 with 5,500ppm of solid concentration, and the result is shown in Table 1.
  • This test is carried out by following steps of : i ) adding 500ml of sludge to each 500ml beaker by using cylinder respectively, ii ) adding each amount of the flocculant to said sludge by using pipet, iii) agitating said mixture in 100 rpm, iv) stop agitating and measuring the flock size at the time of finishing flock growth, v ) agitating said mixture in 300 rpm for 10 seconds, vi) measuring the flock size.
  • * shows the size of the flock which is measured after vigorous stirring of the mixture.
  • the hydrophilic polymer dispersion of the present invention induces equal flock size and improved flock strength as compared with the commercially marketed polymer dispersions. Therefore, the hydrophilic polymer dispersion of the present invention has an excellent effect for removing sludge by forming flock.
  • the hydrophilic polymer dispersion of the present invention may be useful for the manufacture of paper to make an aqueous cellulosic suspension or slurry. Hence, said hydrophilic polymer dispersion will be important for the efficient cost of papermaking manufacture.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

The present invention relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water. More particularly, it relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant, which has the properties of declining and reducing the water content of flock as well as water content of sludge cake obtained after treating the waste water.

Description

METHOD AND COMPOSITION OF A HYDROPHILIC POLYMER DISPERSION CONTAINING AN INORGANIC FLOCCULANT TO BE USED FOR THE TREATMENT OF WASTE WATER
TECHNICAL FIELD
The present invention relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water. More particularly, it relates to the method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant, which has the properties of declining and reducing the water content of flock as well as water content of sludge cake obtained after treating the waste water.
BACKGROUND ART
It has been recognized that the reduction of water content of sludge cake in the waste water is an important technical matter for protecting the environmental contamination. Especially, the reduction of industrial waste and waste water sludge becomes an important matter for the environment. The reduction of sludge has an advantage of the efficient development of land by minimizing the waste treatment space.
To minimize the content of water in the sludge, the method using thermal energy has been used. However, it has a lot of drawbacks to require high energy together with high operation cost. Accordingly, the use of flocculant to treat the waste water has been considered as an efficient method for treating the waste water.
The method of flocculation using a flocculant can be explained by following mechanism. Firstly, colloidal particles are enhanced to be coagulated by the addition of inorganic flocculant in the waste water ; secondly, the coagulated particles become larged by the influence of flocculant ; lastly, the flocculated particles are separated by the difference of sedimental velocity or floating velocity in the waste water.
In the waste water having metal hydroxide, the anionic flocculant is desirable, whereas the cationic flocculant is desirable in the waste water having sulfur compound or clay. Further, the anionic flocculant is effective for treating the water in the neutral waste water.
Recently, the technology using polymer flocculant has been developed. The polymer flocculant used for the treatment of colloidal materials in waste water is high molecular weight compound, and it neutralizes and collects the suspended particles. Further, the polymer flocculant is classified into following groups : i ) anionic polymer flocculant, such as, sodium alginate, sodium polyacrylate, salt of maleic acid copolymer, partly hydrolyzed salt of polyacrylamide, ii ) cationic polymer flocculant, such as, aery late, methacrylate, hydrophilic aniline resin hydrochloride salt, polythiourea hydrochloride salt, polyethylene amino triazole, polyvinyl benzyl trimethyl ammonium fluoride, chitosan, polyethylene amine, vinylpyridine copolymer, and iii) nonionic polymer flocculant, such as, starch, hydrophilic urea resin, polyacrylamide, polyoxyethylene.
Generally, it has been reported that the polymer flocculant forms the flock induced by bridging between colloid particle and polymer flocculant according to the force between them. The commercially marketed polymer flocculant has molecular weight in the range of 10,000 ~- 10,000,000.
The commercially marketed product contains the polymer or copolymer of quaternary acrylate, dimethyl diallyl ammonium chloride, tertiary acrylate and acrylamide.
The flocculation by the polymer flocculant depends upon the degree of linear polymerization of the polymer flocculant, that is, molecular weight and ionic density. Further, the degree of polymerization is controlled by condition of polymerization, whereas the ionic density is controlled by molar ratio of cationic monomer.
Generally, the polymer flocculant having high degree of polymerization makes a large flock, and the polymer flocculant having strong ionic density raises a strength of flock. Also, there is a correlation between degree of polymerization and ionic density, so that the higher molecular weight of polymer flocculant becomes, and the lower ionic density of polymer flocculant becomes.
The flock formed by single injection of the polymer flocculant contains a large amount of water. Therefore, it requires additional steps for lowering water content of the flock. However, it has some limitation for fully drying the flock, because the flock has hygroscopic property in itself.
The water content of the flock can influence the water content of dehydrated sludge cake, which is removed and reclaimed. The smaller water content of the sludge cake induces the smaller amount of cake, which causes the efficient treatment of the sludge. Further, such smaller cake sludge saves the cost for removing and reclaiming it.
The aqueous dispersions of water-soluble nonionic and anionically charged vinyl and allyl addition polymers were disclosed in WO 97/34933. Also, they can be obtained by polymerizing in the presence of an anionically charged water-soluble polymer stabilizer in a saturated salt solution.
Further, the polymerization process of preparing a water-soluble polymer in the form of a water-continuous dispersion was described in European Pat. 0 630,909 Al. In this process, the peak in-production viscosity developed in the aqueous reaction mixture is lower than the peak in-production viscosity developed in an equivalent batch polymerization.
For forming dialkylaminoalkyl (meth)acrylamide polymer dispersions, a novel dispersant system was disclosed in U. S. Pat. No. 5,597,859. Further, European Pat. 0 839,767 A2 suggested a method for clarifying ink-laden water obtained from the recycling of paper stocks by treating said water with a conventional coagulant followed by treatment with a hydrophilic dispersion polymer. In this method, the hydrophilic dispersion flocculant is a copolymer of DMAEA • MCQ [dimethylaminoethyl (meth)acrylate methyl chloride quaternary] and (meth)acrylamide.
The improved process for the preparation of water soluble polymer dispersion was disclosed in European Pat. 0 657,478 A2.
However, none of prior references discloses the far enhanced waste water treatment activity compared to formerly developed hydrophilic polymer dispersion.
DISCLOSURE OF INVENTION
The present invention relates to a hydrophilic polymer dispersion composition containing an inorganic flocculant and a method for preparing such composition which comprises the following steps of : i ) mixing acrylamide, cationic monomer, anionic monomer, polymer of cationic monomer, anionic salt and inorganic flocculant, ϋ ) lst-polymerizing the mixture obtained in previous step, iii) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely, and iv) adding and mixing anionic salt to obtained polymers.
Further, the hydrophilic polymer dispersion containing an inorganic flocculant of the present invention is prepared by following steps of : i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 — 10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40-75 wt % of water ; ii ) lst-polymerizing the mixture in addition to 0.001 —0.1 wt % of polymerization initiator to said mixture ; iii) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely ; and iv) adding and mixing 10—30 wt % of anionic salt to obtained polymers.
Figure imgf000007_0001
formula I
wherein
Ri is hydrogen atom or methyl ;
R2 and R3 are each independently alkyl group having 1 to 3 carbon atoms ;
Ai is oxygen atom or NH ;
Bi is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and
Xi is anionic counter ion.
Figure imgf000007_0002
formula π
wherein
R is hydrogen atom or methyl ;
R5 and R6 are each independently alkyl group having 1 to 2 carbon atoms ;
R7 is hydrogen atom or alkyl group having 1 to 2 carbon atoms ;
A2 is oxygen atom or NH ;
B2 is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and X2 is anionic counter ion.
BEST MODE FOR CARRYING OUT THE INVENTION
The conventional hydrophilic polymer flocculant contains a dispersion of polymer of mixture of cationic monomers and anionic monomers, whereas the hydrophilic polymer dispersion of the present invention contains further inorganic flocculant. Further, the present invention enhances the degree of polymerization of the polymer dispersion by adding and mixing nonionic surfactant to the mixture of cationic monomers.
Acrylamide can be used as monomer, and acrylic acid, methacrylic acid or itaconic acid can be used as anionic monomer.
The cationic monomer of formula I and cationic monomer of formula TJ can be mixed in a ratio of 10 : 0 to 2 : 8.
The reacting materials for the polymer are a cationic monomer of formula I , cationic monomer of formula TJ, and homopolymer of cationic monomer of formula I , homopolymer of cationic monomer of formula LT, or copolymer of cationic monomer of formula I and formula π as polymer in the present invention. The higher content of the cationic monomer induces the higher ionic density, which causes the improved strength of flock. The quantity of monomers and polymers can be determined experimentally in consideration of size and strength of flock in flocculation.
Said monomer is soluble in initial salt solution, but polymer material is insoluble in initial salt solution. Therefore, the anionic salt has the function for preparing dispersion by dispersing polymer materials to fine particles. Said anionic salt is selected from the group consisting of ammonium sulfate, ammonium chloride, sodium sulfate, magnesium sulfate, aluminium sulfate, ammonium hydrogenphosphate, sodium hydrogenphosphate, and potassium hydrogenphosphate. Further, half or more of said anionic salt can be added before polymerization reaction, and the remaining said anionic salt has to be added after polymerization reaction. It is proved as the desirable preparation method for the stable polymer dispersion experimentally.
The inorganic flocculant firstly introduced in the present invention has the functions of improving the strength of flock and reducing the water content of sludge cake. The dehydrating function of inorganic flocculant promotes the patch flocculation of flock, which raises density of flock and reduces the water content of flock. Said inorganic flocculant is selected from the group consisting of polyaluminium chloride, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, aluminium chlorohydrate, and aluminasol. In case that the content of inorganic flocculant is less than 1 wt %, the reducing effect of water content shall not be sufficient. On the other hand, in case that the content of inorganic flocculant is more than 10 wt %, the stability of dispersion shall be declined by inhibiting the dispersed state of polymer flocculant.
Said polymer flocculant and inorganic flocculant can be stabilized by stabilizer, such as, nonionic surfactant and glycerin. The particles of dispersed polymer material is stabilized by following mechanisms of : i ) steric hindrance of said nonionic surfactant and ii ) repulsion caused by high charge of the polymer material. In case that the content of nonionic surfactant is less than 0.01 wt %, stability of dispersion obtained is lowered. Further, in case that the content of nonionic surfactant is more than 1 wt %, wasted surfactant remains. Also, 0—2 wt % of glycerin can be used as subsidiary dispersant. In case that the content of glycerin is more than 2 wt %, glycerin is wasted. Further, the nonionic surfactant of the present invention activates the nuclei formation, which results in the reduction of in-production viscosity and the stabilization of polymer particles caused by the steric hindrance of the surfactant. Therefore, the nonionic surfactant has a role to enhance the mobility of the final product.
The azobis initiator, which is a kind of radical initiator, can be used for polymerizing said cationic monomer of formula I and formula TJ and said anionic monomer. 0.001 —0.1 wt % of said polymerization initiator can be used. In case that the content of initiator is less than 0.001 wt %, there are some drawbacks of : i ) not maintaining polymerization reaction and ii ) obtaining insoluble polymer material having high degree of polymerization. On the other hand, in case that the content of initiator is more than 0.1 wt %, there are some drawbacks of : i ) increasing and generating the heat during the polymerization, ii ) decreasing the yield of polymer material, and iii) preparing polymer material having low degree of polymerization.
The viscosity and pH of said hydrophilic polymer dispersion containing an inorganic flocculant can be controlled less than 1,000 cps and more than pH 3.0. It is desirous that the viscosity and ionic density of 1% aqueous solution of the hydrophilic polymer dispersion is more than 40 cps and more than 1.0 meq. In case that the product is centrifuged to 1,800 rpm for 10 minutes, the precipitation has to be less than 5% of total weight in order to keep the product for a long time.
Further, the hydrophilic polymer dispersion containing an inorganic flocculant of the present invention is prepared by following steps of : [mixing step] i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 —10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40 — 75 wt % of water in the reactor, ii ) nitrogen purging in the reactor, and agitating said mixture more than 30 rpm ;
[initiator adding step] i ) heating said mixture at 30—50X3, ii ) adding 0.00 1 —0.1 wt % of initiator to said mixture ;
[lst-polymerizing step] lst-polymerizing said mixture at 30— 50 °C for 3—6 hours ;
[2nd-polymerizing step] 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.001—0.1 wt % of initiator to said mixture for 3—15 hours ; [finishing step] i ) adding the remaining anionic salt to the polymer, ii ) adjusting pH of the polymer less than 4.0, iii) sieving the polymer using 40 -100 mesh.
In the mixing step, the inside of a reactor is purged with nitrogen, and the raw materials are mixed and agitated homogeneously. Particularly, a part of anionic salt is added in this step, and the remaining part of anionic salt is added after the polymerization. This mixing step is important for raising stability of the dispersion.
In the initiator adding step, the initiator, for example, azobis initiator or redox initiator, such as, ammonium persulfate and sodium bisulfite is added for polymerizing anionic monomer, cationic monomer of formula I and TJ . Said mixture has to be heated at 30— 50 °C where the polymerization is initiated. Further, in the lst-polymerizing step, the reactor has to be cooled to achieve the maintenance of temperature at 30— 50 °C. This step has to be maintained for 3—6 hours until polymerization is finished.
In the 2nd-polymerizing step, unreacted monomers in lst-polymerizing step is completely reacted to form the polymer in addition to said initiator at 30— 50 °C for 3—15 hours. Therefore, the polymer dispersion is obtained.
The final product is obtained by the finishing step. In case that the pH of polymer dispersion is more than 4.0, the stability of dispersion is lowered and the efficiency of dispersion is declined.
The present invention can be more specifically explained by the following examples. However, it should be understood that the examples are intended to illustrate, but not to limit the scope of the present invention in any manner.
EXAMPLE 1
Preparation of the polymer dispersion The polymer dispersion is prepared by following steps of : i ) mixing 138.941g of 50% acrylamide aqueous solution, 126.761g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 36.401g of dimethylaminoethyl acrylate methyl chloride quaternary monomer (80%), 20.0g of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 5.0g of dimethyldiallyl ammonium chloride polymer (40%), 131.707g of ammonium sulfate, 2.0g of aromatic ethoxylate, 6.0g of glycerin, 160.0g of polyaluminium chloride (10%) and 304.897g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 46 "C, iv) adding 0.04g of azobis initiator (V-50) to said mixture, v ) lst-polymerizing said mixture at 46 °C for 3 — 6 hours, vi) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.04g of said initiator (V-50) to said mixture for 3—15 hours, vii) adding 68.293g of ammonium sulfate to the polymer, viii) adjusting pH of the polymer to 4.0, ix) sieving the polymer using 60 mesh.
EXAMPLE 2
Preparation of the polymer dispersion
The polymer dispersion is prepared by following steps of : i ) mixing 190.211g of 50% acrylamide aqueous solution, 102.270g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 38.463g of dimethyldiallyl ammonium chloride monomer (60%), lO.Og of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 10.0g of dimethyldiallyl ammonium chloride polymer (40%), 122.201g of ammonium sulfate, 2.0g of aromatic ethoxylate, lO.Og of glycerin, lOO.Og of ferric sulfate (8%) and 337.055g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 37°C, iv) adding 0.05g of azobis initiator (VA-044) to said mixture, v ) lst-polymerizing said mixture at 37°C for 3 — 6 hours, vi) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.05g of said initiator (VA-044) to said mixture for 3—15 hours, vii) adding 77.108g of ammonium chloride to the polymer, viii) adjusting pH of the polymer to 4.0, ix) sieving the polymer using 60 mesh.
EXAMPLE 3
Preparation of the polymer dispersion
The polymer dispersion is prepared by following steps of : i ) mixing 34.305g of 50% acrylamide aqueous solution, 203.432g of dimethylaminoethyl acrylate benzyl chloride quaternary monomer (80%), 87.627g of dimethylaminoethyl acrylate methyl chloride quaternary monomer (80%), 18.75g of dimethylaminoethyl acrylate methyl chloride quaternary polymer (20%), 15.625g of dimethyldiallyl ammonium chloride polymer (40%), 116.747g of ammonium sulfate, 2.0g of aromatic ethoxylate, 125.0g of aluminium chlorohydrate (10%) and 332.261g of water in the 5-neck flask, ii ) nitrogen purging in the reactor, and agitating said mixture to 200 rpm, iii) heating said mixture at 35 °C, iv) adding 0.05g of azobis initiator (VA-044) to said mixture, v ) lst-polymerizing said mixture at 35 °C for 3 — 6 hours, vi) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.05g of said initiator (VA-044) to said mixture for 3 — 15 hours, vii) adding 63.253g of ammonium chloride to the polymer, viii) adjusting pH of the polymer to 4.0, ix) sieving the polymer using 60 mesh.
The polymer dispersions prepared in Example 1 —3 have less than 2% of water content of flock as compared with conventional polymer dispersions in dry test.
EXAMPLE 4
Test of flocculation effect
The hydrophilic polymer dispersion containing an inorganic flocculant of the present invention and the commercially marketed polymer dispersions not containing an inorganic flocculant, such as, i ) powder flocculant (A), ii ) emulsion flocculant (B), and iii) dispersion flocculant (C) are selected as tested flocculants. The flocculation effect is measured by using the surplus sludge of manure waste water having pH 6.8 with 5,500ppm of solid concentration, and the result is shown in Table 1.
This test is carried out by following steps of : i ) adding 500ml of sludge to each 500ml beaker by using cylinder respectively, ii ) adding each amount of the flocculant to said sludge by using pipet, iii) agitating said mixture in 100 rpm, iv) stop agitating and measuring the flock size at the time of finishing flock growth, v ) agitating said mixture in 300 rpm for 10 seconds, vi) measuring the flock size.
Table 1.
Figure imgf000014_0001
* shows the size of the flock which is measured after vigorous stirring of the mixture.
Further, the flocculation effect is measured by using the dried sludge of leather waste water having pH 7.2 with 18,000ppm of solid concentration, and the result is shown in Table 2.
Table 2.
Figure imgf000015_0001
Further, the flocculation effect is measured by using the dried sludge of food waste water having pH 7.5 with 8,000ppm of solid concentration, and the result is shown in Table 3.
Table 3.
Figure imgf000015_0002
In this test, the hydrophilic polymer dispersion of the present invention induces equal flock size and improved flock strength as compared with the commercially marketed polymer dispersions. Therefore, the hydrophilic polymer dispersion of the present invention has an excellent effect for removing sludge by forming flock.
The hydrophilic polymer dispersion of the present invention may be useful for the manufacture of paper to make an aqueous cellulosic suspension or slurry. Hence, said hydrophilic polymer dispersion will be important for the efficient cost of papermaking manufacture.

Claims

WHAT IS CLAIMED IS :
A hydrophilic polymer dispersion containing an inorganic flocculant prepared by following steps of : i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 —10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40—75 wt % of water ; ii ) lst-polymerizing the mixture in addition to 0.001—0.1 wt % of polymerization initiator to said mixture ; iii) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely ; and iv) adding and mixing 10—30 wt % of anionic salt to obtained polymers.
Figure imgf000017_0001
formula I
wherein
Ri is hydrogen atom or methyl ;
R2 and R3 are each independently alkyl group having 1 to 3 carbon atoms ;
Ai is oxygen atom or NH ;
Bi is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and
Xi is anionic counter ion.
Figure imgf000018_0001
0 = C — AΪ — 8z — N* — ; t R«
formula π
wherein
Ri is hydrogen atom or methyl ;
R5 and R6 are each independently alkyl group having 1 to 2 carbon atoms ;
R7 is hydrogen atom or alkyl group having 1 to 2 carbon atoms ;
A2 is oxygen atom or NH ;
B2 is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and
X2 is anionic counter ion.
2. The hydrophilic polymer dispersion according to claim 1, wherein said inorganic flocculant is selected from the group consisting of polyaluminium chloride, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, aluminium chlorohydrate, and aluminasol.
3. The hydrophilic polymer dispersion according to claim 1, wherein said anionic salt is selected from the group consisting of ammonium sulfate, ammonium chloride, sodium sulfate, magnesium sulfate, aluminium sulfate, ammonium hydrogenphosphate, sodium hydrogenphosphate, and potassium hydrogenphosphate.
4. The hydrophilic polymer dispersion according to claim 1, wherein said dispersion stabilizer is selected from the group consisting of nonionic surfactant and glycerin.
5. The hydrophilic polymer dispersion according to claim 1, wherein the ratio of cationic monomer mixture of compound of formula I and formula II is in the range of 10 : 0 to 2 : 8. process for preparing hydrophilic polymer dispersion containing an inorganic flocculant comprising the steps of : i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula π, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 —10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40—75 wt % of water ; ii ) lst-polymerizing the mixture in addition to 0.001—0.1 wt % of polymerization initiator to said mixture ; iii) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely ; and iv) adding and mixing 10—30 wt % of anionic salt to obtained polymers.
Figure imgf000019_0001
formula I
wherein
Ri is hydrogen atom or methyl ;
R2 and R3 are each independently alkyl group having 1 to 3 carbon atoms ;
Ai is oxygen atom or NH ;
Bi is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and
Xi is anionic counter ion.
Figure imgf000020_0001
0 = C — A2-- Bι — rT— ; t R«
formula TJ
wherein
Rt is hydrogen atom or methyl ;
R5 and R6 are each independently alkyl group having 1 to 2 carbon atoms ;
R7 is hydrogen atom or alkyl group having 1 to 2 carbon atoms ;
A2 is oxygen atom or NH ;
B2 is alkylene group having 2 to 4 carbon atoms or hydroxypropylene ; and
X2 is anionic counter ion.
7. The process for preparing hydrophilic polymer dispersion containing an inorganic flocculant according to claim 6, which further comprising the steps of : i ) mixing 1.0—25 wt % of acrylamide, 0—2 wt % of anionic monomer, 1.0—30 wt % of cationic monomer mixture of compound of formula I and formula TJ, 0.5—5 wt % of polymer selected from the group consisting of homopolymer of compound of formula I , homopolymer of compound of formula TJ and copolymer of compound of formula I and formula TJ, 10—30 wt % of anionic salt, 1 —10 wt % of inorganic flocculant, 0.01 —1 wt % of nonionic surfactant, 0.05—2 wt % of dispersion stabilizer and 40—75 wt % of water in the reactor ; ii ) nitrogen purging in the reactor, and agitating said mixture more than 30 rpm ; iii) heating said mixture at 30— 50 °C ; iv) adding 0.001 —0.1 wt % of initiator to said mixture ; v ) lst-polymerizing said mixture at 30— 50 °C for 3—6 hours ; vi) 2nd-polymerizing the lst-polymerized mixture containing unreacted monomers completely by adding 0.001 —0.1 wt % of initiator to said mixture for 3—15 hours ; vii) adding the remaining anionic salt to the polymer ; viii) adjusting pH of the polymer less than 4.0 ; and ix) sieving the polymer using 40—100 mesh.
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