KR101535996B1 - W/O type emulsion macromolecule coagulant containing aqueous dispersion co-polyacrylamide particles using kosmotropic bases and process for manufacturing the same - Google Patents

Abstract

The present invention relates to a method for preparing a first solution, comprising the first step of dissolving a mixture containing a nonionic water-soluble monomer and a cross-linking agent in deionized water to prepare a first solution, dissolving a cationic monomer and a water- And a third step of adding the cationic water-dispersible polyacrylamide copolymer particles after the second solution is added to an aliphatic solvent in an oil phase, heated and stirred to polymerize, and then the cationic water-dispersible polyacrylamide copolymer particles are added to the W / O emulsion coagulant The present invention relates to a method for producing a coagulant and a coagulant thereof, characterized in that the cationic water-dispersible polyacrylamide copolymer particles prepared by using the cosmotropic salt are contained in a large amount in the emulsion coagulant.

Description

(W / O type emulsion polymer coagulant containing cationic water-dispersible polyacrylamide copolymer particles produced by using cosmotropic salt and a method for producing the coagulant-containing coagulant-containing aqueous dispersion co-polyacrylamide particles using kosmotropic bases and process for manufacturing the same}

The present invention relates to a water-in-oil type emulsion type polymer flocculant, and more particularly to a water-in-oil type emulsion type polymer flocculant comprising a cationic water-dispersible acrylamide copolymer particle prepared by adding cosmotropic salts The present invention relates to a W / O emulsion polymer having good cohesiveness and dehydration ratio of a flock produced by emulsion polymerization, and a process for producing the W / O emulsion polymer.

In the wastewater treatment field, coagulation treatment is used as a method for coagulating and treating colloidal fine particles dispersed in wastewater. In wastewater such as industrial wastewater, clay, organic matter, bacteria, algae, pigment, polymer impurities are often dispersed in colloidal particles. Since coagulant enables to coagulate and remove the colloidal particles, It has been used to purify. Therefore, the polymer flocculant commonly used in the wastewater treatment field is a chemical substance that enables rapid precipitation by binding to suspended particles in water due to the action of active groups having electrical properties on the polymer, Water solubility, adsorptivity and dispersibility are required in order to exhibit such properties.

Polymer flocculants are classified into anionic, cationic or non-ionic types depending on the type of electrostatic charge when they are dissolved in water. Most colloidal particles have positive or negative polarity. Therefore, polymer flocculants are suitably selected When used, very large lumps (flocs) are formed and the turbidity can be effectively lowered. Examples of the synthetic organic flocculant include powder, water-soluble gel, and W / O type emulsion. The emulsion-type coagulant is easy to handle because there is no dust, and the degree of charge can be controlled by controlling the amount of anionic or cationic monomer in the production of the polymer. Among the conventional emulsion-type coagulants, coagulants having long chain molecular structure and excellent in hydrophilicity are widely used because they exhibit excellent coagulation effect even when added in small amounts to colloidal particles.

However, the water-soluble polymer flocculant polymer containing the emulsion-type coagulant generally has different coagulation effect depending on the property change of the wastewater during the wastewater treatment, and the flak is cracked even with a slight impact and the water content of the dehydrated sludge is high, many.

The present invention relates to a water-soluble polymer coagulant having excellent performance, which improves the irregular flocculation effect, the high water content of the dehydrated sludge, and the easily cracking phenomenon of the flocculent polymer, And to provide the above-mentioned objects.

According to a preferred embodiment of the present invention, 33.20 to 40.75 g of ion-exchanged water is injected and a mixture of 12.76 to 25.86 g of 50% acrylamide, 0.75 to 17.68 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, 80% 1.76 to 5.08 g of ethyl acrylate methyl chloride quaternary salt, 0.56 to 0.65 g of 99.5% glycerol, 4.06 to 5.60 g of 20% polydimethylaminoethyl acrylate methyl chloride quaternary salt and 2.44 g of 35% polydiallyldimethylammonium chloride A second step of injecting 5.52 to 25.86 g of ammonium sulfate and 6.54 g of sodium sulfate into a first solution and mixing the first solution with a solution of nitrogen, , And 0.44 to 0.56 g of 1% 2,2'-azobis (2-amidinopropane) dihydrochloride were added and stirred, and polymerization was carried out twice at 48 ° C for 8 hours A third step, and a fourth step of injecting acetic acid in an amount of from 0.58 to 1.01 g of acetic acid in an amount of from 2.58 to 4.20 g of 99.5% ammonium sulfate, of 7.52 g of 30% ammonium sulfate, and of a cationic water-dispersible polyacrylamide copolymer particle .

According to another preferred embodiment of the present invention, the cationic water-dispersible polyacrylamide copolymer particles produced by the above-described production method have different ionic strengths.

According to another preferred embodiment of the present invention, there is provided a method for producing a polymer electrolyte membrane, comprising the steps of: dissolving a mixture containing a nonionic water soluble monomer and a crosslinking agent in deionized water to prepare a second solution; A second step of dissolving dimethyl aminoethyl acrylate (DMAEA) to prepare a third solution; and a third step of adding the third solution to an aliphatic solvent in an oil phase and heating and stirring to polymerize the solution. Type emulsion copolymer according to the present invention.

According to still another preferred embodiment of the present invention, after the third step, a fourth step of adding ammonium persulfate and sodium bisulfate to remove residual monomers is further included in the fourth step And a method for producing the W / O type emulsion copolymer.

According to another preferred embodiment of the present invention, the nonionic water soluble monomer is at least one selected from the group consisting of acrylamide, methacrylamide, N, N-dimethyl acrylamide, N, N-diethylacrylamide, N- Hydroxypropylmethacrylate, N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethylmethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, Nt-butyl acrylamide, And N-methylol acrylamide, and the cross-linking agent is selected from the group consisting of N, N-methylenebisacrylamide, N, N-methylenebismethacrylamide, triallylamine, Triallylammonium salt, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, triethylene But are not limited to, glycol dimethyl acrylate, polyethylene glycol dimethacrylate, N-vinyl acrylamide, N-methylallyl acrylamide, glycidyl acrylate, acrolein, glyoxal, allyltrimethoxysilane, Vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, dimethoxysilane, vinyldimethoxyethoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltrisec- butoxysilane, vinyltrihexyloxysilane, Wherein the cationic monomer is a quaternary salt or acid salt of a dialkylaminoalkyl acrylate or methacrylate having an alkyl group having from 1 to 4 carbon atoms and a quaternary salt of a dialkylaminoalkyl acrylamide or methacrylamide Or a salt of a cationic monomer selected from the group consisting of do.

According to another preferred embodiment of the present invention, the molar percentage of the acrylamide: DMAEA: cationic monomer of the W / O type emulsion copolymer is 75: 20: 5 to 40:10:50.

According to another preferred embodiment of the present invention there is provided a composition comprising 19.81 to 45.12 g of a nonionic water soluble monomer 50% acrylamide, 0.0005 to 0.0011 g of a crosslinking agent methylene bisacrylamide, 1.38 g of adipic acid and 0.0005 to 0.011 g of sodium A first step of dissolving a mixture of 21.191 to 46.5121 g containing formate in deionized water to prepare a fourth solution and a step of adding 10.69 to 42.38 g of dimethylaminoethyl acrylate methyl chloride 4 A second step of preparing a fifth solution by dissolving sodium chloride, 5.02 to 11.39 g of DMAEA and 0.01 g of tetra sodium ethylenediamine tetra acetate (EDTA 4Na) as a chelating agent, Was added to 25.8 g of an aliphatic solvent on an oil phase, and while heating and stirring, 0.92 g of a sorbitan monostearate surfactant and 1.39 g of a sorbitan monostearate Azobis (2,4-dimetivaleronitrile) of 0.027 g and 0.0023 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were fed into a polymerization vessel And a third step of preparing a sixth solution by injecting 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate to remove the residual cationic monomer, and a third step of preparing a W / O emulsion polymer do.

According to another preferred embodiment of the present invention, 1.03 g of ammonium thiosulfate is added to the W / O type emulsion polymer produced by the above production method, the cationic water dispersible polyacrylamide copolymer prepared by the above- 20 g of water, 20 g of particles, and 2.08 g of polyoxyethylene lauryl ether, to obtain a W / O type emulsion polymer flocculant comprising the cationic water dispersible polyacrylamide copolymer particles.

According to another preferred embodiment of the present invention, there is provided a W / O type emulsion polymer flocculant comprising the cationic water dispersible polyacrylamide copolymer particles produced by the above production method.

As described above, in the present invention having the above-described structure, the emulsion polymer containing DMAEA and the cationic water-dispersible polyacrylamide copolymer particles can be obtained by mixing DMAEA with an emulsion containing no cationic water-dispersible polyacrylamide copolymer particles Compared with the polymer flocculant, the amount of coagulant injected is constant according to the change of the wastewater property, and the wastewater treatment results in a large and very strong flocs, which significantly improves the turbidity of the filtrate. In addition, since the water content of the dehydrated sludge is low, it has the advantage of reducing the processing cost such as the recycling of the treated water, the sludge burial, and the incineration.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view briefly showing a method for producing a W / O type emulsion coagulant containing the cationic water-dispersible polyacrylamide copolymer particles according to the present invention.

The present invention relates to a water-in-oil type emulsion polymer flocculant. More particularly, the present invention relates to a water-in-oil type emulsion polymer flocculant, and more particularly to a water- The present invention relates to a flocculant containing coalesced particles in an emulsion. In the present invention, DMAEA and a cross-linking agent are put on a monomer, emulsified with a solvent and an emulsifier, and then an initiator is added to carry out a polymerization reaction. DMAEA was added to the W / O type emulsion at the time of polymerization, and the cationic water dispersible polyacrylamide copolymer particles previously prepared in the polymer modified from the linear polymer to the network structure by adding a cross-linking agent to the network structure To flocculants added into the polymer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view briefly showing a method for producing a W / O type emulsion coagulant containing the above-mentioned cationic water-dispersible polyacrylamide copolymer particles.

Hereinafter, a method for producing the W / O type emulsion flocculant polymer of the present invention will be described.

The manufacturing method of the present invention comprises a first step of preparing a first solution by dissolving a mixture containing a nonionic water-soluble monomer and a cross-linking agent in deionized water; A second step of dissolving the cationic monomer and DMAEA in the first solution to prepare a second solution; And a third step of introducing the second solution into an aliphatic solvent in an oil phase and heating and stirring to polymerize the second solution. In addition, in the method of the present invention, a fourth step of adding ammonium persulfate and sodium bisulfate to the monomer to remove residual monomers may be selectively added.

Non-ionic water-soluble monomers that can be used in the present invention include acrylamide, methacrylamide, N, N-dimethyl acrylamide, N, N-diethylacrylamide, N- Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Nt-butyl acrylamide, N-methylol acrylamide, N-methylpyrrolidone, .

The cationic monomers that can be used in the present invention include quaternary salts or acid salts of dialkylaminoalkyl acrylates or methacrylates having alkyl groups of 1 to 4 carbon atoms and quaternary salts or acid salts of dialkylaminoalkyl acrylamide or methacrylamide Specific examples thereof include dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethyl Aminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride Salts, acrylamidopropyltrimethylammonium chloride, dimethylaminopropylacrylamide methylsulfate quaternary salt, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, dimethylaminopropylmethacrylamide methyl Diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyldiethylammonium chloride, diallyldimethylammonium chloride, and the like can be given as examples of the amphoteric surfactants such as dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, .

In the polymerization reaction of the present invention, it is possible to use a small amount of anionic monomer added to the cationic monomer. In such a case, there is an advantage that the reaction rate and the polymer dispersibility are increased. Examples of the anionic monomer that can be suitably used in the present invention include acrylic acid and its salts such as sodium acrylate and ammonium acrylate, methacrylic acid and salts thereof such as sodium methacrylate and ammonium methacrylate, Examples of the amphoteric surfactant include sulfonic acid (AMPS), sodium salt of AMPS, sodium vinylsulfonate, styrenesulfonate, maleic acid and salts thereof (including sodium salts and ammonium salts), sulfonate isotonate, sulfopropyl acrylate, sulfopropyl methacrylate, Methyl acrylamide, allylsulfonate, sodium vinylsulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, sulfomethylated acrylamide, and phosphonomethylated acrylamide.

The water-soluble polymer coagulant polymer generally has a low molecular weight and a low ion density as a linear structure. Therefore, the flocculant is broken even in a slight impact during wastewater treatment. To solve the above problems, . By containing DMAEA in the monomeric polymer, the linear polymer can be crosslinked to resist external stress, which can reduce the phenomenon that the flak easily breaks.

Further, in the present invention, a cross-linking agent is used in order to increase the agglomeration phenomenon of the emulsion polymer. By using the cross-linking agent, cross-linking property of the monomer can be increased to prevent breakage of the flock and effectively shorten the water content in the flock. That is, examples of the crosslinking agent for improving the structure and solubility of the polymer include N, N-methylenebisacrylamide, N, N-methylenebismethacrylamide, triallylamine, triallylammonium salt, ethylene glycol dimethacrylate, But are not limited to, glycol dimethacrylate, polyethylene glycol diacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, N-vinyl acrylamide, N-methylallyl acrylamide, glycidyl acrylate, acrolein, Allyltrimethoxysilane, allyltrimethoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethoxyethoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltrisec-butoxysilane, vinyltrihexyloxysilane , Vinylmethoxydioxyoxysilane, and the like. The most suitable cross-linking agents are N, N-methylene bisacrylamide and glyoxal.

Representative chain transfer agents include carboxylic acids such as alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butyl alcohol and glycerol, sulfur compounds such as alkylthiol, thiourea, sulfite and disulfide, formic acid and malic acid, Phosphates, phosphites such as sodium hypophosphite, and combinations of phosphate compounds. Of these, sodium hypophosphite and sodium formate can be suitably used as the chain transfer agent of the present invention.

As the salt of ethylenediamine tetraacetate as a chelating agent, an aliphatic hydrocarbon solvent may be used as the solvent. More specifically, it is a mixture of N-paraffin, iso-paraffin, and naphtalenic, which is a mixture of a hydrocarbon having a aromatics component of not more than 0.4% ) Solvent is appropriate. It is an appropriate use for the purpose of the present invention that the surfactant is a sorbitan monooleate type, sorbitan monostearate type. It is appropriate that the initiator is generated by pyrolysis of azo compounds, peroxides, peroxides and ester compounds. Particularly suitable initiators are azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile).

In the present invention, ammonium persulfate and sodium bisulfate are added after completion of the polymerization to remove the remaining anionic or cationic monomers such as acrylamide monomer and acrylic acid to ensure the stability of the product, and W / O (Water-in-oil type) emulsion flocculating agent, and polyoxyethylene aluryl ether may be suitably used.

In the present invention, it is preferable that the crosslinking agent is injected and emulsified in the step of monomer composition, and the chain transfer agent is introduced at the ending stage in which polymerization of the monomer proceeds about 80%.

The amount of acrylamide, DMAEA and cationic monomer used is suitably in the range of 75: 20: 5 to 40:10:50 for acrylamide: DMAEA: cationic monomer (mol%).

The cross-linking agent is used in an amount of not more than 500 ppm, suitably about 20 to about 60 ppm, based on the effective weight of acrylamide. When the amount is less than 20 ppm, the effect due to the use of the cross-linking agent can not be obtained, and if the amount is more than 500 ppm, it is not economically feasible.

The cationic water-dispersible polyacrylamide copolymer particles vary in ionic strength and flocculation efficiency depending on the state of the wastewater to be treated, so that the optimum amount of the water is determined. However, considering the emulsion stability of the polymer flocculant, Is used in an amount of 5 to 70% by weight, preferably 10 to 50% by weight based on the total amount. The pH of the second solution containing DMAEA and the cationic monomer is suitably adjusted in the range of 3.0 to 5.0, and most preferably in the range of 3.8 to 4.8 in terms of emulsion formation and stability.

Hereinafter, the production method of the cationic water-dispersible polyacrylamide copolymer particles of the present invention will be described in detail through Production Examples. However, the technical scope of the present invention is not limited by the following Production Examples.

Manufacturing example  One

36.35 g of ion-exchanged water was charged into a reactor equipped with a stirrer and a temperature controller, and 25.86 g of 50% acrylamide, 0.75 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, 1.78 g of 80% dimethylaminoethyl acrylate methyl chloride quaternary salt, 0.65 g of 99.5% glycerol, 20% of polydimethylaminoethyl acrylate methyl chloride quaternary salt 4.45 g of acrylate methyl chloride quaternary salt and 2.44 g of 35% of poly-diallyldimethyl ammonium chloride were sequentially injected and dissolved. Then, 25.86 g of ammonium sulfate, which is a kind of cosmotropic salt, was injected and mixed . Azobis (2-amidinopropane) dihydrochloride (1%) was added to the reaction mixture while stirring with nitrogen, and the mixture was stirred at 48 ° C for 8 After the polymerization was carried out twice, 2.83 g of 99.5% ammonium sulfate and 0.56 g of acetic acid were added to complete the polymerization.

Manufacturing example  2

33.18 g of ion-exchanged water was charged into a reactor equipped with a stirrer and a temperature controller, and 23.42 g of 50% acrylamide, 7.35 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, 1.76 g of 80% dimethylaminoethyl acrylate methyl chloride quaternary salt, 0.59 g of 99.5% glycerol, 20 g of polydimethylaminoethyl acrylate methyl chloride quaternary salt 4.45 g of acrylate methyl chloride quaternary salt and 2.44 g of 35% of poly-diallyldimethyl ammonium chloride were sequentially injected and dissolved. Then, 23.64 g of ammonium sulfate, which is a kind of cosmotropic salt, was injected and mixed . Azobis (2-amidinopropane) dihydrochloride (0.22 g) was added to the reaction mixture while stirring with nitrogen, and the mixture was stirred at 48 ° C for 8 After the polymerization was carried out twice, 2.58 g of 99.5% ammonium sulfate and 0.52 g of acetic acid were added to complete the polymerization.

Manufacturing example  3

37.93 g of ion-exchanged water was charged into a reactor equipped with a stirrer and a temperature control device, and 20.40 g of 50% acrylamide, 11.52 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, , 3.31 g of 80% dimethylaminoethyl acrylate methyl chloride quaternary salt, 0.56 g of 99.5% glycerol, 20% of polydimethylaminoethyl acrylate methyl chloride quaternary salt acrylate methyl chloride quaternary salt) are successively injected and dissolved. Then, 5.55 g and 6.54 g of ammonium sulfate and sodium sulfate, which are one kind of cosmotropic salts, are respectively injected and mixed. Azobis (2-amidinopropane) dihydrochloride) was added thereto while stirring at room temperature, and the mixture was stirred at 48 占 폚 for 8 After the polymerization was carried out twice, 4.20 g of 99.5% ammonium sulfate and 1.01 g of acetic acid were added to complete the polymerization.

Manufacturing example  4

35.33 g of ion-exchanged water was charged into a reactor equipped with a stirrer and a temperature controller, and 16.57 g of 50% acrylamide, 15.11 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, , 4.34 g of 80% dimethylaminoethyl acrylate methyl chloride quaternary salt, 0.62 g of 99.5% glycerol, 20.0 g of polydimethylaminoethyl acrylate methyl chloride quaternary salt acrylate methyl chloride quaternary salt) were sequentially injected and dissolved, and 15.23 g of ammonium sulfate, which is a kind of cosmotropic salt, was injected and mixed. Azobis (2-amidinopropane) dihydrochloride) was added thereto while stirring at room temperature, and the mixture was stirred at 48 ° C for 8 After the polymerization was carried out twice, 3.48 g of 99.5% ammonium sulfate and 0.95 g of acetic acid were added to complete the polymerization.

Manufacturing example  5

32.19 g of ion-exchanged water was charged into a reactor equipped with a stirrer and a temperature controller, and 12.76 g of 50% acrylamide, 17.68 g of 80% dimethylaminoethyl acrylate benzyl chloride quaternary salt, , 5.08 g of 80% dimethylaminoethyl acrylate methyl chloride quaternary salt, 0.56 g of 99.5% glycerol, 20 g of polydimethylaminoethyl acrylate methyl chloride quaternary salt acrylate methyl chloride quaternary salt) are sequentially injected and dissolved, and 12.28 g of ammonium sulfate, which is a kind of cosmotropic salt, is injected and mixed. Azobis (2-amidinopropane) dihydrochloride) was added thereto while stirring at room temperature, and the mixture was stirred at 48 占 폚 for 8 The polymerization was carried out twice, followed by the addition of 3.48 g of 99.5% ammonium sulfate, 7.52 g of 30% ammonium sulfate and 0.86 g of acetic acid.

The compositions shown in Table 4 are shown in Table 5, and the results of the measurement are shown in Table 5.

Hereinafter, a method for producing the W / O type emulsion polymer flocculant will be described in detail. However, the technical scope of the present invention is not limited by the following examples.

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methylchloride ratio of 72:18:10 (mol%) is prepared.

45.12 g of acrylamide (50%) as a water-soluble monomer, 0.0011 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.011 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution was added 10.69 g of dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution as a cationic monomer, 11.39 g of DMAEA (99.9%), and tetrasodium ethylene diamine tetraacetate , EDTA · 4Na), and the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

Thereafter, 20 g of the cationic water-dispersible polyacrylamide copolymer particles of Preparation Example 1 prepared in advance was injected, and the reactor temperature was lowered to 35 ° C or lower. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 64:16:20 (mol%) is prepared.

37.63 g of acrylamide (50%) as a water-soluble monomer, 0.00094 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.0094 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution was added 20.07 g of a cationic monomer, dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution, 9.50 g of DMAEA (99.9%), and tetrasodium ethylene diamine tetraacetate acetate, EDTA · 4Na) was added thereto, and the mixture was completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

Thereafter, 20 g of the cationic water-dispersible polyacrylamide copolymer particles of Preparation Example 2, which had been prepared in advance, was injected, and the temperature of the reaction vessel was lowered to 35 ° C or lower. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 56:14:30 (mol%) is prepared.

31.01 g of acrylamide (50%) as a water-soluble monomer, 0.00078 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.0078 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution were added 28.38 g of a cationic monomer, dimethylaminoethyl acrylate methyl chloride quaternary salt (80.%) solution, 7.81 g of DMAEA (99.9%), tetra sodium ethylenediamine tetraacetate acetate, EDTA · 4Na) was added thereto, and the mixture was completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

Thereafter, 20 g of the cationic water-dispersible polyacrylamide copolymer particles of Preparative Preparation Example 3, which had been prepared in advance, was injected, and the reactor temperature was lowered to 35 ° C or lower. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 48:12:40 (mol%) is prepared.

25.12 g of acrylamide (50%) as a water-soluble monomer, 0.00063 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.0063 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution was added 35.74 g of a cationic monomer, dimethylaminoethyl acrylate methyl chloride quaternary salt (80.%) solution, 6.34 g of DMAEA (99.9%), tetra sodium ethylenediamine tetraacetate acetate, EDTA · 4Na) was added thereto, and the mixture was completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

Thereafter, 20 g of the cationic water-dispersible polyacrylamide copolymer particles of Preparation Example 4, which had been prepared in advance, was injected, and the reactor temperature was lowered to 35 ° C or lower. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

First, an emulsion copolymer having a ratio of acrylamide: DMAEA: dimethylaminoethyl acrylate methylchloride of 40:10:50 (mol%) is prepared.

19.81 g of acrylamide (50%) as a water-soluble monomer, 0.0005 g of methylene bisacrylamide as a crosslinking agent, 1.38 g of adipic acid and 0.005 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution, 42.38 g of a dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution as a cationic monomer, 5.02 g of DMAEA (99.9%), and a tetra sodium ethylene diamine tetraacetate acetate, EDTA · 4Na) was added thereto, and the mixture was completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

Thereafter, 20 g of the cationic water-dispersible polyacrylamide copolymer particles of Preparation Example 5, which had been prepared in advance, was injected, and the reactor temperature was lowered to 35 ° C or lower. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

Comparative Example 1

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 90: 0: 10 (mol%) was prepared.

76.51 g of acrylamide (50%) as a water-soluble monomer, 0.0011 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.011 g of sodium formate were mixed and completely dissolved to prepare a first solution.

10.69 g of a dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution, which is a cationic monomer, and 0.01 g of a chelating agent, tetrasodium ethylene diamine tetraacetate (EDTA · 4Na) And the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

The reactor temperature is then lowered to below 35 ° C. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

Comparative Example 2

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 80: 0: 20 (mol%) was prepared.

67.13 g of acrylamide (50%) as a water-soluble monomer, 0.00094 g of methylene bisacrylamide as a crosslinking agent, 1.38 g of adipic acid and 0.0094 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution were added 20.07 g of a cationic monomer, dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution, 0.01 g of a chelating agent, tetrasodium ethylene diamine tetraacetate (EDTA .4Na) And the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

The reactor temperature is then lowered to below 35 ° C. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

Comparative Example 3

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 70: 0: 30 (mol%) was prepared.

58.82 g of acrylamide (50%) as a water-soluble monomer, 0.00078 g of methylene bisacrylamide as a crosslinking agent, 1.38 g of adipic acid and 0.0078 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution, 28.38 g of a dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution as a cationic monomer, 0.01 g of a chelating agent tetrasodium ethylene diamine tetraacetate (EDTA .4Na) And the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

The reactor temperature is then lowered to below 35 ° C. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

Comparative Example 4

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 60: 0: 40 (mol%) was prepared.

51.46 g of acrylamide (50%) as a water-soluble monomer, 0.00063 g of methylene bisacrylamide as a crosslinking agent, 1.38 g of adipic acid and 0.0063 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution, 35.74 g of a dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution as a cationic monomer, 0.01 g of tetra sodium ethylenediamine tetraacetate (EDTA .4Na) as a chelating agent, And the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

The reactor temperature is then lowered to below 35 ° C. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

Comparative Example 5

First, an emulsion copolymer having an acrylamide: DMAEA: dimethylaminoethyl acrylate methyl chloride ratio of 50: 0: 50 (mol%) was prepared.

44.83 g of acrylamide (50%) as a water-soluble monomer, 0.0005 g of methylene bisacrylamide as a cross-linking agent, 1.38 g of adipic acid and 0.005 g of sodium formate were mixed and completely dissolved to prepare a first solution.

To the first solution, 42.38 g of a dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) solution as a cationic monomer, 0.01 g of tetra sodium ethylene diamine tetraacetate (EDTA 4Na) as a chelating agent, And the mixture is completely dissolved to prepare a second solution. The pH of the second solution mixture is 4.4.

The oil phase is charged with 25.83 g of an aliphatic solvent (Dearomatized Hydrocarbon), and the temperature is raised to 54 to 57 ° C. When the addition was completed, a mixture of 0.92 g of a sorbitan monooleate type surfactant (HLB of 4.0 to 6.0) and 1.39 g of a sorbitan monostearate type surfactant (HLB of 9.0 to 15.0) was added while vigorously stirring, . The second solution is injected into the oil phase while stirring at 1200 rpm. Once injection is complete, the speed of the agitator is reduced to 600 rpm and the temperature of the reactor is maintained at 45 ° C and purged with nitrogen for 1 hour. After the elapse of the time, 0.027 g of 2,2'-azobis (isobutyronitrile) was added in a nitrogen atmosphere and reacted for 4 hours. Then, 2,2'-azobis (2,4-dimethylvaleronitrile) 2,2'-azobis (2,4-dimethylvaleronitrile)) was added thereto. After 3 hours had elapsed, the temperature of the reaction vessel was raised to 65 ° C and reacted for 1 hour. After this time, 0.05 g of ammonium persulfate and 0.1 g of sodium bisulfate were added and reacted to remove the remaining monomer for 1 hour. Then, 1.03 g of ammonium thiosulfate is injected and reacted for 1 hour.

The reactor temperature is then lowered to below 35 ° C. When the above temperature is reached, 2.08 g of polyoxyethylene lauryl ether is added to ensure the stability of the coagulant prepared.

The components and composition ratios of the W / O type emulsion polymer flocculants of Examples 1 to 5 are shown in Table 1 below. In Table 2, the reduction boiling points of DMAEA and the cationic water dispersible polyacrylamide copolymer particles Reduced Specific Viscosity (RSV) and ion density were measured and the results were shown.

In order to confirm the effect of the coagulant according to the present invention, in order to compare the water content of the sludge after arbitrarily selecting the example 4 and the comparative example 4, the weight of the sludge before drying and the sludge after drying at 105 ° C for 2 hours The turbidity of the sludge was measured by comparing the weights and the turbidity of the dehydrated filtrate was measured in order to determine the degree of turbidity of the water by the impurities. The emulsion coagulant and the emulsion containing the organic coagulant prepared by the present invention The polymer was tested by arbitrarily adjusting the properties of the wastewater. The results are shown in Table 3 below.

The components and compositions of the cationic water-dispersible polyacrylamide copolymer particles of Production Examples 1 to 5 are shown in Table 4 below. The viscosity, pH, solids content and charge density Charge density was measured and the measurement results are shown in Table 5 below.

Component (g) Example 1 Example 2 Example 3 Example 4 Example 5 50% acrylamide 45.12 37.73 31.01 25.12 19.81 Methylene bisacrylamide 0.0011 0.00094 0.00078 0.00063 0.0005 Apidic acid 1.38 1.38 1.38 1.38 1.38 Sodium formate 0.011 0.0094 0.0078 0.0063 0.0005 Dimethylaminoethyl acrylate methyl chloride quaternary salt (80%) 10.69 20.07 28.38 35.74 42.38 DMAEA 11.39 9.50 7.81 6.34 5.02 Tetrasodium ethylenediamine tetraacetate 0.01 0.01 0.01 0.01 0.01 Aliphatic solvent 25.8 25.8 25.8 25.8 25.8 Sorbitan monooleate 0.92 0.92 0.92 0.92 0.92 Sorbitan monostearate 1.39 1.39 1.39 1.39 1.39 2,2'-azobis (isobutyronitrile) 0.027 0.027 0.027 0.027 0.027 2,2'-azobis (2,4-dimethylvaleronitrile) 0.0023 0.0023 0.0023 0.0023 0.0023 Ammonium persulfate 0.05 0.05 0.05 0.05 0.05 Sodium bisulfate 0.1 0.1 0.1 0.1 0.1 Ammonium thiosulfate 1.03 1.03 1.03 1.03 1.03 The cationic water-dispersible polyacrylamide copolymer particles 20 20 20 20 20 Polyoxyethylene lauryl ether 2.08 2.08 2.08 2.08 2.08 Total amount 120.00 120.00 120.00 120.00 120.00

Classification The cationic monomer / cationic monomer
(mol) DMAEA (% by weight) The cationic water-dispersible polyacrylic copolymer particles
(weight%) RSV
(dl / g) Ion density
(meq / g) Example 1 72:18:10 9.5 16.7 0.6 1.4 Comparative Example 1 90: 0:10 - - 1.7 1.6 Example 2 64:12:20 7.9 16.7 1.1 1.8 Comparative Example 2 80: 0: 20 - - 2.1 2.0 Example 3 56:14:30 6.5 16.7 1.5 2.4 Comparative Example 3 70: 0:30 - - 2.5 2.6 Example 4 48:12:40 5.2 16.7 1.8 2.7 Comparative Example 4 60: 0:40 - - 2.8 3.1 Example 5 40:10:50 4.2 16.7 1.9 3.3 Comparative Example 5 50: 0:50 - - 2.2 3.5

(Ion density: equivalent to polyvinylsulfate potassium 0.0025N standard titrant)

Wastewater property ratio Input (350ppm) Sludge moisture content (%) Dehydrated filtrate Turbidity (NTU) Example 4 Comparative Example 4 Example 4 Comparative Example 4 Example 4 Comparative Example 4 Digested land: surplus
4: 0

86.41 86.09 145 138 Digested land: surplus
3: 1

86.04 86.61 143 131 Digested land: surplus
2: 2

85.98 86.81 135 134 Digested land: surplus
1: 3

86.75 87.27 130 129 Digested land: surplus
0: 4

86.98 87.22 129 131

Component (g) Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Deionized water 34.34 33.20 40.75 37.99 34.60 50% acrylamide 25.86 23.42 20.40 16.57 12.76 80% Dimethylaminoethyl acrylate Benzyl chloride Quaternary salt 0.75 7.35 11.52 15.11 17.68 80% Dimethylaminoethyl acrylate methyl chloride quaternary salt 1.78 1.76 3.31 4.34 5.08 Glycerol 0.65 0.59 0.56 0.62 0.56 20% polydimethylaminoethyl acrylate methyl chloride quaternary salt 4.45 4.06 5.60 5.19 4.72 35% polydiallylmethylammonium chloride 2.44 2.44 - - - Ammonium sulfate 25.86 23.64 5.55 15.23 12.28 Sodium sulfate - - 6.54 - - 2,2-azobis (2-amidinopropane) dihydrochloride 0.48 0.44 0.56 0.52 0.46 99.5% ammonium sulfate 2.83 2.58 4.20 3.48 3.48 30% ammonium sulfate - - - - 7.52 Acetic acid 0.56 0.52 1.01 0.95 0.86 Total amount 100 100 100 100 100

Dispersion viscosity
(cps) pH Solid Contents
(%) Charge density
(meq / g) Production Example 1 170 3.6 45.0 0.325 Production Example 2 300 3.7 48.4 0.375 Production Example 3 625 3.7 45.6 0.530 Production Example 4 843 3.8 45.6 0.650 Production Example 5 915 3.8 46.4 0.725

Comparing Examples 1 to 5 and Comparative Examples 1 to 5 in Table 2, it was found that the addition of DMAEA and cationic water-dispersible polyacrylamide copolymer to DMAEA and cationic water-dispersible polyacrylamide The reduction specific viscosity of the comparative example in which the copolymer particles were not added was higher, which indicates that the viscosity of the solution except for the flock was lowered as more flocs solidified firmly. In addition, the ion density showed a similar pattern to the reduction boiling point, which also indicates that ions in the solution aggregate more with the flux, resulting in a lower ion density.

When the sludge moisture content and dehydration filtrate turbidity of Example 4 and Comparative Example 4 in Table 3 were compared, it was found that the sludge moisture content at all ratios except for the ratio of digestion: surplus was 4: 0, . The sludge moisture content means that the purity of Comparative Example 4 is lower than that of Example 4. It can be seen that adding DMAEA and the cationic water dispersible polyacrylamide copolymer particles makes the purity higher. Also, in the dehydrated filtrate turbidity, the turbidity of Comparative Example 4 was higher than that of Example 4 at all ratios of digestion: surplus, which indicates that Comparative Example 4 did not form harder flocs than Example 4 have.

From the above results, it can be seen that the W / O type emulsion polymer flocculant added with DMAEA and cationic water-dispersible polyacrylamide copolymer particles is more effective than DMAEA and cationic water dispersible polyacrylamide copolymer particles in the case of dehydration improvement Which is better than this.

Claims (9)

Ion exchanged water was injected into the reaction system and the reaction was carried out in the same manner as in Example 1, except that acrylamide, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl chloride quaternary salt, glycerol, polydimethylaminoethyl acrylate methyl chloride quaternary salt and polydiallyldimethylammonium chloride Sequentially injecting and dissolving the first solution to obtain a first solution;
A second step of injecting and mixing ammonium sulfate and sodium sulfate, which are one kind of cosmotropic salts, into the first solution;
Azobis (2-amidinopropane) dihydrochloride while being substituted with nitrogen and stirred, and the polymerization is carried out twice at 48 ° C for 8 hours; And
Ammonium sulfate, and acetic acid,
Dispersible polyacrylamide copolymer particles having a viscosity of 710 to 915 cps, a pH of 3.6 to 3.8, a solid content of 45.0 to 48.4%, and a charge density of 0.325 to 0.725 meq / g.
A cationic water-dispersible polyacrylamide, which is produced by the manufacturing method of claim 1 and has a viscosity of 710 to 915 cps, a pH of 3.6 to 3.8, a solid content of 45.0 to 48.4% and a charge density of 0.325 to 0.725 meq / g Copolymer particles.
A first step of dissolving a mixture containing a nonionic water-soluble monomer and a cross-linking agent in deionized water to prepare a second solution;
A second step of dissolving a cationic monomer and dimethylaminoethyl acrylate (DMAEA) in the second solution to prepare a third solution;
A third step of introducing the third solution into an aliphatic solvent in an oil phase, heating and stirring to polymerize the third solution; And
Comprising the step of polymerizing the cationic water-dispersible polyacrylamide copolymer particles produced by the production method of claim 1 and polyoxyethylene oleyl ether,
The nonionic water soluble monomer may be at least one selected from the group consisting of acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, From the group consisting of N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Nt-butyl acrylamide, and N-methylol acrylamide. Is selected from any one of the nonionic water-soluble monomers,
The cross-linking agent is selected from the group consisting of N, N-methylenebisacrylamide, N, N-methylenebismethacrylamide, triallylamine, triallylammonium salt, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacryl Acrylate, glycidyl acrylate, glycerol, glyoxal, allyltrimethoxysilane, allyltriacetoxy, allyltriacetoxysilane, triethyleneglycol dimethylacrylate, polyethylene glycol dimethacrylate, N-vinyl acrylamide, N-methylallyl acrylamide, glycidyl acrylate, And vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Is a cross-linking material selected from the group consisting of < RTI ID = 0.0 >
The cationic monomer is selected from the group consisting of quaternary salts or acid salts of dialkylaminoalkyl acrylates or methacrylates having an alkyl group having from 1 to 4 carbon atoms and quaternary salts or acid salts of dialkylaminoalkyl acrylamide or methacrylamide Is a cationic monomer,
Wherein the molar ratio of the acrylamide: DMAEA: cationic monomer is 75: 20: 5 to 40:10:50.
The method of claim 3,
The method further comprising a fourth step of adding ammonium persulfate and sodium bisulfate to remove the remaining monomer after the third step to prepare a W / O type emulsion polymer flocculant .
delete delete delete delete A W / O type emulsion polymer flocculant produced by the production method according to claim 3 or claim 4, having a reduced specific viscosity of 0.6 to 1.9 dl / g and an ion density of 1.4 to 3.3 meq / g.

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