JP7460067B2 - Inorganic compound-containing aggregation treatment agent composition - Google Patents

Description

The present invention relates to a polyacrylamide-based water-soluble polymer that is widely used as a flocculation treatment agent. Specifically, the present invention relates to a polyacrylamide-based water-soluble polymer that is widely used as a coagulation treatment agent. Specifically, it improves flocculation treatment performance in sludge dewatering applications, wastewater treatment applications, yield improvement applications in papermaking processes, etc. The present invention relates to an aggregation treatment agent composition and a method thereof.

Flocculating agents are used in the dehydration of organic sludge, such as primary raw sludge settled from sewage, excess sludge or mixed raw sludge settled from effluent from an activated sludge tank, and digested sludge obtained by anaerobic digestion of these sludges; in the treatment of industrial wastewater discharged from various factories; as retention aids for improving the retention rate on the wire of pulp fibers, fillers, papermaking chemicals, etc. in the papermaking process; and as drainage improvers that emphasize the function of improving drainage as well as retention.
Polyacrylamide (PAM)-based water-soluble polymers are generally used as these flocculating agents. Various proposals have been made to improve the flocculating performance of these PAM-based water-soluble polymers, and in particular, attempts have been made to improve the flocculating performance by incorporating an inorganic salt into the PAM-based water-soluble polymer.
For example, Patent Document 1 describes a papermaking agent in which an inorganic salt is added to a PAM-based water-soluble polymer consisting of a water-in-oil emulsion, and Patent Document 2 describes a sludge dewatering agent in which an inorganic salt is added to a PAM-based water-soluble polymer consisting of a water-in-oil emulsion. These are added at 0.5 to 15 mass % relative to the amount of water-in-oil emulsion liquid during polymerization, and depending on the properties of the material to which the flocculation treatment agent is added, the effect may not be obtained, and the effect is also limited depending on the composition and physical properties of the polymer.
Patent Document 3 describes an aggregating treatment agent containing an inorganic salt, the purpose of which is to reduce the solution viscosity at 25° C. to 100,000 centipoise or less, thereby improving handleability by lowering the viscosity of the dissolving solution.
Patent Document 4 describes a polymer emulsion composition containing an inorganic salt in a water-in-oil polymer emulsion, in which the inorganic salt is contained in an amount of 0.1 to 20% by weight based on the total weight of the composition, with the aim of improving the storage stability of the composition.
Therefore, there is a demand for a flocculating treatment agent that is not easily affected by fluctuations in the properties of the substance to which it is added, or by the composition and physical properties of the polymer, and a method for improving the effect of the flocculating treatment agent with a relatively simple operation.

JP 2011-99076 A Japanese Patent Application Publication No. 2011-194347 Japanese Patent Application Publication No. 6-329866 Japanese Patent Application Publication No. 7-62254

The present invention relates to a flocculant treatment agent used as a retention improver or freeness improver used in sludge dewatering treatment, industrial wastewater treatment, or paper making process, and relates to a coagulation treatment agent composition or flocculation treatment agent with higher performance. The task is to provide a method.

As a result of intensive studies to solve the above problems, we have achieved improvement in flocculation treatment performance by using a flocculation treatment agent composition containing a sulfuric acid compound or a sulfonic acid compound in the water-soluble polymer solution. We have discovered that this can be done, leading to the present invention.

By using the aggregation treatment agent composition of the present invention, improvement in aggregation treatment performance can be achieved with a simple operation regardless of changes in the properties of the object to be added.

一般式（２）
Ｒ_５は水素、メチル基またはカルボキシメチル基、ＱはＳＯ_３ ^－、Ｃ_６Ｈ_４ＳＯ_３ ^－、ＣＯＮＨＣ（ＣＨ_３）_２ＣＨ_２ＳＯ_３ ^－、Ｃ_６Ｈ_４ＣＯＯ^－あるいはＣＯＯ^－、Ｒ_６は水素またはＣＯＯ^－Ｙ_２ ^＋、Ｙ_１あるいはＹ_２は水素または陽イオンをそれぞれ表わす。 The water-soluble polymer in the present invention includes 0 to 99 mol% of a cationic monomer represented by the following general formula (1), and 0 to 99 mol% of an anionic monomer represented by the following general formula (2). %, and the nonionic monomer constitutes 1 to 100 mol% as a constituent unit. These are broadly classified according to their ionicity. A cationic water-soluble polymer is composed of a cationic monomer represented by the general formula (1) and a nonionic monomer, and a cationic water-soluble polymer is composed of a cationic monomer represented by the general formula (2) and a nonionic monomer. Anionic water-soluble polymers are composed of ionic monomers, cationic monomers represented by general formula (1), anionic monomers represented by general formula (2), and nonionic polymers. Amphoteric water-soluble polymers are composed of monomers, and nonionic water-soluble polymers are composed only of nonionic monomers.
In the case of cationic or amphoteric water-soluble polymers, 1 to 50 mol% of the cationic monomer represented by general formula (1) and 0 to 50 mol% of the anionic monomer represented by general formula (2) , the nonionic monomer content is preferably 0 to 99 mol%. In the case of anionic water-soluble polymers, it is preferable that the anionic monomer represented by general formula (2) be 1 to 50 mol% and the nonionic monomer be 50 to 99 mol%. This is because it is difficult to obtain a high molecular weight when the proportion of the ionic monomer is large. More preferably, the ionic monomer content is 1 to 40 mol%.
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl or alkoxy group having 1 to 3 carbon atoms, R ₄ is an alkyl or alkoxy group having 1 to 3 carbon atoms, an alkyl group or an aryl group having 7 to 20 carbon atoms, A represents oxygen or NH, B represents an alkylene group having 2 to 4 carbon atoms, and X ₁ ^- represents an anion.

General formula (2)
R ₅ is hydrogen, methyl group or carboxymethyl group, Q is SO ₃ ^- , C ₆ H ₄ SO ₃ ^- , CONHC(CH ₃ ) ₂ CH ₂ SO ₃ ^- , C ₆ H ₄ COO ^- or COO ^- , R ₆ represents hydrogen or COO ⁻ Y ₂ ⁺ , and Y ₁ or Y ₂ represents hydrogen or a cation, respectively.

Cationic monomers represented by the general formula (1) include quaternized products of dimethylaminoethyl (meth)acrylate or dimethylaminopropyl acrylamide with halides of lower alkyl groups such as methyl chloride or ethyl chloride. For example, (meth)acryloyloxyethyl trimethylammonium chloride, (meth)acryloyloxyethyl dimethylbenzylammonium chloride, (meth)acryloylaminopropyl trimethylammonium chloride, (meth)acryloylaminopropyl dimethylbenzylammonium chloride, (meth)acryloyloxy-2-hydroxypropyl trimethylammonium chloride, etc. Two or more of these may be combined. Anionic monomers represented by the general formula (2) include (meth)acrylic acid or its alkali metal salts or ammonium salts such as sodium salt, maleic acid or its alkali metal salts, acrylamidoalkanesulfonic acids such as acrylamido-2-methylpropanesulfonic acid, etc. Two or more of these may be combined.

Nonionic monomers used in the present invention include (meth)acrylamide, N,N'-dimethylacrylamide, acrylonitrile, 2-hydroxyethyl (meth)acrylate, diacetone acrylamide, N-vinylpyrrolidone, N- -Vinylformamide, N-vinylacetamide, acryloylmorpholine and the like. Among these, (meth)acrylamide is preferred. There is no problem even if two or more of these are combined.

The water-soluble polymer of the present invention can be produced by known methods. It can be produced by copolymerizing one or more monomers or monomer mixtures selected from cationic monomers, nonionic monomers, and anionic monomers. The copolymerization is carried out by any polymerization method. For example, after polymerization by aqueous solution polymerization, water-in-oil emulsion polymerization, water-in-oil dispersion polymerization, dispersion polymerization in salt water, etc., the product can be in any form, such as an aqueous solution, a dispersion in salt water, a water-in-oil emulsion, or a powder. Among these, water-in-oil emulsion polymerization, which is relatively easy to increase the molecular weight, is preferred because of the large improvement in performance.

In the case of a water-in-oil emulsion, it can be appropriately produced according to the methods listed in JP-A-10-140496, JP-A-2011-99076, and the like. A monomer mixture containing one or more selected from cationic monomers, nonionic monomers, and anionic monomers is mixed with water, an oily substance consisting of a hydrocarbon immiscible with at least water, and oil. An amount effective to form a water-in-oil emulsion and at least one type of surfactant having an HLB are mixed, vigorously stirred to form a water-in-oil emulsion, and then polymerized.

Examples of oily substances made of hydrocarbons used as dispersion media include paraffins, naphthenes, mineral oils such as kerosene, light oil, and medium-weight oil, synthetic hydrocarbon oils having substantially the same range of boiling points, viscosity, and other properties as these, and mixtures of these. The content is in the range of 20% to 50% by mass, and preferably 20% to 35% by mass, based on the total amount of the water-in-oil emulsion.

Examples of at least one surfactant having an effective amount and HLB to form a water-in-oil emulsion are nonionic surfactants with an HLB of 1 to 15, specific examples of which include sorbitan monooleate, Examples include sorbitan monostearate, sorbitan monopalmitate, polyoxyethylene nonylphenyl ether, and the like. The amount of these surfactants added is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.

After polymerization, a hydrophilic surface-forming agent called a phase inversion agent is added as necessary to make the emulsion particles covered with an oil film more compatible with water and to make it easier for the water-soluble polymers inside to dissolve. diluted with water and used for each purpose. Examples of hydrophilic surfactants include cationic surfactants and nonionic surfactants with HLB of 9 to 15, such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alcohol ether, and the like.

The polymerization conditions are usually appropriately determined depending on the monomers used and the copolymerization mol%, and the temperature is 20 to 80°C, preferably 20 to 60°C. A radical polymerization initiator is used to initiate polymerization. These initiators may be either oil-soluble or water-soluble, and any of azo type, redox type, and peroxide type can be used for polymerization. Examples of oil-soluble azo initiators include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis(2-methylbutyronitrile). dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like.

Examples of water-soluble azo initiators include 2,2'-azobis(amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-imidazolin-2-yl)propane] dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), etc. Examples of redox initiators include combinations of ammonium peroxodisulfate with sodium sulfite, sodium hydrogensulfite, trimethylamine, tetramethylethylenediamine, etc. Examples of peroxide initiators include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate, etc.

In order to control the degree of polymerization, it is effective to use isopropyl alcohol in an amount of 0.1 to 5% by weight based on the monomer, or to use sodium formate in an amount of 0.02 to 0.5% by weight based on the monomer.

The polymerization concentration of the monomer is in the range of 20 to 60% by mass, and the polymerization concentration and temperature are appropriately set depending on the composition of the monomer and the selection of the initiator.

In the water-soluble polymer of the present invention, a crosslinkable monomer may be used as a structural modifier during or after polymerization. When used, it is preferably 0.01% by mass or less based on the total amount of monomers. Examples of crosslinking monomers include N,N'-methylenebis(meth)acrylamide, triallylamine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and diethylene glycol dimethacrylate. 1,3-Butylene glycol methacrylate, polyethylene glycol di(meth)acrylate, N-vinyl(meth)acrylamide, N-methylallylacrylamide, glycidyl acrylate, polyethylene glycol diglycidyl ether, acrolein, glyoxal, vinyl trimethoxy Examples include silane, and among these, N,N'-methylenebis(meth)acrylamide is preferred.

The water-soluble polymer in the present invention needs to have a high molecular weight in order to exhibit a certain level of performance as a coagulation agent. The weight average molecular weight measured by the intrinsic viscosity method is in the range of 5 million to 30 million, preferably 8 million to 30 million, and more preferably 10 million to 30 million.

Examples of the sulfate compounds in the present invention include ammonium sulfate, magnesium sulfate, aluminum sulfate, calcium sulfate, sodium sulfate, potassium sulfate, ammonium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, and sulfuric acid. At least one of these compounds is used. Examples of the sulfonic acid compounds include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and octanesulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid, benzenedisulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, and aromatic sulfonic acids having nuclear substituents such as chlorobenzenesulfonic acid, naphthionic acid, dobias acid, peric acid, gamma acid, Jie acid, Koch acid, metanilic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid. At least one of these compounds is used. The sulfuric acid compounds and sulfonic acid compounds may be mixed together. The addition rate of these sulfuric acid compounds or sulfonic acid compounds is in the range of 1 to 600% by mass based on the pure water-soluble polymer. If it is less than 1% by mass, no significant improvement in the flocculation treatment performance is obtained, and even if it is more than 600% by mass, the effect is constant and it is not preferable because of the influence on the target system to which it is added. 2 to 400% by mass is preferable, 2 to 200% by mass is even more preferable, and 3 to 100% by mass is even more preferable.

The sulfuric acid compound or sulfonic acid compound in the present invention is added to a solution prepared by dissolving a water-soluble polymer in water. Distilled water, ion-exchanged water, tap water, industrial water, etc. can be used as the water for dissolving the water-soluble polymer. There is no problem even if these are mixed. A water-soluble polymer is dissolved in a concentration of 0.01 to 1.0% by mass. A sulfuric acid compound or a sulfonic acid compound may be added at the same time as dissolving the water-soluble polymer, but since it can be dissolved in a shorter time and it is easier to respond to changes in the properties of the addition target, the final addition concentration to the system to be added may be 0. 01 to 1.0% by mass is preferred. The inorganic compound may be added in any form or concentration without any restriction as long as it can be added in a specified amount to the pure water-soluble polymer. The mixing time is preferably 1 minute to 60 minutes. Further, even if the solution contains chemicals or substances other than the polymer and water, there is no problem as long as the inorganic compound is contained in a specified amount relative to the pure polymer.
Note that the effect of the aggregation treatment agent composition of the present invention is exhibited as long as the solution of the water-soluble polymer contains a sulfuric acid compound or a sulfonic acid compound, so there is no problem even if an inorganic compound is used during polymerization.

The effect of the flocculating treatment composition of the present invention will be explained. In a polymer solution in which ions are not present, the polymers spread out and interact with each other, reducing mobility and making it difficult for them to be efficiently adsorbed to the target object. On the other hand, when the polymer is contracted by the presence of ions, the interaction is weakened and the polymer is efficiently adsorbed to the target object. The degree of contraction varies depending on the ion species, and sulfate ions and sulfonate ions have a particularly large contraction effect, which is presumed to contribute to the improved performance of the flocculating treatment composition of the present invention.

The coagulation treatment agent composition in the present invention can be used as a wastewater treatment agent for wastewater or sludge treatment, a sludge dehydration agent, a sludge settling agent, or as a papermaking agent such as a retention improver, a freeness improver, a coagulant, or a paper strength enhancer. etc., can be used in a wide range of ways.

When the aggregation treatment agent composition of the present invention is used as a papermaking retention improver or freeness improver, it is added to papermaking raw materials before papermaking. Normally, in the papermaking process, papermaking raw materials are transferred from upstream with a pulp dry solids concentration of 2.0% by mass or more, but immediately before the paper machine, the pulp dry solids concentration is lower than 2.0% by mass due to white water, fresh water, etc. It is diluted in papermaking raw materials. Generally, it is diluted to 0.5 to 1.5% by mass, and these are called inlet raw materials or headbox raw materials. A retention improver or a freeness improver is added to these raw materials (hereinafter referred to as inlet raw materials) and paper is made. The flocculation treatment agent composition of the present invention is also applied to inlet raw materials.

Types of paper for which the papermaking retention aid or drainage aid of the flocculation treatment composition of the present invention is used include newsprint, fine printing paper, medium printing paper, gravure printing paper, PPC paper, coated base paper, lightly coated paper, wrapping paper, liner and core base paper board, etc. The addition location in the papermaking process is before or after the fan pump or screen, which are shearing processes. The addition rate of the water-soluble polymer is in the range of 10 to 1000 ppm based on the solids concentration of the paper stock.

The sludge that can be used as the sludge dewatering agent in the flocculant composition of the present invention is surplus sludge generated when biologically treating wastewater from paper manufacturing, chemical industry, food industry, etc., or from urban sewage, human waste, and industrial wastewater. Organic sludge produced during processing (so-called raw sludge, surplus sludge, mixed raw sludge, digested sludge, flocculated/floated sludge, and mixtures thereof) is added to these sludges after being diluted with water to an arbitrary concentration. . The addition rate to sludge varies depending on the type of sludge and the type of dewatering machine, but is 1 to 1000 ppm based on the amount of sludge liquid. The types of dehydrators used include belt presses, centrifugal dehydrators, screw presses, multi-disc dehydrators, rotary presses, filter presses, etc. Further, it may be used in combination with an inorganic flocculant such as ferric chloride, ferric sulfate, polyferric sulfate, PAC, and band sulfate.

When the flocculant composition of the present invention is used for wastewater treatment, it can be used in food processing wastewater, dyeing wastewater, plating wastewater, chemical factory wastewater, paper manufacturing wastewater, metal processing wastewater, domestic wastewater, human waste treatment wastewater, livestock wastewater, etc. Applicable. The addition rate to wastewater is in the range of 1 to 1000 ppm, but it can be arbitrarily adjusted depending on the target wastewater.

The flocculation treatment agent composition of the present invention will be specifically explained below, but the present invention is not limited to the following examples.

Water-soluble polymer samples 1 to 10 were produced as the water-soluble polymers of the present invention by the conventional method of water-in-oil emulsions disclosed in JP-A-59-130397, JP-A-10-140496, JP-A-2011-99076, etc. Samples 7 to 9 were produced by adding an inorganic salt to an aqueous solution containing a monomer mixture during polymerization. Sample 10 was produced by the conventional method of dispersion polymerization in salt water disclosed in JP-A-62-15251, JP-A-62-20511, JP-A-2007-16086, etc. The compositions and physical properties of these are shown in Table 1.

(Table 1)
*Sample 3 is a product with a branched structure; E: water-in-oil emulsion; D: monomer dispersed in salt water; DMQ: acryloyloxyethyltrimethylammonium chloride; AAM: acrylamide; AAC: added during acrylic acid polymerization. Addition rate of inorganic compounds: mass % vs. polymer purity

Example 1
Water-soluble polymer sample 1 in Table 1 was dissolved in pure water to prepare a 0.1% by mass solution. Ammonium sulfate was added to the solution in an amount of 12% by mass based on the pure water-soluble polymer content, and mixed to prepare flocculating treatment composition sample A. Similarly, flocculating treatment composition samples B to E were prepared using the water-soluble polymer samples in Table 1. These are shown in Table 2.

(Table 2)

(Execution test example 1)
Using newsprint papermaking inlet raw materials, a yield rate measurement test was conducted using a Bullitt type dynamic jar tester (using 30 mesh wire). The physical properties of the paper stock material are pH 7.8, electrical conductivity 121.2 mS/m, solid content concentration 7343 ppm, Ash content such as light calcium carbonate of 30.2% by mass to paper stock solid content concentration, Whatman No. The cation requirement was 0.0327 meq/L and the turbidity was 67 NTU (measured with HACH Co., Ltd. Model 2100P) using a 41 filter paper filtrate model PCD-03 made by Mutec.
Coagulation treatment agent composition sample A in Table 2 was used as a retention aid for paper manufacturing.
Collect a predetermined amount of paper material into a Bullitt-type dynamic jar tester, add 300 ppm of sample A (polymer pure content) to the solid content of paper stock, and stir for 30 seconds at a stirring speed of 1200 rpm. (assuming addition at the inlet), collect the filtrate and transfer it to Whatman No. After filtration with No. 41 filter paper, the SS was measured and the total retention rate was measured.The filter paper was incinerated at 525° C. for 2 hours, and the ash content retention rate was measured. These results are shown in Table 3.

(Comparative Test Example 1) Using the same paper stock as in Test Example 1, a similar test was carried out using the samples in Table 1. The results are shown in Table 3.

(Table 3)

When paper stock A, which contains ammonium sulfate as an inorganic compound, was added to the polymer dissolving solution, the yield rate was improved compared to comparative test examples in which no inorganic compound was added or an inorganic compound was added during polymerization.

(Execution test example 2)
Using newsprint papermaking inlet raw materials, a yield rate measurement test was conducted using a Bullitt type dynamic jar tester (using 30 mesh wire). The physical properties of the paper stock material are pH 7.4, electrical conductivity 87 mS/m, solid content concentration 7743 ppm, Ash content such as light calcium carbonate of 29.4% by mass to paper stock solid content concentration, Whatman No. The cation requirement was 0.0121 meq/L and the turbidity was 19 NTU (measured with HACH Co., Ltd. Model 2100P) using a Mutech Co., Ltd. PCD-03 filtrate of No. 41 filter paper filtrate.
Coagulation treatment agent composition sample D in Table 2 was used as a retention aid for paper manufacturing.
Collect a predetermined amount of paper material into a Bullitt-type dynamic jar tester, add 200 ppm of sample D (polymer pure content) to the solid content of the paper stock, and stir for 10 seconds at a stirring speed of 900 rpm. (assumed to be added at the outlet), collect the filtrate and transfer it to Whatman No. After filtration with No. 41 filter paper, the SS was measured and the total retention rate was measured.The filter paper was incinerated at 525° C. for 2 hours, and the ash content retention rate was measured. These results are shown in Table 4.

(Comparative Test Example 2) Using the same paper stock as in Test Example 2, a similar test was carried out using the samples in Table 1. The results are shown in Table 4.

(Table 4)

When sample D, which contains magnesium sulfate as an inorganic compound, was added to the polymer dissolution solution, the yield rate was improved compared to comparative test examples in which no inorganic compound was added or an inorganic compound was added during polymerization.

(Example Test 3)
Using the newsprint papermaking raw material, a measurement test of the retention rate was carried out using a Britt type dynamic jar tester (using a 30 mesh wire). The physical properties of the paper stock raw material were pH 7.7, electrical conductivity 92 mS/m, solids concentration 13098 ppm, ash content such as light calcium carbonate 24.9 mass% relative to the paper stock solids concentration, cationic demand of Whatman No. 41 filter paper filtrate using a Mutec PCD-03 model was 0.132 meq/L, and turbidity was 60 NTU (measured with a HACH 2100P model).
The flocculation treatment composition sample B or C in Table 2 was used as a papermaking retention aid. A specified amount of paper stock raw material was collected in a Britt-type dynamic jar tester, and 200 ppm of sample B or C was added to the paper stock solids (polymer pure content), and after stirring for 30 seconds at a stirring speed of 500 rpm (assuming addition to the screen inlet of the papermaking process), the filtrate was collected and filtered with Whatman No. 41 filter paper, and the SS and total retention were measured. The filter paper was then incinerated at 525°C for 2 hours, and the ash retention was measured. These results are shown in Table 5.

(Comparative Test Example 3) Using the same paper stock material as in Practical Test Example 3, a similar test was conducted using the samples in Table 1. These results are shown in Table 5.

(Table 5)

When sample B or C, which contains magnesium sulfate as an inorganic compound, was added to the polymer dissolution liquid, the ash retention rate was particularly improved compared to comparative test examples in which no inorganic compound was added or an inorganic compound was added during polymerization.

(Example Test 4)
A drainage test was carried out using a dynamic drainage analyzer (DDA, Matsubo) using recycled cardboard raw material (beaten volume 300 mL). The physical properties of the raw material were pH 7.3, electrical conductivity 24 mS/m, solids concentration 5140 ppm, ash content such as light calcium carbonate 11.1 mass% relative to the solids concentration of the raw material, cationic demand of Whatman No. 41 filter paper filtrate using Myutech PCD-03 type 0.028 meq/L, and turbidity 52 NTU (measured with HACH 2100P type).
Flocculation treatment composition sample E in Table 2 was used as a papermaking drainage improver.
A predetermined amount of raw material was put into a DDA stirring tank with a 62 mesh wire at the bottom. After stirring for 30 seconds at a stirring speed of 600 rpm, 250 ppm of sample E was added (polymer content) to the solid content of the papermaking raw material. After stirring for 30 seconds at a stirring speed of 600 rpm (assuming addition at the screen inlet), the paper stock was sucked under a reduced pressure of 300 mBar, and the drainage time when a sheet was formed on the wire and the sheet moisture content after 15 seconds of sucking were measured. The results are shown in Table 6.

Comparative Test Example 4
The same tests were carried out using the same paper stock as in Example 3 and the samples in Table 1. The results are shown in Table 6.

(Table 6)

When sample E, which contains magnesium sulfate as an inorganic compound, was added to the polymer dissolution solution, the drainage time was shortened and the sheet moisture content was reduced, improving the drainage and water squeezing effects compared to the comparative test example in which no inorganic compound was added.

(Example Test 5)
A dehydration test was conducted using a screw press type dehydrator on paper sludge generated from a paper factory (pH 6.6, electrical conductivity 157 mS/m, SS content 76,000 mg/L, VSS 53.9 mass%, VTS 52.7 mass%, M-alkalinity 760 mg/L, anion amount 6.34 meq/L).
The coagulation treatment composition sample E in Table 2 was used as a sludge dewatering agent.
200 mL of paper sludge was collected in a plastic beaker, and Sample E was added at 25 ppm relative to the sludge liquid volume. The mixture was stirred at 500 rpm for 60 seconds in a CST measuring device, and then filtered through a 40 mesh to measure the amount of filtrate. The sludge was then dehydrated for 60 seconds using a nylon filter cloth (#202) at a press pressure of 4 kg/ ^cm2 , and the cake moisture content (dried at 105°C for 20 hours) was measured. The results are shown in Table 7.

(Comparative Test Example 5) Using the same sludge as in Practical Test Example 5, a similar test was conducted using the samples in Table 1. The results are shown in Table 7.

(Table 7)

When sample E containing magnesium sulfate as an inorganic compound was added to the polymer solution, the amount of filtration was improved and the cake moisture content was decreased compared to comparative test examples in which no inorganic compound was added or an inorganic compound was added during polymerization. The effect has improved.

(Execution test example 6)
A flocculation treatment test of the flocculation treatment agent composition of the present invention was conducted using calcium carbonate slurry. Various compounds were prepared. A sulfuric acid compound or a sulfonic acid compound was added and mixed in a specified amount based on the pure water-soluble polymer to a 0.1% by mass aqueous solution of the water-soluble polymer sample shown in Table 1 to prepare an aggregation treatment agent composition sample. In addition, light calcium carbonate (TP-121, manufactured by Okutama Kogyo Co., Ltd.) was diluted with clear water to prepare a 2.5% by mass calcium carbonate slurry (pH 7.0).
Collect 200 mL of the prepared slurry into a cylinder, add 0.25 g of the prepared coagulation treatment agent composition sample (water-soluble polymer addition rate 50 ppm to calcium carbonate solid content), and after performing up-and-down stirring 5 times, interfacial sedimentation velocity of the slurry was measured. The results are shown in Table 8.

(Comparative Test Example 6) Using the same calcium carbonate slurry as in Practical Test Example 6, a sample of the flocculation treatment agent composition outside the scope of the present invention was prepared and the same test was conducted. The results are shown in Table 8.

界面沈降速度；◎：４５ｃｍ／分以上、○：３０ｃｍ／分以上、
×：３０ｃｍ／分未満 ( Table 8 )

Interfacial settling velocity: ◎: 45 cm/min or more, ○: 30 cm/min or more,
×: Less than 30 cm/min

In the practical test examples in which a specified amount of a compound was added to a polymer solution, it was confirmed that the interfacial settling rate was faster and the flocculation treatment performance was improved compared to the comparative test examples outside the range of the flocculation treatment agent composition of the present invention.

(Execution test example 7)
Using kaolin slurry, a flocculation effect test of the flocculation treatment agent composition using anionic water-soluble polymer sample 6 of the present invention was conducted. Kaolin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was diluted with clear water to prepare a 5% by mass kaolin slurry (pH 8.2).
Aluminum sulfate was added in an amount of 6 or 12% by mass based on the water-soluble polymer purity to a 0.1% by mass aqueous solution of the water-soluble polymer sample shown in Table 1, and mixed to prepare an aggregation treatment agent composition sample.
Collect 200 mL of the prepared slurry into a cylinder, add 0.5 g of the prepared coagulation treatment agent composition sample (water-soluble polymer addition rate 50 ppm to kaolin solid content), and after performing up-and-down stirring 5 times, calculate the interfacial sedimentation rate of the slurry. It was measured. The results are shown in Table 9.

(Comparative Test Example 7) Using the same kaolin slurry as in Test Example 7, a sample of a flocculation treatment composition outside the scope of the present invention was prepared and a similar test was carried out. The results are shown in Table 9.

Table 9
Interfacial settling velocity: ◎: 6 cm/min or more, ○: 4 cm/min or more,
×: Less than 3 cm/min

In the experimental test in which the polymer solution contained a specified amount of inorganic compound, the flocculation state was better than in the comparative test in which no inorganic compound was added. The effect of the flocculation treatment composition using the anionic water-soluble polymer of the present invention was confirmed.

The flocculation treatment composition of the present invention has been confirmed to have performance as a papermaking retention improver, drainage improver, and sludge dewatering agent, as well as flocculation effects on calcium carbonate slurries and kaolin slurries. The flocculation treatment composition of the present invention can be deployed in a wide range of applications where flocculation treatment performance is required, such as sludge dewatering applications, wastewater treatment applications, and applications as a retention improver and drainage improver in the papermaking process.

Claims (5)

A water-soluble polymer whose constituent units are 0 to 99 mol% of a cationic monomer represented by the following general formula (1) and 1 to 100 mol% of a nonionic monomer , or a water-soluble polymer represented by the following general formula (2) ) Dissolution of an anionic water-soluble polymer having a constituent unit of 1 to 50 mol % of an anionic monomer and 50 to 99 mol % of a nonionic monomer at a concentration of 0.01 to 1.0 mass %. An agglomeration treatment agent composition characterized by containing 1 to 600% by mass of a liquid and one or more selected from sulfuric acid compounds and sulfonic acid compounds based on the pure water-soluble polymer.
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl or alkoxy group having 1 to 3 carbon atoms, R ₄ is an alkyl or alkoxy group having 1 to 3 carbon atoms, an alkyl group or an aryl group having 7 to 20 carbon atoms, A represents oxygen or NH, B represents an alkylene group having 2 to 4 carbon atoms, and X ₁ ⁻ represents an anion.

General formula (2)
R ₅ is hydrogen, methyl group or carboxymethyl group, Q is SO ₃ ^- , C ₆ H ₄ SO ₃ ^- , CONHC(CH ₃ ) ₂ CH ₂ SO ₃ ^- , C ₆ H ₄ COO ^- or COO ^- , R ₆ represents hydrogen or COO ⁻ Y ₂ ⁺ , and Y ₁ or Y ₂ represents hydrogen or a cation, respectively. The flocculation treatment composition according to claim 1, characterized in that the water-soluble polymer has a weight-average molecular weight of 5 million to 30 million. The aggregation treatment agent composition according to claim 1 or 2, wherein the water-soluble polymer is in the form of a water-in-oil emulsion. A papermaking retention improver or drainage improver comprising the flocculation treatment agent composition according to claims 1 to 3. A sludge dewatering agent comprising the flocculation treatment composition according to claims 1 to 3.