KR20060121628A - Antimicrobial agent-polymer complexes bead and manufacture method thereof - Google Patents

Abstract

Provided are antimicrobial agent-polymer composite beads, which improve a solubilization efficiency of sludge even at low temperature, have high durability, and exhibit a sludge solubilization effect even after used for a long time, and a preparation thereof. The antimicrobial agent-polymer composite beads are prepared by the steps of: (1) dissolving a polymer having hydroxyl groups in water to prepare a polymer solution; (2) dissolving an organic silicone-based quaternary ammonium salt in an organic solvent; (3) adding the prepared solution of the step (2) to the polymer solution of the step (1) to be reacted at room temperature; (4) adding the quaternary ammonium-polymer composite solution of the step (3) to an aqueous solution of divalent metal ions, and then stirring the admixture to form polymer composite beads; and (5) adding distilled water to the prepared polymer composite beads to be heat-treated at 40-80‹C for 10-120minutes.

Description

Antimicrobial Agent-Polymer Complexes Beads and Manufacture Method

Figure 1. General treatment method of sewage sludge generated in sewage / wastewater treatment process

Figure 2. Process for producing a polymer composite sphere according to the present invention

Figure 3. Si-O-Si covalent bond of the crosslinked polymer composite sphere of the present invention

4. FTIR measurement results according to Experimental Example 1

The present invention relates to a polymer composite sphere used for solubilizing sludge, and a polymer composite sphere crosslinked by reacting an organosilicon quaternary ammonium salt having an antimicrobial activity with a polymer having a hydroxyl group and a method for producing the same.

As shown in FIG. 1, a general method of treating sewage sludge generated in sewage / wastewater treatment processes is that the sewage / wastewater introduced into the aeration tank is partially decomposed by microorganisms and then transferred to the sedimentation tank to discharge water and sludge through solid-liquid separation. Are separated. Some of the separated sludge was returned to the aeration tank as a microbial source, while the remaining sludge was treated as a surplus sludge through a process such as concentration, digestion, dehydration, composting, and incineration. However, these treatments have secondary environmental pollution, cost and time-consuming problems.

Therefore, in recent years, methods to reduce sludge generation in the water treatment process and recycle the sludge's active ingredients have been developed, apart from the technology development focused only on the post-treatment of sewage sludge, and most of the methods are sludge associated with the water treatment method. Sludge solubilization by pretreatment.

As the main pretreatment method, ozone or ultrasonic waves are used to oxidize the cell wall solubilizing the sludge, and then it is introduced into the bioreactor and finally decomposed into carbon dioxide, and part of it is used for biosynthesis to reduce the excess sludge. Method of fermentation to provide organic acid to water treatment process, solubilization of sludge drawn from aerobic digestion process combined with immersion flat membrane, and re-introduction into aerobic digestion tank, concentration of excess sludge into metal mill crusher and metal A method of forcibly breaking and solubilizing cell walls of activated sludge by frictional force and frictional heat between the balls and the balls by mutually flowing the mill.When the activated sludge is heated to a high temperature like the S-TE process, the viscous material that protects the activated sludge is dismantled. And aerobic bacteria are activated by heating Solubilization by various sludge pretreatment methods such as secretion and solubilization of the enzyme by breaking down the cell walls have been shown to reduce sludge reduction efficiency in combination with water treatment processes that have relatively long hydraulic retention times such as long-term aeration or oxidation.

The basic principle of sludge reduction using such a pretreatment promotes hydrolysis of cell components by destroying the cell walls surrounding the microbial components by physical, chemical and biological pretreatment. The organic matter in the solubilized sludge is returned to the water treatment process to be decomposed in the bioreactor, resulting in increased biodegradability of the sludge. Although the sludge reduction technology combined with the water treatment as described above has already been developed in various ways, the operating cost of the pretreatment facility is expensive, disadvantages of having to be treated at high temperatures, problems caused by the use of acid and caustic soda.

Generally, antimicrobial agents contain cations, which disrupt or destroy anionic cell membranes, or diffuse into cells, causing metabolic disorders to kill bacteria. There are many antibacterial agents developed to date, but these antimicrobial agents are largely divided into a release type and a fixed type. The release type antimicrobial agent refers to a mechanism in which the antimicrobial agent is slowly released to kill surrounding bacteria, and this includes inorganic substances, organometallic compounds, amide compounds, and amphoteric surfactants. Fixed antimicrobial agents are sometimes called non-release or defensive types, which have a mechanism of killing bacteria when they come into contact with the antimicrobial agent while the antimicrobial agent is fixed to a material, such as organosilicon quaternary ammonium. . The release type antimicrobial has a disadvantage in that the release concentration is gradually decreased by the continuous release of the antimicrobial agent, and consequently, the antimicrobial activity is reduced. On the other hand, the fixed antimicrobial agent exhibits antimicrobial activity in a fixed state on a certain material, so that the antimicrobial antimicrobial activity can be maintained longer than the release type.

The organosilicon quaternary ammonium salt, a representative example of the fixed antimicrobial agent, has a structure in which a quaternary ammonium salt, a cationic surfactant, and silane are combined [Plueddemann, et al., USP 4933327; Halloran, et al., USP 5707435; Nohr, et al., USP 5569732; Temple, et al., USP 3719711], a representative antimicrobial agent is 3- (trimethoxysilyl) propyl octadecyldimethyl ammonium chloride, the chemical formula of which is represented by the following formula (1).

[Formula 1]

As can be seen in Formula 1, the cationic portion in the quaternary ammonium of the antimicrobial agent is electrostatically adsorbed on the anion site of the microbial cell surface, and then physicochemically destroys the cell surface structure by hydrophobic interaction. Leakage of intracellular material stops the respiratory function of microorganisms and eventually kills them.

When the antimicrobial agents described above are applied to the sludge pretreatment process, in the case of the release type antimicrobial agent, metal ions or cations are released to destroy intracellular protein structures or are terminated by stopping enzymatic reactions. While it is not suitable for solubilization, which is the purpose of the pretreatment process, on the other hand, fixed antimicrobial agents, such as organosilicon quaternary ammonium salts, are very suitable for sludge solubilization because they exert antimicrobial activity by breaking down cell walls and leaking intracellular materials. However, when such an antimicrobial agent is used alone in the sludge pretreatment process, the sludge solubilization is exerted, but since the antimicrobial agent is returned to the water treatment process together with the solubilized organic material in the sludge, other effective strains and sludges are killed in the bioreactor. Since the material is released with the final discharged water, the problem of secondary pollution arises. Therefore, in order for the antimicrobial agent to contribute only to solubilization in the sludge pretreatment process, another immobilization medium is required in which the antimicrobial agent is immobilized without being released. In addition, even if the antimicrobial agent is immobilized, durability and stability that do not fall off even after long-term use in the sludge pretreatment process are required.

A method of applying to a fabric or a sponge using an organosilicon-based quaternary ammonium salt and a polymer having a hydroxyl group is described in Korean Patent No. 10-0295737, "Antibacterial agent with improved washing resistance." However, in the method described in the above publication, an organosilicon-based quaternary ammonium polymer derivative is prepared and immediately applied to a target material such as fabric or sponge to form a film to show antimicrobial activity. When the fabric or sponge coated with the quaternary ammonium polymer derivative is treated with sludge, if the film is dropped, it will not be able to exert its antibacterial activity anymore, and it can be a secondary environmental pollution source. there was.

The present invention seeks to provide a polymeric composite sphere used for solubilizing sludge.

According to the present invention, after preparing a chemically crosslinked polymer composite using an organosilicon quaternary ammonium salt having an antimicrobial activity and a polymer having a hydroxyl group, the polymer composite is crosslinked polymer having a predetermined structural form through a crosslinking reaction with metal ions. The present invention provides a method for producing a composite sphere and an antimicrobial polymer composite sphere produced by the method.

In addition, the present invention not only significantly improves the solubilization efficiency of the sludge even at low temperatures without heating, but also does not decompose the sphere even after repeated use for a long time, its morphological stability is maintained, and solubilization efficiency without dropping of the quaternary ammonium bound to the polymer. It is intended to provide a polymer composite sphere and a method for producing the same that can be continuously exerted.

In addition, the present invention is a problem that the existing sludge pretreatment methods, that is, the operating cost of the pretreatment facility is expensive, disadvantages that must be treated at high temperatures, problems with the use of acid and caustic soda, and stability in use and long-term usability by coating It is to provide a novel polymer composite sphere combined with an antimicrobial agent that can solve the disadvantage.

The present invention relates to a polymer composite sphere used to solubilize sludge, and the polymer composite sphere according to the present invention is reacted with a polymer having a hydroxyl group capable of forming a crosslink with an organosilicon quaternary ammonium salt having antibacterial activity. An ammonium polymer complex is prepared, and the polymer complex thus prepared is prepared into a cross-linked sphere of a certain form through a crosslinking reaction with a metal ion.

When the polymer composite sphere according to the present invention is applied to sludge, the solubilization efficiency of the sludge is notably improved even at low temperature without heating, and the sphere is not decomposed even after repeated use for a long time, and its morphological stability is also maintained and is bound to the polymer. Solubilization efficiency can be continuously exhibited without dropping of the quaternary ammonium, thus completing the present invention.

Referring to the step of producing a polymer composite sphere according to the present invention,

1) dissolving a polymer having a hydroxyl group in water to prepare a polymer solution;

2) dissolving the organosilicon quaternary ammonium salt in an organic solvent;

3) adding the solution prepared in step 2) to the polymer solution of step 1) and reacting at room temperature;

4) adding a quaternary ammoniumated polymer composite solution of step 3) to a divalent metal ion solution and stirring to form a polymer composite sphere;

5) putting the prepared polymer composite sphere in distilled water and heat-treated for 10 to 120 minutes at 40 ~ 80 ℃;

Is prepared by.

The present invention will be described in more detail as follows.

First, in the present invention, a quaternary ammonium polymer composite is prepared by reacting an organosilicon quaternary ammonium salt with a polymer having a hydroxyl group capable of forming a crosslink in a specific content ratio.

Next, the polymer composite is added to a divalent metal ion solution and crosslinked, followed by heat treatment at 40 ° C. to 80 ° C. for 10 minutes to 120 minutes to perform immobilization of various covalent bonds of the polymer composite.

The organosilicon quaternary ammonium salt contained in the polymer composite of the present invention is a compound having an antimicrobial activity, a compound in which a quaternary ammonium salt is bonded to organosilicon, preferably a compound of the formula (2), Preferably, the use of 3- (trimethoxysilyl) propyl octadecyldimethyl ammonium chloride not only forms a covalent bond such as Si-OC and a polymer having a trimethoxysilyl group with a hydroxyl group, but also the antimicrobial agent itself is Si-O-Si. After forming a covalent bond, such as the formation of a polymer composite, even under the harsh conditions, the antimicrobial agent in the polymer composite is difficult to drop off, so it can be used for a long time.

[Formula 2]

(a + b = 4, a> 2, b> 1, R ₁ is a C ₁ to C ₃ alkyl group, R ₂ is a C ₁ to C ₂₅ linear or branched alkyl group, R ₃ , R ₄ and R ₅ are each independently C ₁ to C ₁₂ aliphatic or aromatic hydrocarbons, and X is Br or Cl.)

In the present invention, the polymer material having a hydroxyl group capable of forming a crosslink may include sodium alginate, carrageenan, polyvinyl alcohol, polyacryliacid, polymethacrylicacid, At least one compound selected from polyvinylalkylether, polyethylene glycol, and polyhydroxyethylmethacrylate is used.

It is preferable to use 50 to 500 parts by weight of the polymer material having a hydroxyl group with respect to 100 parts by weight of the organosilicon quaternary ammonium salt, and if the amount thereof is less than 50 parts by weight, the strength of the polymer composite is lowered and it is easy to drop out in the sludge. When the amount is used in excess of 500 parts by weight, solubility is significantly reduced when dissolved in a solvent for forming a polymer composite, the reactivity is greatly reduced when reacting with an organosilicon-based quaternary ammonium salt. .

As the organic solvent for dissolving the organosilicon-based quaternary ammonium salt, lower alcohols such as ethanol, methanol, propanol, and isopropanol are used.

In the present invention, divalent metal ions which crosslink the polymer composite into a sphere are used by dissolving alkaline earth metals which provide divalent metal ions such as Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ²⁺ in water or an organic solvent. In the present invention, the alkaline earth metal compound may preferably be calcium chloride, potassium chloride, magnesium chloride, etc., but may be used without limitation as long as it can provide metal ions. If the use of 50 to 100 parts by weight is less than 50 parts by weight, the crosslinking of the polymer composite is lowered, resulting in weak morphological stability when used for a long time. If the amount is used in excess of 100 parts by weight, unreacted metal ions remain in the polymer composite. May affect sludge solubilization. Moreover, it is also possible to mix and use crosslinking agents, such as glutaraldehyde.

Sodium alginate, which is a representative example of a polymer having a hydroxyl group capable of forming crosslinks used in the present invention, is also called algin and is a kind of polysaccharide extracted from seaweeds such as laver, seaweed and kelp. It is known to have no toxicity and excellent gel forming ability, and the chemical formula is shown in the following Chemical Formula 3.

[Formula 3]

As can be seen from the formula (3), Sodyan alginate is a natural polymer polymer β-D-mannuronate and α-L-guluronate units are bonded by 1-4 glycosidic linkage Ca ²⁺ , as shown in the following Scheme 1, It has strong affinity with divalent ions of alkaline earth metals such as Mg ²⁺ , Sr ²⁺ , Ba ^2+, etc., so that they can be rapidly crosslinked to form gels by substituting Na ⁺ ions in aqueous solution containing divalent ions. have.

Scheme 1

Therefore, 3- (trimethoxysilyl) propyl octadecyldimethyl ammonium chloride, which is a kind of organosilicon-based quaternary ammonium salt shown in Formula 1, as a reaction example for making a sphere of the polymer composite to which the antimicrobial agent is bound to An organosilicon-based quaternary ammonium polymer composite by reaction with sodium alginate, which is a kind of polymer having a hydroxyl group capable of forming a crosslink, as shown in Scheme 2 below.

Scheme 2

As can be seen in the reaction scheme 2, by dissolving a polymer having a hydroxyl group capable of forming a crosslink with the organosilicon-based quaternary ammonium salt in a solvent to cause a liquid phase reaction, these mutual covalent reaction occurs. That is, the organosilicon quaternary ammonium salt dissolves a methoxy group by water as a solvent, and a hydroxyl group is formed. The hydroxyl groups of the organosilicon quaternary ammonium salt formed react with a hydroxyl group of a polymer to form a covalent bond such as CO-Si. An organosilicon quaternary ammonium polymer composite is formed.

The polymer composite formed as described above is an organosilicon-based quaternary ammonium polymer composite sphere cross-linked by the method shown in FIG. 2 using the property that sodibine alginate is easily crosslinked in an aqueous solution containing divalent ion as shown in Scheme 1. Make

As shown in FIG. 2, crosslinking may occur due to the formation of ionic bonds in an aqueous solution of divalent ionic ion between the organosilicon-based quaternary ammonium polymer composites to form spheres having a constant size. In detail, ionic ions, which are cations, are bonded to each other by substitution of Na between CH2COONa ^- groups in the alginate portion of the organosilicon quaternary ammonium polymerized polymer complex to form an ionic bond such as CH ₂ COO-Ca-OOCCH _2. To make a cross-linked organosilicon quaternary ammonium polymer composite. In addition, a chemical reaction occurs between the hydroxyl groups of the organosilicon quaternary ammonium moiety remaining as an unreacted portion to form a covalent bond such as Si-O-Si, which is shown in FIG. 3.

Therefore, when the polymer composite of the present invention is cross-linked and treated with sludge, it is not decomposed in an aqueous solution such as sludge due to covalent bonds such as CO-Si, -COO-Ca-OOC, and Si-O-Si. The quaternary ammonium moiety, which exhibits antimicrobial activity, does not drop off.

The present invention also includes a method for solubilizing the sludge using the polymer composite sphere prepared as described above, when treating the sludge with the polymer composite of the present invention, the solubilization of the sludge is not only significantly improved at room temperature without heating, but continuously Even when the sludge is treated, the components constituting the polymer composite are not dropped due to the covalent bonds of the polymer composite, so that the solubilization effect can be continuously exerted.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.

Example 1

Sodib alginate was dissolved in distilled water at room temperature to form a 3% (w / v) polymer solution. And the polymer solution of 2% (w / v) in a solution in which 3- (trimethoxysilyl) propyldimethyloctadecylammonium chloride as an organosilicon quaternary ammonium salt is dissolved in methanol at 42% (w / v). To the mixture was stirred and reacted at room temperature for 3 hours to synthesize quaternary ammonium alginate. After dropping the quaternary ammonium alginate synthesized in a 5% (w / v) aqueous solution of calcium chloride using a syringe, drop the droplets to form a sphere through the crosslinking reaction, and then complete the quaternary ammonium alginate sphere It was put in distilled water at 60 ℃ and the crosslinking and covalent bond was firm for 1 hour. The finished sphere was washed several times with distilled water to completely remove the unreacted materials.

The average particle diameter of the composite sphere was 5 mm.

Example 2

Carrageenan was dissolved in distilled water at room temperature to form a 3% (w / v) polymer solution. The polymer is prepared so that the solution of 3- (trimethoxysilyl) propyldimethyloctadecylammonium chloride as an organosilicon quaternary ammonium salt is dissolved in methanol at 42% (w / v) to 2% (w / v). Quaternary ammonium carrageenan was synthesized by adding to the solution and stirring and reacting at room temperature for 3 hours. Then, for the purpose of crosslinking of the carrageenan, the quaternary ammonium-carrageenan synthesized in a 5% (w / v) solution of potashyan chloride was dropped drop by drop using a syringe, and the resultant After being made, the crosslinked quaternary ammonium carrageenan spheres were placed in distilled water at 60 ° C. to crosslink and covalently bond for 1 hour. The finished beads were washed several times with distilled water to completely remove the unreacted materials.

The average particle diameter of the composite sphere was 5 mm.

Example 3

Polyvinyl alcohol having a polymerization degree of 1500 was dissolved in distilled water to prepare a 3% (w / v) polymer solution. The polymer is prepared so that the solution of 3- (trimethoxysilyl) propyldimethyloctadecylammonium chloride as an organosilicon quaternary ammonium salt is dissolved in methanol at 42% (w / v) to 2% (w / v). A quaternary ammonium polyvinyl alcohol was synthesized by adding to the solution and stirring and reacting at room temperature for 3 hours. Then, quaternary ammonium synthesized in a mixed solution of 2% by weight aqueous 10% (w / w) magnesium chloride solution and 35% (w / w) glutaaldehyde aqueous solution for the purpose of crosslinking of polyvinyl alcohol After dropping the polyvinyl alcohol drop by drop using a syringe to form a sphere through the crosslinking reaction, the crosslinked quaternary ammonium polyvinyl alcohol beads were placed in distilled water at 60 ° C. for 1 hour for crosslinking and covalent bonding. Solidified. The finished beads were washed several times with distilled water to completely remove the unreacted materials.

The average particle diameter of the composite sphere was 5 mm.

[Experimental Example 1]: Fourier Transform Infrared Spectrophotometer (FTIR) Analysis A FTIR analysis was performed to determine whether a polymer complex of an organic silicon-based quaternary ammonium salt and a polymer was formed. In order to confirm the formation of the polymer composite of Example 1 according to the present invention, first, the crosslinked crosslinked organosilicon-based quaternary ammonium alginate spheres were washed several times with water to completely remove unreacted materials and then lyophilized to perform FTIR analysis. It was done. The results of the investigation are shown in FIG. 4.

As can be seen in FIG. 4, in the silicon-based quaternary ammonium chloride, the characteristic peak attributable to the long alkyl chain (C ₁₈ H ₃₇ ) is large at 2800-2900 cm ⁻¹ , whereas in Sodyan alginate, this alkyl peak is almost absent. It can be seen that a characteristic peak attributable to the hydroxyl group at 3400 cm ⁻¹ is shown. However, in the crosslinked organosilicon quaternary ammonium alginate, in addition to the characteristic peak attributable to hydroxyl groups at 3400 cm ⁻¹ , the long alkyl chain (C ₁₈ H ₃₇ ) of organosilicon quaternary ammonium at 2800-2900 cm ⁻¹ Due to the characteristic peaks appearing at the same time, it was confirmed that a complex was formed between the organosilicon quaternary ammonium and the sodium alginate.

Experimental Example 2 Sludge Solubilization Experiment

In order to determine the sludge solubilization effect of Example 1-3 according to the present invention, the solubilization effect over time was examined through S-COD by treating the sludge with 50 v / v% of crosslinked spheres at room temperature. As a comparative example, an alkali treatment method, which is one of the conventional sludge solubilization methods, was selected to determine the sludge solubilization degree by adjusting the pH of the sludge to 10.

The results are shown in Table 1.

TABLE 1

As can be seen in Table 1, even though the solubilization of the sludge treated with the cross-linked organosilicon polymer composite sphere of the present invention is room temperature, it can be seen that it is much higher than the comparative example, and the longer the treatment time, the higher the solubilization effect. Able to know.

Experimental Example 3 Long-term Sludge Solubilization Persistence Experiment

In order to investigate the long-term sludge solubilization effect, 50 v / v% cross-linked spheres were treated with sludge 10 times at room temperature for 10 hours using the polymer composite sphere according to Example 1, and the results are shown in Table 2.

TABLE 2

As can be seen in Table 2, Example 1, which is a sample of the cross-linked organosilicon polymer composite sphere of the present invention, shows that the S-COD value appears uniformly even after 10 times of treatment for 3 hours in sludge at room temperature. In this regard, it was found that the crosslinked polymer composite sphere of the present invention is excellent in durability and may have a long-term sludge solubilization effect.

In the case of applying the composite sphere according to the present invention to sludge, not only the solubilization efficiency of the sludge is significantly improved even at low temperature without heating, and the sphere is not decomposed even after repeated use for a long time. It is effective to continuously exert solubilization efficiency without dropping quaternary ammonium.

Claims (14)

A polymer composite sphere in which a quaternary ammonium polymer composite in which an organosilicon quaternary ammonium salt and a polymer having a hydroxyl group are mixed is crosslinked with a metal ion. The method of claim 1, The organosilicon quaternary ammonium salt is a polymer composite sphere characterized in that the formula (2). [Formula 2]

(a + b = 4, a> 2, b> 1, R ₁ is a C ₁ to C ₃ alkyl group, R ₂ is a C ₁ to C ₂₅ linear or branched alkyl group, R ₃ , R ₄ and R ₅ are each independently C ₁ to C ₁₂ aliphatic or aromatic hydrocarbons, and X is Br or Cl.) The method of claim 2, The organosilicon quaternary ammonium salt is a polymer composite sphere, characterized in that 3- (trimethoxysilyl) propyl octadecyldimethyl ammonium chloride. The method of claim 1, The polymer having a hydroxyl group is any one or more selected from sodium alginate, carrageenan, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyvinyl alkyl, polyethylene glycol, polyhydroxyethyl methacrylate. A polymer composite sphere made of. The method of claim 1, Polymer composite sphere, characterized in that for use with a polymer having a hydroxyl group of 50 to 500 parts by weight based on 100 parts by weight of the organosilicon quaternary ammonium salt. The method of claim 5, The metal ion is a polymer composite sphere, characterized in that to use a divalent metal compound prepared in an aqueous solution. The method of claim 6, The divalent metal compound is a polymer composite sphere, characterized in that any one selected from calcium chloride, potashyan chloride, magnesium chloride. 1) dissolving a polymer having a hydroxyl group in water to prepare a polymer solution; 2) dissolving the organosilicon quaternary ammonium salt in an organic solvent; 3) adding the solution prepared in step 2) to the polymer solution of step 1) and reacting at room temperature; 4) adding a quaternary ammoniumated polymer composite solution of step 3) to a divalent metal ion solution and stirring to form a polymer composite sphere; 5) putting the prepared polymer composite sphere in distilled water and heat-treated for 10 to 120 minutes at 40 ~ 80 ℃; Method for producing a polymer composite sphere prepared by. The method of claim 8, The organosilicon quaternary ammonium salt is a method for producing a polymer composite sphere characterized in that the formula (2). [Formula 2]

(a + b = 4, a> 2, b> 1, R ₁ is a C ₁ to C ₃ alkyl group, R ₂ is a C ₁ to C ₂₅ linear or branched alkyl group, R ₃ , R ₄ and R ₅ are each independently C ₁ to C ₁₂ aliphatic or aromatic hydrocarbons, and X is Br or Cl.) The method of claim 9, The organosilicon-based quaternary ammonium salt is 3- (trimethoxysilyl) propyl octadecyldimethyl ammonium chloride, and the polymer having a hydroxyl group is sodium alginate, carrageenan, polyvinyl alcohol, polyacrylic acid, polymethacrylic liquid Seed, polyvinyl alkyl, a method for producing a polymer composite sphere, characterized in that any one or more selected from polyethylene glycol, polyhydroxyethyl methacrylate. The method of claim 8, A method for producing a polymer composite sphere, characterized in that a polymer having a hydroxyl group of 50 to 500 parts by weight based on 100 parts by weight of the organosilicon quaternary ammonium salt. The method of claim 8, The divalent metal ion is a method for producing a polymer composite sphere, characterized in that the alkaline earth metal compound. The method of claim 12, The divalent metal ion is a polymer composite sphere, characterized in that any one selected from calcium chloride, potashyan chloride, magnesium chloride. Sludge solubilization method characterized in that the polymer composite sphere of any one of claims 1 to 7 is added to the sludge solubilizing.

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