KR101380328B1 - Multifunctional Al-Fe/Mg-Si Agents for Water Treatment and the Fabrication Method Thereof - Google Patents

Abstract

The method for producing a coagulant for waste water and wastewater treatment according to the present invention comprises the steps of: a) mixing a metal source including an iron source and a magnesium source and an aluminum supply with water to prepare a mixture; b) adding an acid to the mixed solution to hydrate the aluminum providing source; c) sequentially adding a dispersant and a polymerization agent to the mixed solution to which the acid has been added; And d) adding a basic substance and a silicon source to the mixed solution in which the dispersant and the polymer are sequentially added.

Description

TECHNICAL FIELD The present invention relates to a functional Al-Fe / Mg-Si water treatment agent and a method for producing the same.

TECHNICAL FIELD The present invention relates to a multifunctional nano-flocculating agent for treating wastewater, and more particularly, to a multifunctional nano-flocculating agent for treating wastewater and a method for producing the same. More particularly, Fe / Mg-Si based inorganic polymer water treatment agent and a method for producing the same, which are capable of simultaneously removing the total phosphorus (TP), heavy metals, odor, At low cost.

Conventional biological wastewater treatment methods (standard activated sludge process), ie, microorganism treatment methods, have been studied extensively. However, it is difficult to remove COD, TN, TP, heavy metals and odors at the same time. It is not economical.

In the water treatment, the coagulation process is carried out by injecting the coagulant into the polluted waste water or wastewater in order to coagulate and precipitate the floating colloidal substance and other impurities.

Conventionally, chemical coagulants used to achieve these objects include aluminum sulfate (Alum), polychlorinated aluminum (PAC) and ferric chloride, organic coagulants, and coagulants. Among these water treatment agents, aluminum sulfate and polychlorinated aluminum are most commonly used. However, the aluminum-based coagulant may cause the problem that the soluble aluminum remains in the treated water due to the organic acid generated in the wastewater treatment, thereby causing Alzheimer's disease. In addition, the aluminum flocculant has a problem in that the flocculation performance is lowered at a low temperature and the aluminum flocculant must be used in an excessive amount. In addition, ferric chloride has a disadvantage in that the pH range is narrow and remains in the treated water and affects the chromaticity after the treatment. Conventional inorganic flocculants are composed of low molecular weight and have a small particle size in aqueous solution, so that the effect of turbidity removal and the ability to remove organic matters such as suspended solids are not sufficient and the processing ability is deteriorated at the high turbidity of the high- Excessive sludge is generated. When stored for a long period of time, sediment is generated in the coagulant and the product is lost.

The mechanism of chemical flocculation is as follows. The principle of phosphorus removal of aluminum salt and iron salt among the representative coagulants mainly used in coagulant precipitation method is as follows.

1. Al: PO ₄ ^3- + Al ³⁺ → AlPO ₄ ↓

^{Al 3+ + (3-x)} H 2 O + xPO 4- → Al (OH) 3-x (H 2 PO 4) x + (3-x) H +

_{Al (OH) 3 + xH 2} PO 4- → Al (OH) 3-x (H 2 PO 4) x + xOH -

2. Fe: 3Fe ³⁺ + 2PO ₄ ^3- + 3H ₂ O → (FeOH) ₃ (PO ₄ ) ₂ + 3H ⁺

3Fe ²⁺ + 2HPO ₄ ^2- ? Fe ₃ (PO ₄ ) ₂ + 2H ⁺

PH plays an important role in the coagulation reaction. Generally, the reaction is active between pH 4.5 ~ 7.3 for ortho-P and between 4.8 ~ 6.7 for poly-P.

The literature on the prior art discloses a process for purifying a pollutant present in waste water or wastewater by purifying it by flocculating and precipitating the inorganic material such as sulfate, carbonate, calcium salt, iron salt, sulfide, sodium hypochlorite, zeolite, A treating agent used in combination is disclosed in Korean Patent Publication No. 1989-0006523, Korean Patent Publication No. 1991-0004082, Korean Patent No. 10-0469685, Korean Patent No. 10-0497992, Korean Patent Publication No. 1996-0011889 And the like. Korean Patent Registration No. 10-0464714 discloses a technique for preparing a silica sol and mixing it with a water-soluble salt such as ferric chloride to prepare a flocculant. However, such techniques alone are not sufficient for efficient removal of COD, T-N, and T-P of wastewater, and a coagulant of even higher performance is required.

Korea Patent Publication No. 1989-0006523 Korea Patent Publication No. 1991-0004082 Korean Patent No. 10-0469685 Korean Patent No. 10-0497992 Korea Patent Publication No. 1996-0011889 Korean Patent No. 10-0464714

It is an object of the present invention to provide a method for producing an Al-Fe / Al-Fe-based polymer having an ability to simultaneously remove multifunctional, ie, COD, TN, TP, heavy metals, Mg-Si water treatment agent and a process for producing the same.

Hereinafter, the production method of the present invention will be described in detail. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

The present invention relates to a multifunctional Al-Fe / Al alloy which simultaneously removes chemical oxygen demand (COD), total nitrogen (TN), total phosphorus (TP), heavy metals and odors from wastewater, wastewater, Mg-Si-based water treatment agent and a process for producing the same.

The method for producing an Al-Fe / Mg-Si based water treatment agent for treating wastewater according to the present invention comprises the steps of: a) mixing an aluminum supply source and a metal supply source including an iron supply source and a magnesium supply source; b) adding an acid to the mixed solution to hydrate the aluminum source (Haloganation &Sulfonation); c) sequentially adding a dispersant and a polymerization agent to the mixed solution to which the acid has been added (Polymerization); And d) a step of adding a basic material and a silicon source to the mixed solution to which the dispersant and the polymer are sequentially added (Reduction & Nano-micelle Coating).

In the step (a), the aluminum source may be Al (OH) ₃ , AlCl ₃ or a mixture thereof , And preferably the aluminum source is Al (OH) ₃ . The metal source comprises an iron source and a magnesium source, wherein the source of iron comprises iron salts (including hydrates) and the magnesium source comprises magnesium salts (including hydrates).

The iron salt is _{FeSO 4, Fe 2 (SO 4} ) 3, Fe (NO 3) 2 and FeCl _2, will the selected one or more from the magnesium salt is _{MgSO 4, MgCl 2, Mg (} NO 3) the selected at least one from the ₂ will be. Preferably, the metal source comprises iron sulfate (including hydrate) and magnesium sulfate (including hydrate), such as Fe ₂ (SO ₄ ) ₃ and MgSO ₄ ; FeSO ₄ and MgSO _4; Or Fe ₂ (SO ₄ ) ₃ , FeSO ₄ and MgSO ₄ ;

In the mixing of step a), the aluminum source is added in an amount of 10 to 100 parts by weight based on 100 parts by weight of water, and the metal source is added in an amount of 150 to 500 parts by weight based on 100 parts by weight of the aluminum source. At this time, it is preferable that the metal source contains 50 to 90% by weight of an iron source and 10 to 50% by weight of a magnesium source.

In the step b), the acid is dropped into a mixed solution of water, a metal-providing source, and an aluminum-providing source to conduct the hydration reaction of the aluminum-providing source.

The acid in step b) is preferably sulfuric acid, hydrochloric acid or a mixture thereof, more preferably sulfuric acid or a mixture of hydrochloric acid and sulfuric acid. At this time, acid may be added to the aqueous solution. For example, an aqueous sulfuric acid solution of 50 to 98% by weight, an aqueous hydrochloric acid solution of 25 to 35% by weight, or a mixture thereof may be added.

The reaction of step b) is a Halogenation & Sulfonation reaction, and the reaction is carried out at 80 to 120 ° C for 1 to 10 hours. Preferably 90 ° C to 110 ° C for 2 to 5 hours.

An example of the reaction that occurs in step b) is as follows.

2 Al (OH) ₃ + 3H ₂ SO ₄ ? Al ₂ (SO ₄ ) ₃ + 6H ₂ O Reaction formula (1)

Fe ₂ O ₃ + H ₂ SO ₄ ? 2FeSO ₄ + 2H ₂ O +? O ₂ Reaction formula (2)

MgO + H ₂ SO ₄ → MgSO ₄ + H ₂ O (3)

2Al (OH) ₃ + 6HCl → 2AlCl ₃ + 3H ₂ O Reaction formula (4)

Fe ₂ O ₃ + 6HCl? 2FeCl ₃ + 3H ₂ O Reaction formula (5)

MgO + 2HCl → MgCl ₂ + 2H ₂ O Reaction formula (6)

The acid to be added in the step b) is added in an amount of 100 to 300 parts by weight based on 100 parts by weight of the aluminum providing source contained in the mixed solution, and the acid is added in an amount of 1 g / min to 10 g / min By weight.

The step c) is a step of sequentially adding a dispersant and a polymerization agent to the reactant produced by adding the acid to the mixed solution, thereby preparing a polymer and a nano-micelle.

By the addition of the dispersing agent in the step c), it is possible to control the dispersion effect and the size of the nano-metal by preventing the aggregation of the nano metals while converting the metal park into the nano-metal micelles.

The dispersing agent is preferably polyacrylamide, sodium alginate, polyethylene oxide, polyvinyl alcohol, carboxymethylcellulose, gelatin, or a mixture thereof.

In detail, the metal nanoparticles of the park are prepared by the dispersing agent and bound to the aluminum polymer. By the addition of the dispersant, aggregation of nano metals is prevented and uniform dispersion is achieved, and the size of the nano metal can be controlled to a certain size. The amount of the dispersant to be added is 0.1 to 5 parts by weight based on 100 parts by weight of the aluminum source.

When the dispersant is added, the reaction is carried out at 60 ° C to 110 ° C for 1 hour to 10 hours, preferably at 80 ° C to 110 ° C for 1 to 3 hours.

The polymerization agent for polymerizing the reactant generated by adding the acid to the mixed solution may include hydrogen peroxide (H ₂ O ₂ ), and the polymerizer may be introduced into the aqueous solution. For example, An aqueous hydrogen peroxide solution of 35% by weight can be used as the polymerizer.

An example of the main reaction at the time of introducing the polymerization agent is as follows.

₅ (OH) (SO ₄ ) ₇ + 3H ₂ O Reaction formula (7): ???????? 5FeSO ₄ + 2H ₂ SO ₄ + 5 / 2H ₂ O ₂ ?

5MgSO ₄ + 2H ₂ SO ₄ + 5 / 2H ₂ O ₂ → Mg ₅ (OH) (SO ₄ ) ₇ + 3H ₂ O Reaction formula (8)

In step c), 1 to 40 parts by weight of a polymerization agent (based on 100 parts by weight of an aluminum source) is added to the dispersion, based on hydrogen peroxide, When the polymerization agent is added, the reaction is carried out at 80 ° C to 120 ° C for 1 hour to 10 hours, preferably at 80 ° C to 100 ° C for 1 to 3 hours.

The step (d) may include adding a basic material and a silicon source to the mixed solution in which the dispersant and the polymer are sequentially added, and adding sodium carbonate, sodium hydroxide, and sodium carbonate to the product produced in step (c) Sodium bicarbonate or a mixture thereof is added to neutralize the excess acid, and the degree of polymerization of the water treatment agent to be prepared is controlled. The monomolecular compounds generated by the addition of the basic substance react with the metal salt to polymerize from a single molecule to a multimolecular. That is, a monomer → a dimer → an oligomer → a polymer.

An example of the main reaction of the aluminum compound upon addition of a basic substance is as follows.

Al ₂ (SO ₄ ) ₃ + 6 NaOH → Al (OH) ₃ + ₃ Na ₂ SO ₄ Reaction formula (9)

_{2Al (OH) 3 + Al 2} (SO 4) 3 → Al 4 (OH) 6 (SO 4) 3 Scheme 10

An example of the main reaction of iron and magnesium compounds is as follows.

Fe ₂ (SO ₄ ) ₃ + 6NaOH? 2Fe (OH) ₃ + 3Na ₂ SO ₄ Reaction formula (11)

MgSO ₄ + 2 NaOH → Mg (OH) ₂ + Na ₂ SO ₄ Reaction formula (12)

In addition, by adding the silicon source as a polymer of nano metals, it is converted into a polymer material having a more stable structure by reacting with the aluminum polymer material, and excellent in sedimentation property, ) Having excellent cohesive performance.

The silicon source includes sodium silicate, and the sodium silicate (nSiO ₂ .Na ₂ O, n is a real number) includes sodium silicate having a content of silicon oxide (SiO ₂ ) of 5 to 40 wt% , And Na ₂ SiO ₃ .

An example of the main reaction when the silicon source is added is as follows.

8Al ₂ (SO ₄ ) ₃ +0.2 (SiO ₂揃 Na ₂ O) + 12H ₂ O

→ 4Al ₄ (OH) ₆ (SO ₄ ) _2.94 (SiO _2.31 ) _0.2 + 3.06 Na ₂ SO ₄ Reaction formula (13)

반응식(14)

Reaction (14)

10 to 30 parts by weight of a basic substance and 0.5 to 10 parts by weight of a silicon source are preferably added based on 100 parts by weight of the aluminum source in the step d). In the step d), the reaction is carried out at 50 ° C to 100 ° C for 1 hour to 5 hours, preferably at 50 ° C to 80 ° C for 1 to 3 hours. At this time, it is preferable that the pH of the solution after step d) is in the range of 1.0 to 3.0.

According to the above-described manufacturing method, an Al-Fe / Mg-Si-based water treatment agent in which an effective metal such as iron or magnesium is coated with a nano-sized micelle is produced in an aluminum sulfate polymer. In the present invention, the process is characterized in that the product has an aluminum-silicate polymer material having a molecular weight of 100,000 to 500,000, more preferably 200,000 to 300,000.

The present invention provides an Al-Fe / Mg-Si-based water treatment agent which can be simultaneously prepared by the above-mentioned production method and can remove multifunctional properties such as COD, TN, TP, heavy metals and odors for waste water treatment. Provides a method for treating waste water that is effectively treated at low cost by using a water treatment agent prepared by the above-described production method.

Specifically, the present invention includes a step of mixing the water treatment agent prepared by the above-described method with water and wastewater, adjusting the pH to neutral (6.5 to 8), stirring the pH-adjusted mixed solution and precipitating . At this time, it is preferable that 0.01 to 1 mL of the water treatment agent is mixed per liter of the waste water to be treated.

The present invention is advantageous in that a multifunctional Al-Fe / Mg-Si-based water treatment agent having excellent ability to remove floating colloid particles from waste water and wastewater and to remove COD, TN, TP, heavy metals, , Cost reduction, energy conservation and processing capacity increase, processing facility cost reduction, processing site reduction, disposal of treated sludge, etc., can be effectively performed at low cost.

Fig. 1 shows the particle size distribution of the flocculant prepared in Example 5,
Fig. 2 shows the particle size distribution of the flocculant prepared in Example 4. Fig.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

≪ Example 1 >

300 ml of distilled water was added to a four-necked round flask, and 212 g of Fe ₂ SO ₄ .7H ₂ O (98 wt% special grade reagent, Samcheon Chemical Co., Ltd.) and MgSO ₄ ㅇ 7H ₂ O (99.2 wt% g and Al (OH) ₃ (KC, Dry basis) 91.8 g were added to prepare a mixed solution. To the mixed solution, 192.8 g of H ₂ SO ₄ (95 wt% special grade reagent, Samcheon Chemical Co., Ltd.) was added dropwise over the flask over about 30 minutes. At this time, the liquid in the flask was heated up to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. Then, 220 ml of a 0.5 wt% polyacrylamide aqueous solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 14.4 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 1.01 and an effective content of a specific gravity of 1.228 is 8 wt% as a pale yellowish brown solution.

≪ Comparative Example 1 &

250 ml of distilled water was added to a four-necked round flask, and 122.4 g of Al (OH) ₃ (KC, dry basis) was added with stirring, and 257 g of H ₂ SO ₄ (95 wt% The dropping reaction was carried out at the top of the flask. At this time, the temperature was raised to 90 ° C due to self-heating, and the solution was heated to 108 ° C and maintained for 3 hours to prepare a transparent solution. 300 ml of distilled water was added to the prepared transparent solution, and the solution was diluted and maintained at 80 ° C.

100 ml of a 0.5 wt% polyacrylamide aqueous solution (Polyacrylamide, manufactured by YAYYANG CHEMICAL Co., Ltd.) was added to the diluted solution at 80 DEG C and maintained for 2 hours to prepare a product. At this time, the product has a pH of 0.81 and an effective content of a specific gravity of 1.26 is a pale yellowish brown solution of 8 wt%.

≪ Example 2 >

300 ml of distilled water was added to a four-necked round flask, and 142 g of Fe ₂ SO ₄ .7H ₂ O (98 wt% special grade reagent, Samcheon Chemical Co., Ltd.) and 62 g of MgSO ₄ ㅇ 7H ₂ O (99.2 wt% And 93 g of Al (OH) ₃ (KC, Dry basis) were charged to prepare a mixed solution. 246 g of H ₂ SO ₄ (95 wt% special grade reagent, Samcheon Chemical Co.) was added dropwise to the prepared mixed solution over the flask over about 30 minutes. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 60 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 1.06 and an effective content of a specific gravity of 1.32 is a pale yellowish brown solution of 11 wt%.

≪ Comparative Example 2 &

In a four-neck round flask, 150 ml of distilled water was added and 93 g of Al (OH) ₃ (KC, dry basis) was added while stirring. 246 g of H ₂ SO ₄ (95% . The solution was heated to 108 ° C. and maintained for 3 hours to prepare a transparent solution. Then, 177 g of Fe ₂ SO ₄ 7H ₂ O (98 wt% special grade reagent, Samcheon Chemical Co., Ltd.) ₄ O 7H ₂ O (99.2 wt% special grade reagent, Samcheon Chemical Co., Ltd.) was added and 60 g of 35 wt% aqueous hydrogen peroxide was added at 90 ° C to convert the solution color from transparent green to clear reddish brown solution do. After cooling to 60 캜, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous NaOH solution were added, and the mixture was maintained for 2 hours to prepare a product. At this time, the product has a pH of 1.34 and an effective content of a specific gravity of 1.28 is a pale yellowish brown solution of 11 wt%.

≪ Example 3 >

250 ml of distilled water was added to a four-necked round flask and 177 g of Fe ₂ SO ₄ .7H ₂ O (98% by weight special grade reagent, Samcheon Chemical Co., Ltd.) and 62 g of MgSO ₄ ㅇ 7H ₂ O (99.2% And 78 g of Al (OH) ₃ (KC, Dry basis) were added to prepare a mixed solution. 206 g of H ₂ SO ₄ (95 wt% special grade reagent, Samcheon Chemical Co., Ltd.) was added dropwise over about 30 minutes to the prepared mixed solution at the top of the flask. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 60 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 1.44 and an effective content of a specific gravity of 1.308 is 11 wt% as a pale yellowish brown solution.

<Example 4>

250 ml of distilled water was added to a four-necked round flask, and 212 g of Fe ₂ SO ₄揃 7H ₂ O (98% by weight of special grade reagent, Samcheon Chemical Co., Ltd.) and 62 g of MgSO ₄ ㅇ 7H ₂ O (99.2% And 62 g of Al (OH) ₃ (KC, Dry basis) were added to prepare a mixed solution. 164 g of H ₂ SO ₄ (95% by weight special reagent, Samcheon Chemical Co., Ltd.) was added dropwise to the prepared mixed solution over the flask over about 30 minutes. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 60 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 1.92 and an effective content of a specific gravity of 1.289 is 11 wt% as a pale yellowish brown solution.

&Lt; Example 5 >

250 ml of distilled water was added to a four-neck round flask, and 138 g of Fe ₂ SO ₄ .7H ₂ O (98 wt% special grade reagent, Samcheon Chemical Co.) and 31 g of MgSO ₄ ㅇ 7H ₂ O (99.2 wt% And 62 g of Al (OH) ₃ (KC, Dry basis) were added to prepare a mixed solution. 85 g of H ₂ SO ₄ (95 wt% special grade reagent, Samcheon Chemical Co.) and 74 g of HCl (35 wt% special grade reagent, Samcheon Chemical Co., Ltd.) were added dropwise to the prepared mixed solution over about 30 minutes. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 60 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product is a pale yellowish brown solution having a pH of 1.23 and an effective content of a specific gravity of 1.25 of 11 wt%.

&Lt; Example 6 >

300 ml of distilled water was added to a four-necked round flask, and 212 g of Fe ₂ SO ₄ .7H ₂ O (98 wt% special grade reagent, Samcheon Chemical Co., Ltd.) and 62 g of MgSO ₄ ㅇ 7H ₂ O (99.2 wt% And 62 g of Al (OH) ₃ (KC, Dry basis) were added to prepare a mixed solution. 164 g of H ₂ SO ₄ (95% by weight special reagent, Samcheon Chemical Co., Ltd.) was added dropwise to the prepared mixed solution over the flask over about 30 minutes. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Thereafter, the temperature of the solution in the flask was adjusted to 90 캜, 60 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 1.3 and an effective content of a specific gravity of 1.25 is a pale yellowish brown solution of 16 wt%.

&Lt; Example 7 >

300 ml of distilled water was added to a four-necked round flask, and 277 g of Fe ₂ SO ₄揃 7H ₂ O (98% by weight of special grade reagent, Samcheon Chemical Co., Ltd.) and 245 g of MgSO ₄ ㅇ 7H ₂ O (99.2% And 122.4 g of Al (OH) ₃ (KC, Dry basis) were added to prepare a mixed solution. 242 g of H ₂ SO ₄ (95 wt% special grade reagent, Samcheon Chemical Co., Ltd.) was added dropwise over about 30 minutes to the prepared mixed solution at the top of the flask. At this time, the liquid in the flask was heated to 90 ° C by self heat generation, and the mixture was heated to 108 ° C and maintained for 3 hours. 300 ml of 0.5% by weight aqueous polyacrylamide solution (Polyacrylamide, The temperature was maintained at 108 [deg.] C for 2 hours. At this time, the color of the solution was changed from opaque blue to transparent green. Then, the temperature of the solution in the flask was adjusted to 90 캜, 95 g of 35% by weight aqueous hydrogen peroxide was added, and the temperature was maintained for 2 hours. The solution color was changed from a transparent green to a clear reddish brown solution by oxidation reaction by the addition of hydrogen peroxide which is a polymerization agent. After cooling to 60 ° C, 100 g of a 2 wt% Na ₂ SiO ₃ aqueous solution and 30 g of a 50 wt% aqueous solution of NaOH were added and maintained for 2 hours to prepare a flocculant. At this time, the product has a pH of 2.02 and an effective content of a specific gravity of 1.48 is a pale yellowish brown solution of 24 wt%.

&Lt; Example 8 > Performance test

Chemical Oxygen Demand (COD), Total Nitrogen (T-N), and Total Phosphorus (T-P) were measured by adding coagulants to the wastewater of Daejeon Facilities Management Corporation. That is, 0.2 ml of the coagulant prepared in each of Examples 1 to 8 was added to 1 L of the collected sample, and the pH was adjusted to about 7 with NaOH, followed by stirring and precipitation for 15 minutes. The analytical method was carried out in accordance with the method specified in the water pollution process test method.

- odor is test result by sensory method, 1: minimum detection level, 2: normal level not to be recognized as odor, 3 ~ 5: odor intensity, The sensory method is based on the odor expression method.

Direct sensory method Odor indication (Ministry of Environment, Odor Management Manual)

&Lt; Example 9 > Performance test by input amount

Chemical Oxygen Demand (COD), Total Nitrogen and Total Phosphorus were measured by adding coagulant to the wastewater from Daejeon Facilities Management Corporation. That is, 0.1 ml of the coagulant (coagulant prepared in Example 4) was added in a total amount of 0.1 ml, 0.1 ml, 0.2 ml, 0.3 ml, 0.5 ml or 1 ml to 1 L of the collected sample, 7, stirred for 15 minutes, sedimented and analyzed. The analytical method was carried out in accordance with the method specified in the water pollution process test method.

&Lt; Example 10 > Performance test by input amount

Chemical Oxygen Demand (COD), Total Nitrogen (T-N) and Total Phosphorus (T-P) were measured by adding coagulant to concentrations of municipal waste water and wastewater. That is, 0.1 ml of the coagulant (coagulant prepared in Example 2) was added in a total amount of 0.1 ml, 0.2 ml, 0.3 ml, 0.4 ml or 0.5 ml to 1 L of the collected sample, and the pH was adjusted to about 7 with NaOH After adjustment, the mixture was stirred for 15 minutes, settled and then analyzed. The analytical method was carried out in accordance with the method specified in the water pollution process test method.

&Lt; Example 11 > Performance test by input amount

Chemical Oxygen Demand (COD), Total Nitrogen and Total Phosphorus were measured by adding coagulant to the wastewater of the Hanwha E & C wastewater treatment facility (Yangzhou Sincheon Sewage Treatment Plant). Namely, 0.1 ml of the flocculant (the flocculant prepared in Example 3) was added in a total amount of 0.1 ml, 0.2 ml, 0.3 ml, 0.4 ml or 0.5 ml to 1 L of the collected sample, and the solution was added with 30% Na ₂ CO ₃ The pH was adjusted to about 7, stirred for 15 minutes, settled and analyzed. The analytical method was carried out in accordance with the method specified in the water pollution process test method.

Example 12: Performance comparison of existing coagulant

Performance comparison test was performed using waste water collected from Daejeon facility. Collecting a sample of flocculant 0.2㎖ 1L, PAC produced in Example 4, the (poly aluminium chloride) 0.2㎖, Fe 2 (SO 4) 3 solution, the addition of Alum (aluminum sulfate solution) 0.2㎖ respectively and 30% Na ₂ CO ₃ , the pH was adjusted to about 7, stirred for 15 minutes, settled and analyzed. The analytical method was carried out in accordance with the method specified in the water pollution process test method. As a result, it has been confirmed that the flocculant prepared according to the present invention exhibits a wastewater treatment ability similar to or superior to the conventional flocculant (particularly, in terms of TN removal ability).

(In parentheses in COD, TN and TP,% refers to the amount removed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (13)

a) mixing a metal source and an aluminum supply comprising an iron source and a magnesium source to form a mixture;
b) adding an acid to the mixed solution to hydrate the aluminum providing source;
c) sequentially adding a dispersant and a polymerization agent to the mixed solution to which the acid has been added; And
d) adding a basic material and a silicon source to the mixed solution in which the dispersant and the polymer are sequentially added;
/ RTI &gt;
Wherein the iron supply source is an iron salt, the magnesium supply source is a magnesium salt, and the metal source including the iron source and the magnesium source is prepared as nano-micelle by the step c). A method for producing a coagulant for treatment. The method according to claim 1,
The aluminum source of step a) is selected from the group consisting of Al (OH) ₃ , AlCl _3, or a mixture thereof. delete The method according to claim 1,
The iron salt is _{FeSO 4, Fe 2 (SO 4} ) 3, Fe (NO 3) 2 and FeCl _2, at will the selected one or more of said magnesium salt is MgSO _4, MgCl ₂ and Mg (NO ₃₎ the selected at least one from the ₂ Wherein the coagulant is used as a coagulant. The method according to claim 1,
In the step a), the aluminum supply source is charged in an amount of 10 to 100 parts by weight based on 100 parts by weight of water, and the metal supply source is charged in an amount of 150 to 500 parts by weight based on 100 parts by weight of the aluminum supply source. (Method for producing coagulant for waste water treatment). 6. The method of claim 5,
Wherein the acid in step b) is added in an amount of 100 to 300 parts by weight based on 100 parts by weight of the aluminum source contained in the mixed solution. The method according to claim 1,
wherein the polymerization agent in step (c) is hydrogen peroxide. The method according to claim 1,
wherein the dispersing agent of step (c) is polyacrylamide, sodium alginate, polyethylene oxide, polyvinyl alcohol, carboxymethyl cellulose, gelatin, or a mixture thereof. The method according to claim 6,
The dispersing agent of step (c) is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the aluminum providing source, and the polymerizing agent is added in an amount of 1 to 40 parts by weight based on 100 parts by weight of the aluminum supplying source. &Lt; / RTI &gt; The method according to claim 1,
Wherein the basic substance is sodium carbonate, sodium hydroxide, sodium hydrogencarbonate or a mixture thereof. The method according to claim 1,
Wherein the silicon source is sodium silicate. 10. The method of claim 9,
10 to 30 parts by weight of a basic substance and 0.5 to 10 parts by weight of a silicon source are introduced in the step d) based on 100 parts by weight of the aluminum source. A method for treating ozone / wastewater using a flocculant produced by the method of any one of claims 1, 2, and 4 to 12.

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