KR100335961B1 - High effective polymeric coagulant and manufacturing method of same - Google Patents

Abstract

The present invention relates to a high functional polymer flocculant and a method for preparing the same, (a) activating sodium silicate to prepare active silicic acid, and (b) mixing 3 to 5 kg of biopolymer in 1 m3 of water to prepare a lysate. And (c) injecting the active silicic acid prepared in step (a) to the flocculant of aluminum salt or iron salt and mixing methyl alcohol thereto, and then further mixing the biopolymer melt prepared in step (b). By providing a polymer flocculant to provide a polymer flocculant and a method for producing the same, characterized in that it comprises. The polymer flocculant of the present invention has a high removal efficiency of organic substances and heavy metals, and thus a small amount of the polymer flocculant may be used, and thus economical efficiency may be achieved. In addition, the polymer flocculant of the present invention is environmentally friendly due to its high storage stability and high biodegradability of the sludge generated during the flocculation process.

Description

High functional polymeric coagulant and manufacturing method of same

The present invention relates to a high-functional polymer flocculant and a method for manufacturing the same, and more particularly, to synthesize a flocculant of aluminum salt and iron salt using active silicic acid in the form of a polymer, wherein the natural biopolymer is a polymer composition It relates to a high functional polymer flocculant prepared by adding.

Coagulants used in various conventional water treatment sites include aluminum sulfate (Alum) and polyaluminum chloride (PAC), which are aluminum-based flocculants, and ferric chloride and ferric sulfate. The aluminum-based coagulant and the iron salt-based coagulant generate coagulation by aluminum ions and iron ions containing trivalent ions in the amount of the coagulant. The various coagulants described above have various problems when applied to water treatment sites. First, in the case of aluminum-based flocculant, the range of applicable pH is narrow and it is difficult to use in various cases. In addition, in the case of iron salt, despite the wide range of applicable pH, by-products discharged from steel and steel mills are manufactured as a coagulant raw material, so the coagulant contains various kinds of heavy metals, so if special care is not taken when applying the water treatment site There is a fear that heavy metals are contained in the treated water discharged.

Agglomeration in water treatment is caused by metal salts such as aluminum and iron contained in the flocculant. The metal salt induces destabilization and adsorption of underwater particles and removes various contaminants. Therefore, the use of tetravalent ions in the same amount as silica can effectively remove particulate matter and organic matter in the water. Silica has a higher charge than the positive charge of aluminum and iron, so it is excellent in destabilization and adsorption of underwater particles. Conventionally, silica was applied to water treatment, and this was carried out using activated silica. However, active silicic acid has been briefly used as a coagulant, and is currently not used.

The polymer, the floc forming agent used in water treatment processes, is primarily polyacrylamide, but the US Environmental Protection Agency (EPA) regulates it as a carcinogenic substance. In addition, in Korea, polyacrylamide is used for wastewater treatment, but its use is limited for the purpose of water treatment. Currently used polyacrylamide polymer is excellent in the flocculation efficiency by crosslinking is used in wastewater treatment, sludge generated after use is treated by landfill or ocean dumping. Therefore, there is an urgent need to develop a polymer flocculant having excellent flocculation efficiency and biodegradability that does not cause environmental pollution.

An object of the present invention is to provide a polymer flocculant excellent in flocculation efficiency.

It is also an object of the present invention to provide a biodegradable polymer flocculant.

Figure 1 shows the active silica production process of the present invention,

Figure 2 shows the biopolymer melt manufacturing process of the present invention,

Figure 3 shows a polymer flocculant manufacturing process of the present invention.

In order to achieve the above object, the present invention provides 28 vol% to 42 vol% active silicic acid, 0.001 vol% to 0.005 vol% methyl alcohol, and 15 vol% to 20 vol% biopolymer in a flocculant of aluminum salt or iron salt. It provides a polymer flocculant comprising a solution.

In addition, the present invention

(a) activating sodium silicate to produce activated silica;

(b) mixing 3 to 5 kg of the biopolymer into 1 m 3 of water to prepare a melt; And

(c) Injecting the active silicic acid prepared in step (a) to the flocculant of aluminum salt or iron salt, and then mixed with methyl alcohol, and further mixed with the biopolymer melt prepared in step (b) to obtain a polymer flocculant It provides a method for producing a polymer flocculant comprising the step of preparing.

Hereinafter, the present invention will be described in detail.

The present inventors synthesized in the form of a polymer to an aluminum salt or an iron salt coagulant by using an active silicic acid containing silica that maintains a large amount of charge, and added a natural biopolymer as a polymer composition to form a high functional polymer. A flocculant was prepared.

The method for producing a high functional polymer flocculant of the present invention comprises the steps of (a) preparing the active silicic acid, (b) preparing the biopolymer melt, and (c) the flocculant of aluminum salt or iron salt in step (a). It is characterized in that it comprises the step of preparing a polymer flocculant by injecting the prepared active silicic acid and methyl alcohol mixed therein and then further mixing the biopolymer melt prepared in step (b).

The active silicic acid of the present invention is preferably used as a colloidal polymerized silicic acid by adding a dilute acid to a dilute solution of sodium silicate, and a typical method for preparing active silicic acid is shown in Table 1 below.

Table 2 below shows the active silicic acid properties according to the conventional method of preparing silicic acid.

As shown in Table 2, depending on the concentration of silicic acid contained in the dilution of sodium silicate to be activated, the gel state may cause storage problems. (Source: Pukcheon Engineering Co., Ltd., Japan, Water Treatment Pharmaceutical , Wastewater Management Manual, No. 6) However, the present invention is characterized in that the active silicic acid is prepared by using sodium hydroxide which is a strong base instead of sodium bicarbonate which is a method of applying the sodium bicarbonate method of Table 1 above. Therefore, the active silicic acid of the present invention does not change into a gel even when stored at room temperature for 2 months.

The step of preparing the active silicic acid of the present invention is performed by filling dilute sodium hydroxide in a stirred reactor and injecting it with sodium silicate for 1 hour while stirring. Sodium silicate mixed with the diluted sodium hydroxide is preferably 5% by weight to 8% by weight, and most preferably 6% by weight.

In the step (b), the biopolymer is preferably an amine-based biopolymer of Formula 1 below.

N is from 3,170 to 3,200.

The biopolymer of the present invention is preferably purchased and used or manufactured and used, and as shown in FIG. 2, 1 m 3 of water is filled in a constant temperature reactor maintained at a temperature of 50 ° C. and a stirring speed of 250 rpm, and the amine synthetic biopolymer 3 Kg to 5 kg is added and dissolved with stirring for 4 hours to prepare a biopolymer solution for preparing a polymer flocculant.

The method for preparing a biopolymer may include (a) adding urea to ammonia water to dissolve at low temperature, (b) swelling the starch by mixing starch in the lysate, and (c) drying the mixture at room temperature and then again. Evaporating ammonia at 0 ° C., and (d) placing the mixture in a drier to fill the nitrogen gas and reacting at 135 ° C. for 4 hours to cause a synthesis reaction.

Step (a) is further titrated to -35 ° C by dissolving 10% by volume of urea in the total volume of ammonia water in -33 ° C ammonia water.

Starch mixed in the melt in step (b) is preferably 20 to 40% by weight, most preferably 30 to 35% by weight of the melt. In addition, the reaction temperature is preferably -35 ℃ and starch is preferably all starch, but most preferably corn starch containing amylose and amylopectin in a 1 to 4 ratio.

In addition, the final step of the polymer flocculant of the present invention is made as shown briefly in FIG. The polymerized flocculant of the present invention is prepared by mixing and dissolving the active silicic acid prepared above and methyl alcohol as a stabilizer in the flocculant of aluminum salt or iron salt, and then adding and mixing the dissolved biopolymer. In addition, the polymer flocculant of the present invention includes 28 vol% to 42 vol% active silicic acid, 0.001 vol% to 0.005 vol% methyl alcohol, and 15 vol% to 20 vol% biopolymer solution in the flocculant of aluminum salt or iron salt. do.

In another aspect, the present invention provides a high-functional polymer flocculant prepared by the above method of producing a polymer flocculant. The polymer coagulant of the present invention has a wide range of coagulation pH that can be applied including active silicic acid, biopolymer, and conventional coagulant, and is superior in performance to organic coagulants in removing organic materials or heavy metals, and particularly, adsorption capacity of heavy metals. This is very excellent. In addition, the polymer flocculant of the present invention does not cause gelation on the product even when stored at room temperature for about 2 months, and thus has a storage stability and biodegradability because it contains a biopolymer.

In addition, the polymer flocculant of the present invention can be used for treatment of municipal sewage, industrial wastewater, especially paper waste, and the like, and is not limited to the above.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

(1) Preparation of Activated Silica

The production process of activated silica is briefly shown in FIG. 1 m 3 of 0.1 M dilute sodium hydroxide was charged in a reactor stirred at 250 rpm, and sodium silicate (28% SiO ₂ ) was continuously injected at an injection rate of 1.67 L / min for 1 hour, followed by stirring and maintaining for 1 hour.

(2) Dissolution of Biopolymer

In order to synthesize the amine-based biopolymer starch was used commercially used corn starch. The corn starch contains amylose and amylopectin in a 1 to 4 ratio. Amylose and amylopectin are both used in this synthesis. Ammonia water and urea to be used for the synthesis were used commercially.

Ammonia water was added in an ultra low temperature chamber equipped with a stirrer, and the temperature was adjusted to -33 ° C. Then, 10% by volume of urea was added and slowly dissolved while stirring at 100 rpm. After dissolving the solution at -35 ° C., the starch was swelled with starch at a weight ratio of 1/3 of the solution and slowly stirred at 100 rpm. The swollen starch was dried at room temperature, charged with nitrogen gas, and reacted at 135 ° C. for 4 hours to obtain an amine biopolymer. 2 shows a dissolution process of the biopolymer. 1 m 3 of water was filled in a constant temperature reactor maintained at a temperature of 50 ° C. and a stirring speed of 250 rpm, and 4 kg of the obtained amine-based synthetic biopolymer was added and dissolved for 4 hours with stirring.

(3) Preparation of Active Silicate and Biopolymer-Containing Polymer Coagulant

The manufacturing method proceeded to the process shown in FIG. First, 500 L of polyaluminum chloride was charged in a constant temperature reactor stirred at a stirring speed of 250 rpm at a temperature of 25 to 30 ° C., and the active silicic acid prepared above was injected at 4.2 L / min for 2 hours, and then 500 ml of methyl alcohol was used as a stabilizer. Inject at a time. After stirring for 1 hour, the dissolved biopolymer was injected for 2 hours at an injection rate of 1.7 L / min, and then stirred and reacted for 1 hour to prepare a high functional polymer.

Example 2

Same as Example 1, but in step (3) a high functional polymer was prepared using ferric chloride instead of polyaluminum chloride.

Experimental Example

The properties of the polymers prepared in Examples 1 and 2 were examined. The property test was carried out by the Korean Industrial Standard (KSM1510) and the Standard Method (AWWA) method to measure the heavy metal content and specific gravity contained in the polymer polymer and the results are shown in Table 3 below.

As shown in Table 3, the polymer flocculant of the present invention contains little heavy metal, so there is no risk of heavy metal contamination during water treatment.

In addition, the polymer coagulant of Example 1 and Example 2 A and B was applied to the plant wastewater, and then compared with the conventional coagulant of the aluminum salt or iron salt, the analysis is shown in Table 4 below.

As shown in Table 4, the polymer flocculant of Example 1 and Example 2 was found to be superior to the conventional flocculant of aluminum salt or iron salt in both organic material and heavy metal removal despite the small amount of administration. Small amounts of flocculants such as polyacrylamide, known as carcinogens, were used to induce high efficiency aggregation. In addition, the polymer coagulant of Example 1 showed a slightly better coagulant effect than the polymer coagulant of Example 2. In addition, the polymer coagulant of the present invention was excellent in the adsorption capacity of heavy metals, even when stored at room temperature for about 2 months it was found that the gelation phenomenon does not occur on the product, the storage stability is high.

As mentioned above, the polymer flocculant of the present invention has a high removal efficiency of organic substances and heavy metals, and thus a small amount may be used, so it is economical. In addition, the polymer flocculant of the present invention is environmentally friendly due to its high storage stability and high biodegradability of the sludge generated during the flocculation process.

Claims (7)

A polymer flocculant comprising: 28 vol% to 42 vol% active silicic acid, 0.001 vol% to 0.005 vol% methyl alcohol, and 15 vol% to 20 vol% biopolymer solution in a flocculant of aluminum salt or iron salt . delete The polymer flocculant of claim 1, wherein the biopolymer is an amine-based biopolymer represented by Chemical Formula 1. N is from 3,170 to 3,200. The polymer flocculant according to claim 1, wherein the polymer flocculant is used for water treatment. (a) activating sodium silicate to produce activated silica; (b) mixing 3 to 5 kg of the biopolymer into 1 m 3 of water to prepare a melt; And (c) Injecting the active silicic acid prepared in step (a) to the flocculant of aluminum salt or iron salt, methyl alcohol is mixed therein, and the biopolymer melt prepared in step (b) is further mixed to obtain a polymer flocculant. Manufacturing steps Polymer flocculant manufacturing method comprising a. The method of claim 5, wherein the sodium silicate activation of step (a) is performed by mixing 5 wt% to 8 wt% of sodium silicate with diluted sodium hydroxide. According to claim 5, wherein the polymer flocculant of step (c) is 28 vol% to 42 vol% active silicic acid, 0.001 vol% to 0.005 vol% methyl alcohol, and 15 vol% to the flocculant of the aluminum salt or iron salt Method for producing a polymer flocculant, characterized in that it comprises a 20% by volume biopolymer solution