KR101841059B1 - COMPOSITE FOR RECOVERING HEAVY METAL AND METHOD OF MANUFACTURING THE SAME, REMOVAL METHODS OF HEAVY METAl - Google Patents

Abstract

The present invention relates to a composite for collecting heavy metal, of which a polyphenolic polymer is coated on the surface of a substrate, a production method thereof, and a method for eliminating heavy metal.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heavy metal recovery complex, a method for producing the heavy metal recovery complex,

The present invention relates to a heavy metal recovery complex having excellent heavy metal adsorption amount, a production method thereof, and a heavy metal removal method.

Recently, environmental damage and pollution have been attracting attention, and environment friendly technology and technology for preventing environmental pollution have been attracting attention. Various techniques for adsorbing or detecting environmental pollutants have been actively studied. Especially, studies on the removal of heavy metals are actively researched as the interest in environmental pollution and human welfare promotion increases.

Generally, heavy metals are generated from industrial wastewater, agricultural activities, industrial water, etc., and the discharged heavy metals are a fatal danger to mankind and ecosystem through various routes. In particular, when heavy metals enter the body, they interfere with or interfere with the essential chemical action of cells or biomaterials present in the body, and cause a fatal risk to the biochemical function of biological species through the action of destroying the properties of the body's biomembranes .

For this reason, stringent environmental regulations must be applied to industry to remove heavy metals from the wastewater before it is released or reused.

As a method for removing heavy metal ions contained in wastewater or groundwater, chemical precipitation method using hydroxide or sulfide, adsorption method using ion exchange resin or activated carbon, filter method using membrane, and electroadsorption method using metal material as electrode Methods are being utilized.

However, when using the chemical precipitation method, a large amount of sludge generated after the treatment acts as a secondary pollutant source, and there is a problem that a low concentration of heavy metals can not be removed. In the case of using ion exchange resin or membrane, There is a problem in that it is difficult to treat the contaminated water and the cost is high.

Among them, the adsorption method is known as the most effective method, and Korean Patent No. 10-0704929 discloses a method of removing heavy metals by using activated carbon as an adsorbent. However, the synthesis of such an adsorbent requires a complex process and a high synthesis temperature, which is difficult to mass-produce, takes a long time to remove heavy metals, incompletely removes some substances, and produces environmentally hazardous byproducts.

As such, the adsorption method is also widely used, so there is a limit to the cost of the adsorbent to be purchased and reused. In order to solve these limitations, it is necessary to maximize the efficiency of the adsorbent by using an environmentally friendly adsorbent which is cost competitive and does not generate secondary byproducts, so as to minimize the amount of the adsorbent to be used even if the same amount of heavy metals is treated .

Korean Patent No. 10-0704929

In order to solve the above problems, it is an object of the present invention to provide a heavy metal recovery complex capable of adsorbing a heavy metal ion present in a solution containing heavy metal ions, for example, wastewater, ground water, do.

It is another object of the present invention to provide a heavy metal recovery composite capable of further improving the stability of a composite and further increasing the heavy metal adsorption amount by coating a polyphenolic polymer on a support having a wide specific surface area.

In the heavy metal recovery complex of the present invention, the polyphenolic polymer may be coated on the surface of the substrate.

The polyphenolic polymer of the present invention may be a condensation polymer of a polyphenol compound and an aldehyde compound.

The polyphenolic compounds of the present invention include any one or a mixture of two or more selected from the group consisting of phenolic acids, flavonoids, stilbenoids,

The aldehyde-based compound of the present invention may include any one or a mixture of two or more selected from formaldehyde, acetaldehyde, propionaldehyde and glutaraldehyde.

The substrate of the present invention may comprise any one or a mixture of two or more selected from metals, natural polymers, synthetic polymers, carbon and ceramics.

The substrate of the present invention may be of a particulate, fibrous or fabric type.

The porosity of the substrate of the present invention may be between 0.3 and 0.85.

The substrate of the present invention and the polyphenolic polymer may be in a weight ratio of 1: 0.5 to 5.

The heavy metal recovery complex of the present invention may have a heavy metal adsorption amount of 100 to 400 mg / g at pH 3 to 6.

The method for producing a heavy metal recovery complex of the present invention comprises the steps of: a) dropping an aldehyde compound into a polyphenol compound solution to prepare a mixed solution;

b) immersing the substrate in the mixed solution; And

c) mixing a base material with an immersion liquid immersed in the base material to coat a surface of the base material with a polyphenolic polymer;

. ≪ / RTI >

In step c) of the present invention, a basic substance may be added to adjust the pH to 8 to 12.

The heavy metal removal method of the present invention can adsorb heavy metal ions by immersing the above heavy metal recovery complex in a solution containing heavy metal ions.

The solution containing the heavy metal ions of the present invention may have a pH of 3 to 6.

The heavy metal recovery complex of the present invention may have a heavy metal adsorption amount of 100 to 400 mg / g at pH 3 to 6.

The heavy metal recovery complex according to the present invention is advantageous in that it can have an excellent heavy metal adsorption amount by stably coating a polyphenol-based polymer on a composite itself or a support having a large specific surface area.

In addition, the method for producing a heavy metal recovery composite according to the present invention has an advantage that a polyphenol-based polymer can be simply coated on a base material, hydrophilicity can be imparted to the surface of the base material, and mass production can be achieved.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photograph of a natural kapok fiber and an observation according to one embodiment of the present invention. Fig. 1 (a) is a natural kapok fiber, (b) is Comparative Example 1, (c) Example 1 and (d)
2 is a scanning electron microscope photograph according to an embodiment of the present invention. Fig. 2 (a) is Example 1 and (b) is Comparative Example 2. Fig.
3 is a result of energy dispersive spectroscopy according to an embodiment of the present invention.

Hereinafter, the heavy metal recovery complex according to the present invention, the preparation method thereof, and the heavy metal removal method will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In order to exhibit high adsorption efficiency, it has been necessary to broaden the surface area of the adsorbent, which was conventionally used for removing heavy metals. However, when the surface area of conventional adsorbents is widened, it is difficult to treat heavy metals such as wastewater, ground water and surface water in a short time, and even if they have a large surface area, it is difficult to make the surfaces of functional groups water-soluble at the same time. In addition, when heavy metals are removed by using a liquid material rather than a solid, adsorbents are not affected by surface area and can be mass-processed in a short period of time. However, it is difficult to separate them by redissolving the pH- There was a problem.

Accordingly, the applicant of the present invention has found that, in order to solve this problem, there is no way to remove heavy metals with high efficiency without being affected by the concentration of heavy or heavy metals without secondary byproducts. And a heavy metal recovery complex according to the constitution of the present invention which facilitates the removal of heavy metals, thereby completing the present invention.

The present invention relates to a heavy metal recovery complex, a production method thereof, and a heavy metal removal method.

The present invention will be described in detail,

In the heavy metal recovery complex of the present invention, the polyphenolic polymer may be coated on the surface of the substrate.

The heavy metal recovery composite according to the present invention is advantageous in that the polyphenolic polymer is coated on the surface of the substrate to exhibit excellent reaction stability, dispersibility and mobility in water-soluble pollutants, and no secondary byproducts are produced. At the same time, it can be coated on the surface of a substrate having a wide specific surface area to adsorb heavy metals with high efficiency.

According to an embodiment of the present invention, the polyphenolic polymer may be a condensation polymer of a polyphenol compound and an aldehyde compound. As the condensation polymerization is performed as described above, the polyphenol-based polymer is coated on the surface of the substrate, so that the coating layer can be more uniformly formed.

In the present invention, the polyphenolic compound means a substance in which two or more hydroxyl groups (-OH) of the benzene ring (C ₆ H ₆ ) are substituted in hydrogen.

According to one embodiment of the present invention, the polyphenol compound may include any one or a mixture of two or more selected from the group consisting of phenolic acids, flavonoids, stilbenoids, and lignoglyphs.

For example, the phenolic acid group is a group consisting of compounds having a hydroxyl group (-OH) and a carboxyl group (-COOH) in a benzene ring (C ₆ H ₆ ), and the flavonoids are anthocyanins, Is a compound selected from the group consisting of Flavanone, Flavanol, Flavonol and Isoflavone. In addition, the stilbenoids are derivatives that are hydroxylated in stilbenes, for example, a compound selected from the group consisting of Resveratrol, and the steric turbulence is a compound selected from sesamin derivatives.

And preferably one or two or more polyphenol compounds selected from phenolic acids and flavonoids. Specific examples thereof include gallic acid, syringic acid, ferulic acid and the like of phenolic acids, and flavonoid catechins, catechin gallates, Epigallocatechin, epicatechin, epicatechin, epicatechin, epicatechin gallate, epigallocatechin gallate, catechin gallate, gallocatechin gallate, and the like. When such a polyphenolic compound is used, the adsorption efficiency of heavy metal ions, particularly, the adsorption of lead ions can be improved.

According to one embodiment of the present invention, the aldehyde-based compound may include any one or a mixture of two or more selected from formaldehyde, acetaldehyde, propionaldehyde and glutaraldehyde.

By the condensation polymerization of the polyphenol compound and the aldehyde compound as described above, the polyphenol-based polymer is coated on the surface of the base material, so that it can be uniformly and stably coated on the surface of the base material with stable polymerizability. In addition, the polyphenol-based polymer coated on the surface of the substrate has an increased surface area capable of coordinating with heavy metal ions, and thus has an excellent amount of heavy metal adsorption. Furthermore, it is more preferable that it is applied to the recovery or removal of lead ions because of its excellent binding force with lead ions and its excellent lead ion adsorption amount.

According to one embodiment of the present invention, the substrate and the polyphenol-based polymer may be used in a weight ratio of 1: 0.5 to 5, preferably 1: 0.5 to 3. When the polyphenolic polymer is coated on the base material at the above weight ratio, the heavy metal adsorption amount is increased, which is preferable.

According to one aspect of the present invention, the substrate may include any one or a mixture of two or more selected from metals, natural polymers, synthetic polymers, carbon, and ceramics.

According to an embodiment of the present invention, the metal may be selected from transition metals of Groups 3 to 12, transition metals of Groups 13 to 17, and metalloids.

The natural polymer may include any one or two or more selected from proteins, polysaccharides, and mixtures thereof. For example, the proteins may be milk-derived proteins such as casein and whey protein; Plant-derived proteins such as soybean protein, wheat protein, rice protein, angelica protein, pea protein, lentil protein, oat protein, barley protein, corn protein, brown rice protein; Animal proteins such as serum proteins, placental proteins, albumin, collagen, elastin, gelatin, gliadin; And a decomposition product thereof, and the like, or a mixture of two or more thereof. The polysaccharide may be selected from the group consisting of cellulose, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose acetate propionate, carboxymethylcellulose, alginate, hyaluronic acid, starch, pectin, chitosan, chitin, Oz, xylan and the like, or a mixture of two or more thereof.

The synthetic polymer may be any one or a mixture of two or more selected from polyolefin, polyester, polyurethane, polycarbonate, polyamide, and polyacrylate. Specific examples thereof include polyethylene, polypropylene, polybutylene, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polycarbonate, polyamide 6, polyamide 6,6, polyamide 4,6, poly Amide 6,10, polyamide 6,12, polyamide 11, polyamide 12, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polymethyl methacrylate and polyurethane.

The carbon may be selected from graphene, oxide graphene, reduced graphene grains, single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes, carbon fibers, graphite, graphite, charcoal, carbon black, coke and activated carbon .

The ceramic may be selected from the group consisting of silica, alumina, magnesia, titania, calcium carbonate, barium titanate, strontium titanate, calcium titanate, lead titanate, titanium dioxide, tin dioxide, calcium oxide, iron oxide, , Magnetite, boron oxide, silicon carbide, silicon nitride, nickel ferrite, zinc ferrite, nickel zinc ferrite, barium ferrite and zirconia.

Preferably, the polyphenol-based polymer may be a natural polymer or a synthetic polymer, or a mixture of two or more thereof, for the purpose of improving the binding property of coating the surface of the base material stably.

According to an embodiment of the present invention, the substrate includes any one or a mixture of two or more materials selected from a metal, a natural polymer, a synthetic polymer, carbon, and ceramics, and the substrate may be in the form of a particle, a fiber or a fabric.

Preferably, it is a fiber type or a fabric type which contains any one or a mixture of two or more kinds of natural polymers and synthetic polymers and which is easy to remove after immersion in a solution containing heavy metal ions.

According to one embodiment of the present invention, the porosity of the substrate may be 0.3 to 0.85, preferably 0.5 to 0.7, and the density may be 0.1 to 0.6 g / cm 3, preferably 0.2 to 0.5 g / cm 3. When the porosity and density are as described above, the specific surface area to be coated of the polyphenol compound is increased, and thus the heavy metal adsorption efficiency can be further improved. As the mass is significantly lower than that of the same volume adsorbent, The weight of the waste is also significantly smaller.

As a preferable example of such a substrate, a hollow fiber structure having a large specific surface area can be used.

According to an embodiment of the present invention, the fibers of the hollow structure may have a diameter of 1 to 30 μm, preferably 5 to 25 μm. The porosity means the volume of pores present in the substrate / volume of the substrate. When the inside diameter is as described above, a wide specific surface area can be secured to the inside of the fiber, and hydrophilicity of the carnauba fiber is improved by improving the hydrophilization reaction of the carnauba fiber, which was difficult in the conventional reaction. As a result, -Type structure, it is possible to secure a more excellent heavy metal adsorption efficiency.

In addition, when the hollow structure fiber is immersed in a solution containing a heavy metal ion as a tubular structure is formed in the fiber, the solution can easily penetrate into the fiber due to the capillary phenomenon, can do. In addition, heavy metals adsorbed into the fibers are less likely to be desorbed, which is more advantageous for recovering heavy metals.

In addition, when the hollow fiber-reinforced composite of the present invention is used as a base material of a hollow structure, it can be easily injected by lightening the weight of the same volume, has excellent adverse effect and can be recovered easily, .

As a concrete example of the fiber having the hollow structure, carnauba fiber can be used.

The kapok fiber is a fiber taken from the fruit of Ceiba pentandra whose main origin is Southeast Asia and has a hollow structure with a hollow tube shape, so that it can be applied to various fields for absorption in a wide specific surface area This has the advantage. The surfaces of such kapok fibers contain a large amount of aromatic residues and are stable and strongly hydrophobic. Conventionally, the carpow fiber is utilized as a material for adsorption of oil or the like mainly by utilizing the hydrophobicity of the fiber.

Research has been carried out to hydrophilize the surface of carowon fiber in order to utilize carowon fiber having a hollow structure as a material for adsorption etc. However, the surface of carowon fiber has a large amount of aromatic moieties and is very stable, There has been a problem that it is difficult to make the surface hydrophilic even if a topical agent is used. Further, even if the hydrophilization reaction proceeds, the hydrophilization reaction on the surface of the kapok fiber may be island-shaped, which may result in nonuniform properties of the surface. Also, in order to treat the kapok fiber, a high concentration of a hydrophilic agent, The hollow structure of the kapok fiber itself is destroyed and it is difficult to take advantage of the kapok fiber itself.

Therefore, in order to improve the hydrophilicity of the surface of the kapok fiber while preventing the breakage of the hollow structure of the kapok fiber, the polyphenolic polymer is stably coated on the surface of the kapok fiber to secure the hydrophilicity on the surface and have an excellent amount of heavy metal adsorption Were prepared. Further, the polyphenol-based polymer is coated on the surface of the kapok fiber to further increase the adsorption efficiency of heavy metal ions. In particular, since the adsorption efficiency and adsorption amount of lead ions are excellent, excellent effects can be exhibited in the recovery or removal of lead ions.

The heavy metal recovery complex of the present invention may have a heavy metal adsorption amount of 100 to 400 mg / g at a pH of 3 to 6, preferably 200 to 400 mg / g at a pH of 4 to 6, And more preferably 300 to 400 mg / g at a pH of 4 to 6. This is because the polyphenol-based polymer is coated on the surface of a substrate having a wide specific surface area of the heavy metal recovery composite, thereby having a high heavy metal adsorption efficiency and an excellent heavy metal adsorption amount.

The heavy metal may be one or two or more selected from the group consisting of lead, manganese, cadmium, mercury, arsenic, zinc, copper, nickel, chromium, antimony, barium, indium and bismuth, And more preferably a divalent lead ion.

The method for producing the heavy metal recovery composite as described above will now be described in detail.

The method for producing a heavy metal recovery complex of the present invention comprises the steps of: a) dropping an aldehyde compound into a polyphenol compound solution to prepare a mixed solution;

b) immersing the substrate in the mixed solution; And

and c) coating a base material with a polyphenol-based polymer by mixing a base material with an immersion liquid in which the base material is immersed.

The polyphenol compound solution of the present invention may be prepared by mixing water such as distilled water and purified water; Based alcohol such as methanol, ethanol, methoxyethanol, propanol, isopropanol, butanol, and isobutanol; or a mixed solvent thereof.

According to one embodiment of the present invention, the polyphenol compound solution may be dissolved in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the solvent. When the solution is prepared by the above-mentioned content, it can sufficiently react with the aldehyde-based compound, and the reacted polyphenol-based polymer is uniformly coated on the substrate to secure hydrophilicity on the surface of the substrate and exhibit a more excellent amount of heavy metal adsorption desirable.

According to one embodiment of the present invention, the aldehyde-based compound is not particularly limited, but may be added dropwise at a dropping rate of 0.1 to 10 ml / min. If it is dripped at the above-mentioned rate, heat generation due to rapid reaction rate with the polyphenolic compound can be prevented, and homogeneous heavy metal adsorption efficiency of the polyphenolic polymer can be obtained.

According to one embodiment of the present invention, the polyphenol compound and the aldehyde compound are selected from the group consisting of a hydroxyl group / aldehyde compound of the polyphenol compound and a hydroxyl group / aldehyde compound of the aldehyde group (-CHO) The number of the aldehyde groups (-OH / -CHO) of the system compound may include, but is not limited to, 2 to 20, preferably 2 to 10. When it is included as the above-mentioned functional group water, the polyphenol-based polymer having an excellent amount of heavy metal adsorption can be coated while imparting hydrophilicity to the surface of the substrate.

According to an embodiment of the present invention, it is possible to adjust the pH to 8 to 12, preferably to 9 to 11 by adding a basic substance in step c). When the pH is controlled within the above range, the polymerization efficiency of the polyphenolic polymer is improved, so that the polyphenolic polymer can be coated on the surface of the substrate with high efficiency and at the same time, a high amount of heavy metal adsorption can be obtained.

According to an embodiment of the present invention, the basic substance may include any one or two or more selected from ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. The basic substance can be used for pH control to increase the polymerization efficiency of the polyphenolic polymer in the reaction system.

At this time, the mixed solution to be reacted can be stirred, and the stirring can be appropriately controlled in consideration of the size of the reaction vessel, and may be stirred at 100 to 1,000 rpm, preferably 200 to 800 rpm according to an embodiment, But is not limited thereto.

According to an embodiment of the present invention, it is preferable to use a basic substance having a concentration of 1 to 10 M, preferably 5 to 10 M in order to easily adjust the pH of the basic substance and appropriately adjust the reaction rate. It is not.

According to an embodiment of the present invention, the method may further include d) washing after the step c), and drying at 70 to 100 ° C for 1 to 20 hours. It is preferable to remove the residual material through the washing to increase the heavy metal adsorption efficiency, to prevent the aggregation phenomenon through drying, and to obtain a heavy metal recovery composite coated with a uniform thickness.

The thus-prepared heavy metal recovery complex of the present invention can be applied to a purpose of recovering or removing heavy metal ions with high efficiency in a solution such as waste water or raw water containing heavy metal ions. Particularly, since the adsorption efficiency and the adsorption amount of lead ion are excellent, when indium is recovered from wastewater generated after using ITO, it is often the case that a very small amount of indium can not be recovered. The heavy metal recovery complex can be recovered with a high efficiency even with a trace amount of indium of 200 to 500 ppm and thus can be applied to a trace amount of indium recovery.

The method for removing heavy metals using the heavy metal recovery composite of the present invention as described above will now be described in detail.

The heavy metal removal method of the present invention may be one in which the heavy metal recovery complex is immersed in a solution containing heavy metal ions to adsorb heavy metal ions.

The heavy metal recovery complex of the present invention is immersed in a solution containing a heavy metal ion, and a polyphenol-based polymer coated on a substrate having a wide specific surface area forms a complex with various heavy metal ions through coordination bonding to efficiently recover heavy metal ions Or removed. Further, the bonding area with heavy metal ions increases depending on a wide specific surface area, and thus a higher heavy metal adsorption amount can be exhibited.

According to an embodiment of the present invention, the solution containing the heavy metal ions may have a pH of 3 to 6, preferably 4 to 6. When the solution containing the heavy metal ions at the above pH is used, the heavy metal adsorption amount of the heavy metal recovery complex of the present invention can be optimally improved.

Further, when the heavy metal recovery complex of the present invention is immersed, the temperature is more efficient for heavy metal ion removal when immersed at 20 to 30 DEG C, preferably 24 to 26 DEG C according to an embodiment.

In addition, the heavy metal recovery composite may have an immersion time of 30 minutes to 5 hours according to an embodiment. Preferably 1 to 5 hours. More preferably 2 to 4 hours. Even when immersed in a solution containing heavy metal ions in such a short time as the above range, the heavy metal recovery complex of the present invention can have a heavy metal adsorption amount with high efficiency.

When the heavy metal recovery complex of the present invention produced by the method of the present invention is immersed in a solution containing heavy metal ions, the heavy metal recovery complex may have a heavy metal adsorption amount of 100 to 400 mg / g at pH 3 to 6 Preferably at a pH of 4 to 6 at 200 to 400 mg / g, more preferably at a pH of 4 to 6 of 300 to 400 mg / g. This is because the heavy metal recovery complex can be coated with a polyphenolic polymer on the surface of a substrate having a wide specific surface area, thereby producing a heavy metal recovery complex having a high heavy metal adsorption efficiency and an excellent heavy metal adsorption amount.

INDUSTRIAL APPLICABILITY The heavy metal recovery complex of the present invention is excellent in recovery efficiency or removal efficiency of heavy metal ions and is applicable to the efficient recovery or removal of heavy metal ions in a solution containing heavy metal ions such as wastewater, raw water or drinking water. Particularly, since the adsorption efficiency and adsorption amount of lead ions are excellent, it is applicable to the efficient recovery or removal of lead ions.

Hereinafter, the heavy metal recovery complex according to the present invention, the preparation method thereof, and the heavy metal removal method will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Example 1]

In a three-necked flask, 5 g of gallic acid (GA, 99%, SAMCHUN pure chemical, Korea) and 20 mL of distilled water were mixed and completely dissolved at 65 ° C. 11 mL of a 37% by weight aqueous solution of formaldehyde (SAMCHUN pure chemical, Korea) was added dropwise through the syringe at a rate of 1 ml / min. The solution was washed with distilled water and immersed in 1 g of dried kapok fiber. An 8M sodium hydroxide solution was added to the solution in which the kapok fiber was immersed until the pH reached 9, and the precipitate was formed by refluxing for 2 hours. The precipitate was yellow and was washed three more times with cooling and acid washing followed by distilled water. The finally washed precipitate was dried in a vacuum oven at 80 DEG C for 4 hours.

[Example 2]

Except that a woven polypropylene-polyethylene mixed fiber was used in place of the kapok fiber in Example 1.

[Example 3]

Except that catechin mixture (CC, Kangbaotai Fine-Chemicals Co., Ltd., Hubei, China) was used in place of gallic acid in Example 1 above.

[Comparative Example 1]

The same procedure was carried out except that caraway fibers were not used in Example 1 above.

[Comparative Example 2]

Except that formaldehyde aqueous solution was not added in Example 1 above.

[Comparative Example 3]

Except that sodium hydroxide solution was not added in Example 1 above.

[Comparative Example 4]

The acid treated kapok fiber prepared by immersing 1 g of kapok fiber in a mixed solution of 0.4 g of NaClO ₂ and 0.08 ml of acetic acid and reacting at 80 ° C for 1 hour was used.

[Comparative Example 5]

Natural kapok fibers which had not been treated were used. At this time, the surface of natural kapok fiber showed lipophilicity, and heavy metal ions were not adsorbed even when pH conditions were changed.

[Experimental Example 1]

Observation of the appearance of heavy metal recovery complex.

FIG. 1 is a graph showing changes in the color of the natural callow fiber and the heavy metal recovery composite prepared in the order of Comparative Example 1, Example 1, and Comparative Example 2 according to the present invention.

As shown in FIG. 2, the surface of the heavy metal recovery complex of Example 1 and Comparative Example 2 of the present invention was observed with a scanning electron microscope (FEI company, Sirion) after the lead ion adsorption, The shape was observed.

As shown in FIG. 3, when confirmed by energy dispersive spectroscopy (EDS) to confirm the lead ion adsorption of the heavy metal recovery complex of Example 1 of the present invention, Ion was confirmed.

Element Atomic% C 63.80 O 34.85 Pb 1.35 Total: 100.00

[Experimental Example 2]

Analysis of Heavy Metal Ion Adsorption by pH Control of Heavy Metal Recovery Complex

According to the present invention, heavy metal recovery complexes prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to a heavy metal ion removal reaction in the following manner to analyze heavy metal ion adsorption amount.

0.03 g of each of Examples 1 to 3 and Comparative Examples 1 to 4 were immersed in 30 ml of a Pb ^{2 +} solution containing PbNO ₃ at a concentration of 180 mg / l to adsorb heavy metal ions. The pH of the Pb ^{2 +} solution was adjusted to 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 and 6.0, the reaction temperature was 25 ° C, and the reaction time was 3 hours. After completion of the reaction by analyzing the concentration (㎎ / g) of the Pb ^{+ 2} by AAS (Atomic Absorption Spectrometer, Shimadzu) is shown in Table 2.

pH Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 3.0 138 84 15 20 4 One 0 3.5 214 117 64 88 5 0 0 4.0 347 215 107 110 9 0 2 4.5 361 238 118 132 8 One One 5.0 392 254 132 138 15 3 2 5.5 386 231 131 137 18 2 5 6.0 382 248 73 94 17 5 4

As shown in Table 1, it was confirmed that the heavy metal recovery complex of the present invention had an excellent adsorption amount of heavy metal ions. Particularly, when a carpowder fiber is used as a base material and a polyphenolic compound is coated with a phenol-based polymer by polymerization with a phenolic acid such as gallic acid, the adsorption efficiency with lead ion is excellent and a more excellent amount of heavy metal ion adsorption is exhibited Respectively.

In the case of Comparative Example 1, when the polyphenol-based polymer was used without using a substrate, heavy metal ions could be adsorbed, but the adsorption efficiency of the polyphenol-based polymer was lower than that of the heavy metal recovery complex of the present invention containing the same amount of polyphenolic polymer I could confirm. Further, there is a problem that the polyphenolic polymer is lost during heavy metal adsorption.

In the case of Comparative Example 2, it was confirmed that the polyphenol-based polymer was not produced, and the adsorption of heavy metal ions was remarkably reduced by the coating of only the polyphenol-based compound. In addition, in the case of Comparative Example 3, polymerization efficiency of the polyphenolic polymer was decreased, and it was confirmed that the coating of the substrate was not smooth and the adsorption of heavy metal ions was hardly achieved. Further, in the case of Comparative Example 4, the hydrophilicity of the caraway fiber was secured through the acid treatment, but it was confirmed that the caraway fiber alone hardly adsorbed heavy metal ions.

The heavy metal recovery complex of the present invention is excellent in recovery efficiency or removal efficiency of heavy metal ions and can be applied to efficiently recover or remove heavy metal ions from a solution containing heavy metal ions such as wastewater, raw water or drinking water. Particularly, since the adsorption efficiency and the adsorption amount of lead ions are excellent, they can be applied to the efficient recovery or removal of lead ions.

As described above, in the present invention, the heavy metal recovery complex, the manufacturing method thereof, and the heavy metal removal method have been explained through the specified matters and the limited embodiments. However, the present invention is provided for better understanding of the present invention, It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

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 polyphenolic polymer in which a polyphenolic compound and an aldehyde-based compound are condensation-polymerized on the surface of a hollow fiber structure is coated,
Wherein the polyphenolic compound comprises phenolic acids which are any one or a mixture of two or more selected from gallic acid, syringic acid and ferulic acid. delete The method according to claim 1,
Wherein the aldehyde-based compound comprises any one or a mixture of two or more selected from formaldehyde, acetaldehyde, propionaldehyde and glutaraldehyde. The method according to claim 1,
Wherein the hollow structure fiber comprises any one or a mixture of two or more selected from a metal, a natural polymer, a synthetic polymer, carbon, and a ceramic. delete The method according to claim 1,
Wherein the hollow structure fiber has a porosity of 0.3 to 0.85. The method according to claim 1,
Wherein the fiber of the hollow structure and the polyphenolic polymer are in a weight ratio of 1: 0.5 to 5: 1. The method according to claim 1,
Wherein the lead ion recovery complex has a lead ion adsorption amount of 100 to 400 mg / g at a pH of 3 to 6. a) an aldehyde compound is added dropwise to a solution of a polyphenol compound containing phenolic acid, which is one or a mixture of two or more selected from gallic acid, syringic acid and ferulic acid, Preparing a solution;
b) dipping the hollow fiber into the mixed solution; And
c) coating a polyphenolic polymer on the surface of the fiber of hollow structure by mixing a basic material with the immersion liquid in which the fiber of the hollow structure is immersed;
≪ / RTI > 10. The method of claim 9,
Wherein the basic substance is added in the step (c) to adjust the pH to 8 to 12. Section 1. A lead ion removal method for adsorbing lead ions by immersing the lead ion recovery complex according to any one of claims 3, 4 and 6 to 8 in a solution containing lead ions. 12. The method of claim 11,
Wherein the solution containing the lead ions has a pH of 3 to 6. 13. The method of claim 12,
Wherein the lead ion-recovering complex has a lead ion adsorption amount of 100 to 400 mg / g at a pH of 3 to 6.

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