WO2014129763A1

WO2014129763A1 - Method for manufacturing capsule and capsule for absorbent which is obtained therefrom

Info

Publication number: WO2014129763A1
Application number: PCT/KR2014/001070
Authority: WO
Inventors: 윤영상; 원성욱; 프라탑코테
Original assignee: 전북대학교산학협력단
Priority date: 2013-02-19
Filing date: 2014-02-07
Publication date: 2014-08-28
Also published as: KR101513792B1; KR20140104553A

Abstract

The present invention relates to a method for manufacturing a capsule with which the selectivity in relation to specific metals and valuable metal recovery performance are improved by including functional substances on the surface or in the inside; and a capsule for an absorbent which is obtained by the method. The capsule for an absorbent of the present invention is capable of including required functional substances in the inside the capsule unlike with conventional beads, and the capsule is capable of maintaining its form while storing the substances for a long period of time. According to the present invention, by providing a high-molecular capsule in which functional substances such as a metal extraction agent are granulated, the metal recovery performance is improved and specific metals are selectively recovered. The method according to the present invention allows a solid/liquid separation for a valuable metal recovery, and thus the process can be simpler than a conventional hydrometallurgy mode, and since there is no second production of sludge, the process can be carried out in the more environmentally friendly manner.

Description

【Specification】

[Name of invention]

Capsule manufacturing method and capsule for adsorbent thereby

Technical Field

The present invention relates to a capsule manufacturing method and a capsule for adsorption by the same, and more particularly, a capsule manufacturing method for improving valuable metal recovery performance and selectivity to the tackifier metal by containing a functional material on the surface or inside thereof, and a capsule for the adsorbent thereby. It is about.

Background Art

As demand for electronic products increases rapidly, various waste electronic products are discharged as waste along with industrial wastewater generated during the manufacturing process of electronic products. Industrial wastewater and electronic waste products are the main contributors to the environment, but they also contain valuable metals such as gold, silver, and copper, and they have high recycling value. For example, the average valuable metal contained in one waste cell phone is worth 0.024g of gold, 0.14g of silver, and 10.5g of copper, which is worth more than 1,500 won. Resource conservation effect of about 750 million won will occur.

In order to cope with the recent resource exhaustion crisis, the recycling of resources is a global issue. The discovery of new resources is reaching its limit, and there is a great need to find fundamental solutions such as the use of alternative materials and waste resources to address the crisis of resource depletion.

The most important way to recover resources through industrial wastewater and waste electronic products is to recover valuable metals. The currently commonly used method for the recovery of valuable metals from waste water is the use of metal extractants. However, the use of a metal extractant has a problem of requiring a large-scale continuous process and generating secondary pollutants. In order to solve this problem, researches to recover the poultry in the poultry are being actively conducted, and a representative method is to use hydrogels such as alginate, chitosan and salloose.

For example, Korean Unexamined Patent Publication No. 10-2012-87678 discloses a method of removing a heterometal oxide adsorbent for removing bromate using a hydrogel. The method is characterized in that the bimetal oxide adsorbent containing two metals has higher surface charge than the one iron oxide adsorbent, so that the adsorption performance is improved, and the hydrogel cannot contain a reducing agent or the like. It is difficult to selectively recover bays. 1 shows a mechanism for producing beads by a conventional method. Referring to FIG. 1, conventionally, a capsule was prepared by dropping a polymer bead into an uncoagulant (eg, chloride). In the method for preparing beads according to FIG. 1, as the uncoagulant diffuses into the beads, the polymers in the solution are cured from the outside to the inside to prepare the beads. However, the method is limited in the content of the functional material, and it is difficult to contain the hydrophobic functional material. There are a number of problems, such as the release of functional materials.

[Detailed Description of the Invention]

[Technical problem]

<7> The present invention is to provide a capsule for the adsorbent with improved recovery capacity of valuable metals.

The present invention provides an adsorbent capsule capable of selectively recovering a specific metal and a method for manufacturing the same.

The present invention provides a new capsule manufacturing method that can easily contain the desired functional material in the capsule, unlike the conventional bead manufacturing method.

The present invention is to provide a new capsule and a method for manufacturing the same that can maintain the shape while receiving a functional material therein for a long time.

Technical Solution

<u> One aspect of the present invention comprises the steps of mixing a functional material and a quaternary agent;

<12> A step of dropping the mixed solution into a polymer solution, wherein the step of curing the polymer from the outside of the drop-shaped mixing solution in which the polymer is dropped to form a film having a predetermined thickness, and containing a functional material in the film It relates to a capsule manufacturing method comprising a.

In another aspect, the present invention relates to a cap for adsorbent prepared by the above method.

Advantageous Effects

Unlike the conventional beads, the capsule for adsorption of the present invention may contain a desired functional material in the capsule, and it is possible to maintain the shape while receiving them for a long time.

According to the present invention, by providing a polymer capsule granulated with a functional material such as a metal extracting agent, it is possible to improve the metal recovery performance and to selectively recover only a specific metal.

The method according to the present invention can simplify the process compared to the conventional wet smelting method because the solid-liquid separation is possible in the recovery of valuable metals, and secondary sludge does not occur. This makes the process more environmentally friendly.

[Brief Description of Drawings]

1 is a schematic view showing a conventional bead manufacturing method.

2 shows a schematic view of a capsule for an adsorbent according to the present invention.

3 is a schematic diagram of an apparatus for making a capsule of the present invention.

4 illustrates a process of forming a capsule in the capsule former 130.

<2i> FIG. 5 is a schematic diagram showing that when the capsule prepared in FIG. 4 is injected into a separate unpacking agent solution, the unpacking agent diffuses from the outside to the inside.

6 is an electron micrograph of the capsule or the beads obtained in Example 1, Example 4 and Comparative Example 1.

FIG. 7 is a graph showing that the adsorption test was performed using the capsule of Example 1. FIG.

8 is a graph showing that the adsorption test was performed using the capsule of Example 2. FIG.

9 is a graph showing that the adsorption test was performed using the camshade of Example 3. FIG.

<26>

[Form for implementation of invention]

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention relates to a method for preparing a capsule by injecting a mixed solution of a functional substance and a male agent in a polymer solution.

In the present invention, first, a functional substance and an ointment are mixed, and then dropped into a polymer solution to prepare ¾ slots.

The mixed solution is preferably added dropwise to the polymer solution in the form of beads. In the dropping step, the polymer surrounds the dropped mixed solution to form a wall having a predetermined thickness, and the uncoagulant pressurizes the inside of the formed polymer wall to the outside to maintain the shape of the polymer wall.

Through the dropping step, the functional material is contained within the formed polymer wall. Capsules prepared by the present invention contain a functional material therein or on the surface, where the expression "containing" means that the functional material is contained or contained within the capsule, and is precipitated or adsorbed on the capsule surface. It may indicate that it is coated. Furthermore, the expression "contains" means that the functional material, together with the polymer, forms the outer layer (shell) of the capsule. It does not exclude forming or supporting in the outer layer.

2 shows a schematic view of a capsule for an adsorbent according to the present invention. 3 is a schematic diagram of an apparatus for manufacturing the capsule of the present invention. Referring to FIG. 2, the capsul 100 of the present invention includes an interior region 10 and a wall 20.

The inner region 10 contains the functional material and the ointment. The wall 20 forms a wall surrounding the mixed solution as the polymer solidifies.

The thickness of the wall 20 may be 1-5,000, preferably 10-1,000.

Referring to FIG. 3, the manufacturing apparatus of the present invention includes a mixer 110, an injector 120, and a capsule former 130.

In the mixer 110, a mixed solution is prepared by mixing a functional solution and an ointment agent. The mixer may further mix high viscosity materials.

The injector 120 drops the mixed solution provided from the mixer 110 to the capsule former 130. The injection unit 120 may be provided with a nozzle that can drop the mixed solution at predetermined intervals.

The manufacturing apparatus of the present invention may include a transfer unit 140 for providing the mixed solution to the injection unit.

The capsule former 130 is filled with a polymer solution. In the capsule former 130, when the mixed solution is dropped into the polymer solution in the form of beads, the polymer in contact with the interface of the beads is cured to form a wall of a predetermined thickness.

The capsule former 130 may be provided with a stirrer.

4 illustrates a capsule formation process in the capsule former 130. In FIG. 4, CaC12 is used as an unpacking agent. Ca ²⁺ ionized inside the beads diffuses into the polymer solution surrounding the beads, thereby curing the polymer in the solution from the bead surface.

The method and manufacturing apparatus of the present invention can arbitrarily adjust the curing rate or thickness of the polymer wall by controlling the concentration of uncoagulant, such as Ca ²⁺ , and the polymer concentration in the capsule maker 130 inside the bead.

The capsule manufacturing method of the present invention may contain a large amount of functional material compared to the conventional bead or hydrogel manufacturing method, and the conventional technology has a great difficulty in containing a hydrophobic functional material, but the present technology provides a hydrophobic functional material easily. It may contain.

In addition, the present invention is a polymer material modification and containing according to the functional material containing There is no leakage of functional material and the capsule thickness can be easily adjusted, so high adsorption rate can be expected in terms of mass transfer.

The capsule manufacturing method and apparatus of the present invention may further include a step and a device for injecting the capsule formed by the dropping step into a separate coagulant solution. Figure 5 shows the action of the uncoagulant appearing after injecting the capsule prepared in Figure 4 into the coagulant solution. In FIG. 4, the coagulant is present only in the inside, but in the case of FIG. 5, the coagulant is also present in the polymer outer wall, and the uncoagulant diffuses from the outer wall to the inside to form the polymer outer wall more firmly.

The functional material may be any one or more of a metal reducing agent, a metal extractant, and a chelating compound.

The metal reducing agent is a natural antioxidant, tocopherols, flavone derivatives, phyl lozurcins, gal lie acid derivatives, catechin, nordihydroguaiaret ic acid, gossypol, lignan glycosides, plant extracts and polymers having metal reducing power, glutaraldehyde ( Glutaraldehyde), Sodium borohydride (NaBH ₄ ), Hydrazine (Ν ₂ Η ₄ ),

Borohydride, Dimethylamine borane [(CH ₃ ) ₂ NH.HBH ₃ ], Formaldehyde [CH ₂ 0], Sodium dithionite [Na2S2], Ascorbic acid [(¾06], Ethylene glycol, Sodium alkoxide,

_{Hydroquinone ((¾0 2), Sodium} oxalate (Na 2 C2H 2 0 4), Formic acid, may be at least one selected from Dimethylamine borane, Dithiothreitol, and Tris (2-carboxyethyl) phosphine.

The metal extractant may be an organophosphorus derivative (eg, tri isobutyl phosphine sulfide, trioctylphosphine oxide, tri alky lphosphine oxide), trioctylamine, methyl isobutyl ketone, trioctylmethyl Trioctylmethylammonium chloride, dibutyl sulfoxide, tris-iso-octyl amine, LIX 841 (tri pheny 1 hosph i ne, 2 一 hydroxyl— 5 一 nonylacetophenoneoxime), phospho 1 ic acid di (2- ethylhexyl) ester, tri—butyl phosphate, elex-100 (7- (4-ethyl-l-methyloctyl) -8-hydroxyquinol ine), alkyl sulfides, phosphine sulfide, hydroxyoxime derivatives (hydroxyoximes), secondary amines, tertiary amines, amonium salts, tri-n-butyl phosphate and quinoline Amines (trialkylmethylamine, n-dodecynylalkylmethylamine, triox Tilamine), trioctylphosphine oxide and ethylenediamineacetic acid There may be more than one.

Examples of the chelating agent include polyphosphate (for example, sodium triplyphosphate, nucleus metaphosphate, sodium pyrophosphate, sodium pyrophosphate, sodium pyrophosphate, sodium metaphosphate and sodium metaphosphate. ); Aminocarboxylic acids (e.g., ethylenediaminetetraacetic acid (EDTA), 1,2-bis (2-amino ᅳ phenoxy) ethane-N, Ν, Ν'Ν'-tetraacetic acid (EGTA), ethylenebis (Oxyethylenenitrilo) tetraacetic acid (ΒΑΡΤΑ), Ν- (hydroxyethyl) -ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), Ν-dihydroxyethylglycine (2- HxG), ethylenebis (hydroxyphenyl-glycine) (EHPG), glutamic acid, aspartic acid, glycine, lysine); 1,3—diketones (eg, acetylacetone, trifluoroacetylacetone, ^{tenoyltrifluoroacetone} , ascorbic acid); Hydroxycarboxylic acids (eg, tartaric acid, citric acid, malic acid, gluconic acid, peric acid, lactic acid, glucuronic acid); Polyamines (eg, diethylenetriamine, triethylenetriamine); Aminoalcohols (eg triethanolamine, N-hydroxyethyl ethylene-diamine, aminoethylethane amine (AEEA); phenols (eg disulfopyrocatechol, chromotropic acid); aminophenol (E.g., oxinsulfonic acid); Schiff base (e.g., disalicylaldehyde 1,2-propylenediimine); tetrapy (e.g., tetraphenylphosphine, phthalocyanine Silicates (aluminum calcium silicates, calcium silicates, sodium aluminosilicates, sodium aluminosilicates (hydrates), tricalcium silicates); sulfur compounds (e.g., potassium ethyl xantate, sodium diethyldithiocarbamate , Diethyl dithiophosphoric acid, thiourea, magnesium sulfate), synthetic macrocyclic compounds (e.g., nucleosamethyl- [14] -4,11-diene N4,2.2.2—cryptate); For example, polyethylene Min, polymethacryloylacetone, poly (ρ-vinylbenzyliminodiacetic acid), phosphonic acid (e.g. nitrilotrimethylenephosphonic acid, ethylenediaminetetra- (methylenephosphonic acid), hydroxy to Thylidenediphosphonic acid), melamine L-cystein, Phosphatidylcholone, and alamin.

Preferably, as the chelating agent, melamine, L-cystein,

Phosphatidylcholone or alamin can be used.

The uncoagulant may be sodium polyphosphate, calcium chloride, ethane, water or caustic soda solution.

The polymer is chitosan, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, agarose. ), Carageenan, amylopectin amylopectin, amylose, glycogen, starch, salose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate, dermatan sulfate dermatan sulfate, keratan sulfate, pectins, xanthanGum, carboxymethyl cellulose, homopolymers and copolymers of acrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, polyvinyl It may be at least one selected from the group consisting of alcohol-polyvinylacetate copolymer, poly (N-vinylpyridone), polyhydroxyethyl acrylate, polysulfone, and polyurethane.

The polymer may be dissolved in an appropriate solvent and used as the solvent.

， Alcohol ， ether ， ketone ， ionic liquid ， Ν, Ν-dimethylacrylamide methyl acylate, methyl acrylate, methacrylonitrile, methyl Methyl-methacrylate, Styrene, Vinyl acetate, Vinyl chloride, 4-vinyllpyndine, n-vinylpyrrolidone , Dimethyl formamide, dimethylsulfoxide, diphenylamine: ethylene carbonate, iron (III) iron, magnesium perchlorate, Sulfur dioxide, Triethylamine, Trimethyl amine, Tripropylamine, Zinc chloride, Acrylamide You may use one or more selected from the group consisting of nitriles (Acrylonitri le) acryloyl.

The polymer is cured from the outside of the bead-shaped mixed solution to the inside to form a film having a predetermined thickness.

The concentration of the polymer solution is 0.01 to 80% (w / v), 0.01 to 50% (w / v) of the functional material and 0.01 ~ 40¾> (w / v) of the coagulant in comparison to the polymer solution Can be used.

The method further includes a high viscosity material in the mixed solution, and the functional material may be granulated by the high viscosity material.

In more detail, when the highly viscous material, the functional material and the arch agent are made into a physically mixed emulsion state, beads of the emulsion in the emulsion state are added to the polymer solution. As the polymer solution is cured by the ointment agent, a capsule may be formed in the form of coating the complex beads from the outside.

According to the present invention, a predetermined viscosity is obtained by mixing a functional material and a high viscosity material. The functional substance can be stably contained in the capsule because it is in the state of the excitation emulsion.

The highly viscous material may be added in an amount of 0.01 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the functional material so that the functional material does not elute to the outside of the capsule. If it is less than 0.01 part by weight, it is difficult to block the granulation of the functional material and to elute out of the capsule, and when it exceeds 50 parts by weight, it is difficult to drop the solution with excessive viscosity.

The high viscosity material may be used having a viscosity of 2 ~ 10,000 mPa s.

* The highly viscous materials include Carboxymethyl Cellulose, Hydroxyethyl Cellulose, Xanthan Gum, Hycel, Carbomer, Gelatin ), Pectin, Guargum, Sodium Alginate, Calcium Glycerophosphate, Carrageenan, Tragacanth gum, Propylene Glycol Glycol Alginate, Methylethylcel lulose, Potassium Alginate and Carboxymethylcelulose calcium (Calcium Carboxymethylcel lulose)

In another aspect the invention relates to a capsule for adsorbent prepared in the above process. Capsule for the adsorbent of the present invention is a functional material melamine, L-cystein, Phosphatidylcholone, dibutyl sulfoxide, LIX

Selective for palladium including 841 (tri heny 1 phosphine, 2-hydroxy 1 -5-nony 1 acet ophenoneox i me), trioctylphosphine oxide, trialkylphosphine oxide It can have adsorption capacity. The capsule may have a selective adsorption capacity for gold, including aamine (alamine), methyl isobutyl ketone as a functional material.

The capsule for the adsorbent may be visually determined by the replacement cycle of the capsule using an oil component among the aforementioned functional materials. Having an oily component may be alumina, melamine and the like.

The capsule is settled to the bottom at the top of the solution by increasing the specific gravity as the valuable metal adsorbs. In addition, when the capsule settled on the bottom is collected and put into the desorption solution, the adsorbed metal floats to the top of the desorption process.

<67> In the valuable metal recovery method according to the present invention, a specific valuable metal can be selectively recovered. In addition, the method according to the present invention can be separated by solid-liquid separation in valuable metal recovery, it is possible to operate an environmentally friendly process.

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

<70>

Example 1

50mL 1.5% CaC12 solution and 1.5% carboxymethyl salloose (CMC) solution were mixed, and 4 g of melamine was added to the mixture to prepare a mixed solution. The mixed solution was dropped in 0.6% w / v Na-alginate solution and stirred for 5 minutes to obtain a capsule.

After washing the capsule obtained above was added to 100 mL of 2% CaC12 solution and stirred for about 30 minutes. After reaction was completed, the ¾ capsule was washed several times with deionized water.

<74>

Example 2

A capsule was prepared in the same manner as in Example 1 except for adding 4 g of L-Cistein instead of melamine.

<77>

<78> Example 3

Capsules were prepared in the same manner as in Example 1 except for adding 4 g of Phosphatidylcholone instead of melamine.

<80>

Example 4

Into a 50mL solution (1.5% CaC12 solution and 1.5% carboxymethyl cell containing rose (CMC)) 10ml alaminol to prepare a mixed solution. The mixed solution was dropped into 0.6% w / v Naginal solution and stirred for 5 minutes to obtain a capsul.

After the capsules obtained above were washed, 100 ml of 2% CaC12 solution was added and stirred for about 30 minutes. After the reaction was completed, the capsules were washed several times with deionized water.

<84>

<85> Comparative Example 1

Inject a 0.6% w / v Na-alginate solution into 1000 ml of a 2% CaC12 solution at room temperature

After 30 minutes of reaction, the beads were obtained and washed several times.

<87> " exam

Mixed solution of Au (III), Pd (II), Pt (IV) to evaluate the adsorption selectivity of the prepared materials (each metal ion in 0.1M HC1 solution contains 100mg / L). 0.05 g of the capsules obtained in Examples 1 to 3 were added to a mixed solution, and then adsorption was performed by adjusting the pH to a range of 2 to 12 using 1M NaOH and 1M HC1. Figure 6 is an electron micrograph of the capsule or bead obtained in Example 1, Example 4 Comparative Example 1.

Referring to Figure 6, the capsule of the present invention can be seen that the outer wall is formed to a predetermined thickness, but the wall of the predetermined thickness is not formed in the beads of Comparative Example 1.

In addition, FIG. 6 shows that the functional material is mixed with the high viscosity material and granulated in an emulsion state.

7 is a graph showing that the adsorption test was carried out using the capsule of Example 1, Figure 8 is a graph showing that the adsorption test was performed using the capsule of Example 2, Figure 9 is carried out It is a graph showing that the adsorption test was performed using the capsule of Example 3.

Referring to FIG. 7, in the case of using the capsule of Example 1, Au increased the adsorption performance at pH 2 ~ 4, the adsorption performance was slowly decreased at pH 4 ~ 10 and the adsorption performance rapidly decreased from pH 10 . On the other hand, Pt showed an increase in adsorption performance above pH 10 and Pd showed the highest adsorption selectivity over the entire pH range. Melamine-containing capsules selectively adsorb palladium over platinum in the range of pH 4 to pH 12, and melamine-containing capsules have very high selectivity to palladium over platinum and gold near pH 2 or pH 12. It can be seen that high.

Referring to Figure 8, when using the capsul of Example 2, it can be seen that the selective adsorption of palladium and gold rather than platinum. In other words, when the pH is 3 to 6 or more than pH 9, the selectivity to paladin and gold is superior to platinum.

Referring to Figure 9, when using the capsule of Example 3, it can be seen that the selectivity to gold is superior to platinum and palladium over the entire pH range. So far, specific embodiments of the present invention have been described. Those of ordinary skill in the art to which the present invention pertains do not depart from the essential characteristics of the present invention. It will be appreciated that the present invention may be embodied in a modified form. The scope of the present invention is shown in the appended claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

Industrial Applicability

The present invention relates to a method for preparing a capsule having a functional material contained on or inside a surface thereof, and to improving the valuable metal recovery performance and selectivity with respect to a specific metal, and to a capsule for the adsorbent, which can be used in the valuable metal recovery industry.

<101>

Claims

[Range of request]

[Claim 1]

Mixing a functional substance with a coagulant;

And dropping the mixed solution into a polymer solution, wherein the dropping step surrounds the bead-shaped mixed solution to form a wall having a predetermined thickness.

[Claim 2]

The method of claim 1, wherein the method further comprises the step of injecting the capsule formed in the dropping step into the uncoagulant solution.

[Claim 3]

The method of claim 1, wherein the functional material is at least one of a metal reducing agent, a metal extractant, and a chelating compound.

[Claim 4]

4. The metal reducing agent according to claim 3, wherein the metal reducing agent is a natural antioxidant, tocopherols, flavone derivatives, phyllozurcins, gal lie acid derivatives, catechin, nordihydroguaiaretic acid, gossypol, lignan glycosides, plant extracts, and metal-reducing agents, glutarum Aldehyde (Glutaraldehyde), Sodium borohydride (NaBH), Hydrazine (Ν ₂ Η ₄ ),

Borohydride, Dimethyl amine borane [(C¾) 2NH.HB], Formaldehyde [CH ₂ 0], Sodium dithionite [Na ₂ S ₂ 0 ₄ ], Ascorbic acid [C ₆ H ₈ 0 ₆ ], Ethylene glycol, Sodium alkoxide,

A method for preparing a capsule, characterized in that at least one selected from hydroquinone ((¾0 ₂ ), sodium oxalate (N C2H ₂ 04), formic acid, dimethyl amine borane, dithiothreitol, and tris (2-carboxyethyl) phosphine.

[Claim 5]

4. The chelating agent of claim 3 wherein the chelating agent is melamine, L-cystein, Phosphatidylcholone, alamin, polyphosphate, aminocarboxylic acid. 1,3-diketone, hydroxycarboxylic acid, polyamine and amino alcohol of any one or more of the capsule manufacturing room

[Claim 6]

The method of claim 3, wherein the metal extracting agent is an organophosphorus derivative (e.g., tr i isobutyl hosphine sulfide, tr ioctylphosphine oxide, tr ialkylphosphine oxide), trioctylamine, methyl isobutyl ketone), trioctylmethylamonium chloride, dibutyl sulfoxide, tris-iso-octyl amine, LIX 841 (tri heny 1 phosphine, 2-hydr oxy 1 -5- nony 1 ace t ophenoneox i me), phosphol ic acid di (2-ethylhexyl) ester, tri-butyl phosphate, Kelex-100 (7- (4-ethyl-l-methyloctyl) 一 8— hydroxy qui no 1 ine) ， Alkyl sulfides, phosphine sulfides, hydroxyoximes, secondary amines, tertiary amines, ammonium salts, tribune n- Tri-n-butyl phosphate, quinoline derivatives, polymeric amines (trialkylmethylamine, n—dodecynylalkylmethylamine, trioctylamine), trioctylphosphineoxide and ethylenediamineacetic acid Capsule production method characterized in that at least one selected from the group.

[Claim 71

According to claim 1, wherein the polymer is chitosan, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, agarose (agarose), carageenan, amylopectin, amylopectin, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, Dextran sulfate, dermatan sulfate, keratan sulfate, pectin, pectins, xanthanGum, carboxymethylcellose, homopolymers and copolymers of acrylamide, polya Krylic acid, polyethylene oxide, polyvinyl alcohol, polyvinyl alcohol—polyvinylacetate copolymer, poly (Ν—vinylpyrrolidone), polyhydroxyethyl acrylate, polysulfate Kaemsyul Article method, and poly group consisting of polyurethane, characterized in that at least one selected.

[Claim 8]

The method of claim 1, wherein the method further comprises a high viscosity material in the mixed solution, and the functional material is granulated by the high viscosity material.

[Claim 9]

The method of claim 7, wherein the high viscosity material is Carboxymethyl Cellulose, Hydroxyethyl Cellulose, Xanthan Gum, Hycel, Carbomer ， Gelatin, Pectin, Guargum, Sodium Alginate, Glycerophosphate (Calcium Glycerophosphate, Carrageenan, tragacanth gum, Propylene Glycol Alginate, Methylethylsalose

(Methylethylcel lulose), Potassium alginate (Potassium Alginate) and carboxymethyl cellulose calum (Calcium Carboxymethylcel lulose) A method for producing a capsule, characterized in that one selected from the group consisting of.

[Claim 10]

The method according to claim 1, wherein the uncoagulant is sodium polyphosphate, calcium chloride, ethanol, water or caustic soda solution.

[Claim 11]

A capsule for adsorbent prepared according to any one of claims 1 to 10.

[Claim 12]

The method of claim 11, wherein the capsule is a functional substance melamine, L-cystein, Phosphatidyl chol one, dibutyl sulfoxide, LIX

841 (t r pheny 1 hosph i ne, 2-hydr oxy 1 -5-nony 1 ace t ophenoneox i me), a capsule for adsorbent, characterized in that it has a selective adsorption capacity to palladium, including tr ioctylphosphine oxide and tr ialkylphosphine oxide.

[Claim 13]

The capsule of claim 10, wherein the capsul has a selective adsorption capacity to gold, including aamine and methyl isobutyl ketone as functional materials.