KR20130055168A - Polymer gel containing metal extractant, method for manufacturing the same and method for recovering precious metal using the same - Google Patents

Abstract

PURPOSE: A polymer gel containing metal extract is provided to improve metal collection performance, to selectively collect a specific metal, and to separate solid and liquid from each other. CONSTITUTION: A manufacturing method of a polymer gel containing metal extract comprises a step of manufacturing a mixture by mixing a metal extract, highly viscous material, and a polymer solidifier; and a step of spinning the mixture to polymer solution which is dissolved in solvent. The highly viscous material is 0.01-50 parts by weight, based on 100.0 parts by weight of the metal extract. A polymer gel including a metal extract comprises an inner layer including the mixture of the metal extract and highly conductive material; and a polymer gel outer layer surrounding the inner layer. [Reference numerals] (A) Metal extracting agent; (AA) Add into a biopolymer solution; (B) Highly viscous material; (BB) Coagulate biopolymer; (C) Biopolymer coagulant; (CC) Purify the biopolymer by the coagulated liquid of the biopolymer; (DD) Wash; (EE) Metal extracting agent + Highly viscous material; (FF) Hydrogel capsule containing metal extracted liquid

Description

TECHNICAL FIELD The present invention relates to a polymer gel containing a metal extractant, a method for producing the polymer gel, and a method for recovering valuable metals using the same.

The present invention relates to a polymer gel containing a metal extractant, a process for producing the polymer gel, and a method for recovering valuable metals using the polymer gel. More particularly, the present invention relates to a polymer gel used for separating and recovering metals, A method for preparing the same, and a method for recovering valuable metals using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polymer gel, .

As the 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 or waste electronic products are the main cause of polluting the environment, but they also contain valuable metals such as gold, silver, and platinum group metal, which is high in 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, and is worth more than about 1,500 won. Resource conservation effect of 150 million won will occur.

In order to cope with the recent resource depletion crisis, the recycling of resources is a global issue. The discovery of new resources is reaching its limit, and it is necessary to take fundamental measures such as substitute materials or waste resources to cope with the resource depletion crisis.

The most important way to recover resources through industrial wastewater or electronic waste is to recover valuable metals. Researches are currently under way to utilize biodegradable polymers such as alginate, chitosan, and cellulose, using a metal extractor, an ion exchange resin, or environmentally friendly methods for collecting valuable metals. However, when a metal extractant is used, a large-scale process is continuously required. In the case of using a hydrogel, the recovery method is simple, but the recovery performance is low and it is difficult to selectively recover only a specific metal.

In order to solve the above problems, the present invention provides a polymer gel comprising a metal extractant capable of improving work stability while improving physical properties and providing convenience in storage and use of a metal extractant, a method for producing the same, And a method for recovering valuable metals using the same.

The method for preparing a polymer gel containing a metal extractant according to the present invention comprises: preparing a mixture by stirring a metal extracting agent, a high viscosity material and a polymer coagulant; And spinning the mixture in a polymer solution dissolved by a solvent.

The polymer gel comprising the metal extractant according to the present invention comprises an inner layer comprising a mixture of a metal extractant and a high viscosity material; And a polymer gel outer layer formed in the form of coating the inner layer externally.

The method for recovering valuable metals according to the present invention comprises the steps of: adsorbing a valuable metal by injecting a polymer gel containing a metal extractant prepared according to the above production method into a solution containing a valuable metal; And recovering the valuable metal by adding the polymer gel adsorbed on the valuable metal to the desorbing solution.

According to the present invention, metal recovery performance can be improved by providing a polymer gel in which a metal extractant is granulated, and only a specific metal can be selectively recovered. In addition, solid-liquid separation is possible, and it can be operated in an eco-friendly process. It is also possible to provide convenience in storage and use of the metal extractant.

FIG. 1 is a schematic view illustrating the production of a polymer gel containing a metal extracting agent according to an embodiment of the present invention. Referring to FIG.
FIG. 2 is a microscopic photograph of a polymer gel prepared according to Example, Comparative Example 1, and Comparative Example 2. FIG.
Fig. 3 shows the metal recovering performance of the polymer gel prepared according to Example, Comparative Example 1, and Comparative Example 2. Fig.
4 shows the metal recovery selectivity of the polymer gel prepared according to Example, Comparative Example 1 and Comparative Example 2. FIG.
FIG. 5 shows the desorption efficiency of a valuable metal recovered by a polymer gel produced according to an embodiment.

Hereinafter, the present invention will be described in detail.

The method for preparing a polymer gel comprising a metal extractant according to an embodiment of the present invention includes the steps of preparing a mixture by stirring a metal extractant, an agglomerating agent and a polymer coagulant, and radiating the mixture to a polymer solution dissolved by a solvent .

In the present invention, the polymer gel is formed in such a manner that a polymer solidified by the polymer coagulant externally coats a mixture of the metal extractant and the high-viscosity material, and the mixture of the metal extractant and the high- In the state of being granulated.

More specifically, when the mixture of the highly viscous substance, the metal extractant and the polymer coagulant is physically mixed into an emulsion state through an agitation process and then the emulsion mixture is added to the polymer solution, The polymer solution may solidify in the form of a polymer gel by a coagulant, and a capsule may be formed in which the mixture of the high-viscosity material and the metal extract is coated externally.

In the case of preparing a polymer gel containing a metal extracting agent, most of the metal extracting agents are released to the outside of the polymer gel, so that it may be difficult to exert the expected effects. However, according to the present invention, since the metal extractant and the high viscosity material are mixed to form an emulsion state having a predetermined viscosity, the metal extractant can be stably contained in the polymer gel.

The metal extractant may be selected from the group consisting of alkyl sulfides, phosphine sulfide, hydroxyoximes, secondary amines, tertiary amines, ammonium salts, Tri-n-butyl phosphate, sodium diethylthiocarbamate, potassium cresentate, couperone, couperone-like compounds,? -Dioxime, ditizone (diphenylthiocarbazone), 1-nitroso-2-naphthol, 1-nitroso-2-naphthol-like compound, 1-nitroso-2-naphthol, 2-naphthol (PAN), ethylenediamine acetic acid, 1,10-pentantronine, neocuproine (2,9-dimethyl-1,10-phenanthroinine) 2'-dipyridyl, alcohols, ketones, ethers, trioctylphosphine oxide (TOPO), halogen salt anions, pseudohalogen salt anions, polymeric amines (trialkylmethylamine, Sinil alkyl may be at least one selected from methyl amine, trioctylamine, etc.), and the group consisting of crown ethers (12C4, 15C5, 18C6, etc.). Metal extractants are generally useful for the separation of desired valuable metals because they have selectivity for certain metals. According to the present invention, there is an advantage that a desired metal can be easily separated and recovered without further processing by a metal extracting agent contained in the polymer gel inner layer.

The highly viscous material may be selected from the group consisting of Carboxymethyl Cellulose, Hydroxyethyl Cellulose, Xanthan Gum, Hycel, Carbomer, Gelatin, Pectin, Guargum, Sodium Alginate, Calcium Glycerophosphate, Carrageenan, Tragacanth Gum, Propylene Glycol Alginate, Methyl Ethyl Cellulose, And may be at least one selected from the group consisting of methylethylcellulose, potassium alginate and calcium carboxymethylcellulose, preferably carboxymethylcellulose.

In order to prevent the metal extractant from leaching out of the polymer gel, the content of the highly viscous substance is 0.01 to 50 parts by weight, preferably 1 to 20 parts by weight, Can be added. When the amount is less than 0.01 part by weight, it is difficult to block the granulation of the metal extracting agent and elution to the outside of the polymer gel, and when the amount is more than 50 parts by weight, it is difficult to spin the solution at the time of producing the material due to excessive viscosity. but, Depending on the kind of the high-viscosity material, a viscosity may be sufficient even when a very small amount thereof enters, and therefore, a more important factor may be viscosity than the above-mentioned content.

The highly viscous material may have a viscosity of 2 to 10,000 mPa · s, preferably 10 to 5000 mPa · s. If the viscosity is less than 2 mPa · s, the viscosity is too small to effectively granulate the extracting agent, and if the viscosity is 10000 mPa · s or more, the spinning of the mixed solution becomes difficult.

In the present invention, the polymer coagulant solidifies the polymer solution in a polymer gel state to allow the polymer gel to form a capsule in the form of coating the mixture of the metal extract and the highly viscous material on the outside.

The polymer is chitosan, alginate, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, agarose, and carrageenan. carageenan, amylopectin, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate, dermatan Sulfates (dermatan sulfate), keratan sulfate, pectins, xanthan gum, carboxymethylcellulose, homo and copolymers of acrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, poly At least one selected from the group consisting of vinyl alcohol-polyvinylacetate copolymer, poly (N-vinylpyrrolidone), polyhydroxyethyl acrylate, polysulfone, and polyurethane And preferably alginate.

The solvent may be selected from the group consisting of water, alcohol, ether, ketone, ionic liquid, N, N-dimethylacrylamide methyl acylate, methyl acrylate, ), Methyl methacrylate, styrene, vinyl acetate, vinyl chloride, 4-vinylpyridine, n-vinylpyrrolidone, ), Dimethyl formamide, dimethylsulfoxide, diphenylamine, ethylene carbonate, iron (III) chloride, magnesium perchlorate, sulfur dioxide And examples thereof include sulfur dioxide, triethylamine, trimethylamine, tripropylamine, zinc chloride, acrylamide, and acrylonitride. rile "). < / RTI > For example, when the solvent is water, the polymer gel may be a hydrogel. A hydrogel is a hydrophilic polymer containing water as a three-dimensional network structure of a polymer chain. The hydrogel of the electrolytic polymer is highly absorbent and is widely used as an absorbent polymer in various fields.

The ionic liquid may be composed of a cation and an anion containing a single 5-membered or 6-membered ring which is not fused with another ring structure. Specifically, the cation may be selected from the group consisting of pyridinium pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, oxazolium, 1,2,3-triazolium, 4-triazolium cation, and the anion may be acetate, halogen, pseudohalogen or a C1-6 carboxylate anion.

The temperature of the polymer solution may be in the range of 0 to 150 ° C, preferably in the range of 20 to 80 ° C.

The polymer solution may be maintained at a concentration of 0.01 to 50% (w / v), preferably 0.1 to 20% (w / v). If the concentration is less than 0.1% (w / v), the efficiency of forming a coating film by the polymer coagulant is low. If it exceeds 20% (w / v), it is difficult to dissolve and stir the polymer.

The method may further comprise the step of washing or drying the mixture of the metal-extracting agent and the high-viscosity material after the polymer gel is coated on the outside. The washing and drying method is not particularly limited. The remaining coagulant may be removed through the washing process.

In another aspect, the invention features an inner layer comprising a mixture of a metal extractant and a high viscosity material; And a polymeric gel outer layer formed in such a manner as to coat the inner layer externally.

The inner layer can be granulated into a plurality of granules. The present invention can improve the metal recovering performance of the polymer gel and selectively recover the metal by granulating the metal extractant in the inner layer. It is also possible to provide convenience in storage and use of the metal extractant.

The thickness of the outer layer may be 1 to 5000 탆, preferably 10 to 1000 탆. If the thickness is less than 1 mu m, the stability of the material is lowered and the granulated metal extractant may be eluted again. If the thickness is more than 5000 mu m, the reaction of the metal extractant becomes difficult to occur efficiently.

The thickness can be controlled by controlling the kind, concentration, temperature, reaction time, etc. of the polymer solution.

The metal extractant, the high viscosity material, the polymer coagulant, and the polymer may be mentioned in the foregoing.

In another aspect, the present invention relates to the use of a polymer gel comprising a metal extractant prepared by the above method in a method for recovering a valuable metal.

The method for recovering valuable metals according to an embodiment of the present invention includes the steps of adsorbing a valuable metal by injecting a polymer gel containing a metal extractant prepared according to the above method into a solution containing a valuable metal, Into the desorption solution to recover the valuable metal.

Examples of the above-mentioned valuable metal-containing solution include industrial wastes generated mainly in industrial and electric and electronic industries using a valuable metal catalyst as a catalyst in a chemical process.

The method for recovering valuable metals may further include the step of injecting a polymer gel to adsorb a valuable metal, and then washing the polymer gel adsorbed on the valuable metal with distilled water.

The present invention includes a step of charging a polymer gel containing the metal extractant prepared according to the above method into the above-mentioned metal-free metal-containing solution to adsorb the metal-free metal. When a polymer gel is used for recovering valuable metals, the metal can be recovered by a relatively simple method, but its performance is lower than that of the metal extractant, and there is a problem that it does not have selectivity for a specific metal. In addition, when a metal extractant is used, a large-scale process is required for recovering metal, and there is also a problem of harmfulness due to the use of an organic solvent. However, according to the present invention, it is possible to improve the metal recovering performance and increase the selectivity to a specific metal by using a polymer gel in which the metal extracting agent is granulated in the inner layer. In addition, solid-liquid separation can be performed by a polymer gel, which simplifies the process and enables operation in an eco-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.

Example

Preparation of alginate gel containing tertiary amine (Alamine 304)

10 mL of tertiary amine (Alamine 304) was added to a mixture of 1.5% (w / v) calcium chloride and 1.5% (w / v) carboxymethyl cellulose (CMC) and stirred for 12 hours at room temperature. . The emulsion mixture was spun into a 0.6% (w / v) alginate solution dissolved in water and stirred at room temperature for 5 minutes. Then, the gelated alginate gel was washed several times with deionized water, and then charged in 1000 mL of 2% (w / v) calcium chloride and stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed with deionized water several times to remove residual coagulant, and finally an alginate gel containing tertiary amine (Alamine 304) was prepared.

Comparative Example 1

The solution was spun into a 0.6% (w / v) alginate solution dissolved in water using 1.5% (w / v) calcium chloride and 1.5% (w / v) carboxymethyl cellulose (CMC) Lt; / RTI > Then, the gelated alginate gel was washed several times with deionized water, and then charged in 1000 mL of 2% (w / v) calcium chloride and stirred at room temperature for 30 minutes. After the completion of the reaction, the remaining coagulant was removed by washing several times with deionized water to finally prepare a capsular alginate gel.

Comparative Example 2

A 0.6% (w / v) alginate solution dissolved in water was spun into 2 mL (w / v) calcium chloride 1000mL and stirred at room temperature for 30 minutes. After the completion of the reaction, the remaining coagulant was removed by washing several times with deionized water, and finally a bead type alginate gel was prepared.

Test Example 1

Comparison of the recovery of valuable metals

The recoveries of valuable metals were compared with those of gold - containing, metal - containing solutions containing gold, platinum and palladium dissolved in 1M hydrochloric acid. 0.06 g of the alginate gel prepared according to the example was added to a solution (30 mL) containing a gold metal, platinum and palladium, and the mixture was stirred for 24 hours to adsorb the valuable metal. Alginate gels prepared according to Comparative Examples 1 and 2 were also evaluated for recovering valuable metals in the same manner as above. As a result, as shown in Table 1 and FIG. 3, alginate gel containing tertiary amine (Alamine 304) exhibited the best metal adsorption performance as compared with Comparative Examples 1 and 2. That is, the method of recovering the metal metal by the polymer gel by granulating the metal extracting agent can recover the valuable metal in an environmentally friendly manner through a simple process as compared with the conventional solvent extraction method. It can also be seen that the recovery performance can be significantly improved as compared with the conventional hydrogel recovery method.

Adsorption amount (mg / g) Comparative Example 1 Comparative Example 2 Example Au (mg / g) 0.078 1.363 52.731 Pd (mg / g) 0.361 1.184 4.795 Pt (mg / g) 0.048 1.621 10.533

The adsorption amount indicates the adsorption amount of the valuable metal by the adsorbent material.

Test Example  2

Comparison of selectivity of crude metal recovery

Comparative Example 1 Comparative Example 2 Example K _{Au / Pd} 0.13 0.70 19.42 K _{Au / Pt} 1.05 0.54 8.15

(K is metal selectivity, Q is adsorption amount, and C is metal concentration after reaction).

(Au), palladium (Pd), and platinum (Pt) in the alginate gel (Example) containing the metal extractant (Alamine 304) Au) adsorbed on the surface. Therefore, in order to confirm the selectivity for gold (Au) in the mixed solution, it was calculated using the above formula. As shown in Table 2 and FIG. 4, the selectivity to gold (Au) of the alginate gel (example) including the metal extractant was significantly higher than that of Comparative Example 1 and Comparative Example 2. In particular, the selectivity of gold (Au) to palladium (Pd) was excellent. That is, the inclusion of the metal extractant (Alamine 304) shows that the selectivity to gold (Au) is improved. This indicates that the desired metal can be selectively recovered depending on the kind of the metal extractant contained in the polymer gel.

Test Example  3

Valuable metal recovery test

After the adsorbent material was adsorbed using the adsorbent material (alginate gel) prepared in the above example, the adsorbent material was washed with distilled water and then 30 mL of 1M HCl, 30 mL of 1M thiourea (thiourea), and 1M HCl / And 30 mL of a 1 M thiourea mixed solution was subjected to desorption test of a valuable metal for 24 hours. As shown in FIG. 5, when 1 M HCl / 1 M thiourea mixed solution and 1 M thiourea were used, it was confirmed that desorption of the valuable metal was effectively performed. This means that the adsorbed metal can be effectively recovered by the adsorbent material produced by the embodiment.

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

Claims (18)

Preparing a mixture by stirring the metal extractant, the highly viscous material and the polymer coagulant; And
Polymer gel manufacturing method comprising a metal extracting agent comprising the step of spinning the mixture in a polymer solution dissolved by a solvent. The method of claim 1, wherein the polymer gel is formed in such a manner that a polymer solidified by the polymer coagulant externally coats a mixture of the metal extractant and the high-viscosity material, Wherein the mixture is granulated in an emulsion state. The method of claim 1, wherein the metal extracting agent is alkyl sulfides, phosphine sulfide, hydroxyoximes, secondary amines, tertiary amines, ammonium Salt (ammonium salt), tri-n-butyl phosphate, sodium diethylthiocarbamate, potassium xenogenate, couperone, couron-like compound, α-dioxium, ditizone (di Phenylthiocarbazone), 8-quinolinol, 8-quinolinol substituents, β-diketones, acetylacetone, tenoyltrifuroracetone (TTA), 1-nitroso-2-naphthol, 1-nitroso-2 Naphthol-like compounds, 1- (2-pyridylazo) -2-naphthol (PAN), ethylenediamineacetic acid, 1,10-petanetronin, neocouferin (2,9-dimethyl-1,10-fer Nantronin), 2,2'-dipyridyl, alcohols, ketones, ethers, trioctylphosphine oxide (TOPO), halogen anions, pseudohalogenated anions, polymer amines (trials Methylamine, N- dodecyl during carbonyl alkyl methyl amine, trioctylamine, etc.) and crown ethers (12C4, 15C5, method for producing a polymer gel comprising a metal extractant, characterized in that at least one selected from the group consisting of 18C6, etc.). The method of claim 1, wherein the high viscosity material is selected from the group consisting of Carboxymethyl Cellulose, Hydroxyethyl Cellulose, Xanthan Gum, Hycel, Carbomer, Gelatin Pectin, Guargum, Sodium Alginate, Calcium Glycerophosphate, Carrageenan, Tragacanth gum, Propylene Glycol, Wherein the metal extracting agent is at least one selected from the group consisting of alginate, methylethylcellulose, potassium alginate and calcium carboxymethylcellulose. The method of manufacturing a polymer gel according to claim 1, wherein the high viscosity material is 0.01 to 50 parts by weight based on 100 parts by weight of the metal extractant. The method of claim 1, wherein the high viscosity material is a polymer gel manufacturing method comprising a metal extracting agent, characterized in that having a viscosity of 2 ~ 10000 mPa s. The method of claim 1, wherein the polymer is chitosan, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, agarose. (agarose), carageenan, amylopectin, amylose, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate dextran sulfate, dermatan sulfate, keratan sulfate, pectin, xanthan gum, carboxymethylcellulose, acrylamide alone and copolymers, polyacrylic acid, polyethylene oxide , Polyvinyl alcohol, polyvinyl alcohol-polyvinylacetate copolymer, poly (N-vinylpyrrolidone), polyhydroxyethyl acrylate, polysulfone, and polyurethane Method for producing a polymer gel comprising a metal, characterized in that the extract is more than one. The method of claim 1, wherein the solvent is water, alcohol, ether and ketone polymer gel production method comprising a metal extract, characterized in that at least one selected from the group consisting of ketones. The method of claim 1, wherein the polymer solution is maintained at 0 to 150 ° C. The method for preparing a polymer gel according to claim 1, wherein the polymer solution is maintained at a concentration of 0.01 to 50% (w / v). An inner layer comprising a mixture of a metal extractant and a high viscosity material; And
Polymer gel comprising a metal extracting agent including an outer layer of the polymer gel formed in the form of coating the inner layer from the outside. 12. The polymer gel according to claim 11, wherein the inner layer is granulated into a plurality of grains. 12. The polymer gel according to claim 11, wherein the outer layer has a thickness of 1 to 5000 mu m. 12. The method of claim 11, wherein the metal extracting agent is alkyl sulfides, phosphine sulfides, hydroxyoximes, secondary amines, tertiary amines, ammonium Salt (ammonium salt), tri-n-butyl phosphate, sodium diethylthiocarbamate, potassium xenogenate, couperone, couron-like compound, α-dioxium, ditizone (di Phenylthiocarbazone), 8-quinolinol, 8-quinolinol substituents, β-diketones, acetylacetone, tenoyltrifuroracetone (TTA), 1-nitroso-2-naphthol, 1-nitroso-2 Naphthol-like compounds, 1- (2-pyridylazo) -2-naphthol (PAN), ethylenediamineacetic acid, 1,10-petanetronin, neocouferin (2,9-dimethyl-1,10-fer Nantronin), 2,2'-dipyridyl, alcohols, ketones, ethers, trioctylphosphine oxide (TOPO), halogen anions, pseudohalogenated anions, polymer amines (trials Kylmethylamine, N-dodecynylalkylmethylamine, trioctylamine and the like) and crown ether (12C4, 15C5, 18C6, etc.) is a polymer gel comprising a metal extracting agent, characterized in that at least one selected from the group consisting of. 12. The polymer gel according to claim 11, wherein the high viscosity material is 0.01 to 50 parts by weight based on 100 parts by weight of the metal extractant. 12. The polymer gel according to claim 11, wherein the high viscosity material has a viscosity of 2 to 10000 mPa s. The method of claim 11, wherein the polymer is chitosan, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, agarose. (agarose), carageenan, amylopectin, amylose, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate dextran sulfate, dermatan sulfate, keratan sulfate, pectin, xanthan gum, carboxymethylcellulose, acrylamide alone and copolymers, polyacrylic acid, polyethylene oxide , Polyvinyl alcohol, polyvinyl alcohol-polyvinylacetate copolymer, poly (N-vinylpyrrolidone), polyhydroxyethyl acrylate, polysulfone, and polyurethane Polymer gel comprising a metal extract, characterized in that more than one. Adsorbing a valuable metal to a valuable metal containing solution by adding a polymer gel containing a metal extracting agent prepared according to any one of claims 1 to 11; And
And recovering the valuable metal by adding the polymer gel adsorbed on the valuable metal to the desorption solution.

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