KR20130070907A - Hydrogel having reducing agents and method for preparing the same - Google Patents

Abstract

PURPOSE: A manufacturing method of hydrogel is provided to be able to simplify the process compared to the conventional hydrometallurgy method as solid-liquid separation is possible in recovery of valuable metals, and to be able to operate the process in an environment-friendly manner as the secondary sludgy is not generated. CONSTITUTION: A manufacturing method of hydrogel comprises a step of injecting a polymer solution to a mixture solution of metal reduction material and a coagulating agent. The injection step comprises a step of containing the metal reduction material in the inside or on the surface while the dissolved polymer is coagulated. The concentration of the polymer solution is 0.01-50% (w/w). The concentration of the metal reduction material is 0.01-25% (w/v) to the polymer solution. The concentration of the coagulating agent is 0.01-20% (w/v). The coagulating agent is sodium polyphosphate, calcium chloride, ethanol, water or sodium hydroxide solution. [Reference numerals] (AA) 096 GA hydro-gel; (BB) 396 GA containing hydro-gel

Description

Hydrogel containing reducing substances and method for preparing the same {Hydrogel having reducing agents and method for preparing the same}

The present invention relates to a hydrogel containing a reducing material and a method for producing the same, and more particularly, to a hydrogel containing a reducing material on the surface or the inside thereof, and to a recovery of valuable metals and improved selectivity to a specific metal. It is about.

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. Although industrial wastewater and waste electronic products are the main contributors to the environment, they also contain valuable metals such as gold, silver, and copper, and thus 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, 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 find fundamental solutions such as the use of alternative materials or waste resources to cope with 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, when using a metal extractant has a problem that requires a large-scale continuous process and generates secondary pollutants. Researches to recover valuable metals using environmentally friendly materials to solve this problem are being actively conducted, and a representative method is to use hydrogels such as alginate, chitosan and cellulose. However, 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.

The present invention is to provide a hydrogel with improved recovery capacity of valuable metals.

The present invention provides a hydrogel capable of selectively recovering a specific metal and a recovery method using the same.

One aspect of the present invention relates to a method for producing a hydrogel comprising injecting a polymer solution into a mixed solution of a metal reducing material and a coagulant.

Hydrogel containing a metal reducing material according to the present invention includes a reducing material and a high viscosity material as needed.

In another aspect, the present invention comprises the steps of preparing a biocompatible polymer having a molecular weight of 10,000 to 1,000,000, mixed solution of a metal solution having a polyvalent cation of 0.1 to 10 wt% in a solvent with a metal reducing material and a mixed solution of the metal reducing material; And injecting beads of the mixed solution dropwise into the polymer coagulant solution, wherein the injecting step is cationic polymer that was present inside by the electrostatic attraction as the polymer coagulant diffuses into the mixed solution beads. The chain is moved and solidified to the surface of the beads to form a shell of the bubble and the metal reducing material is related to a method for producing a hydrogel comprising the step of supporting the inside of the bubble.

In another aspect, the present invention comprises the steps of adsorbing the valuable metal by adding a hydrogel prepared according to the production method to a solution containing a variety of valuable metals; A desorption step of separating the valuable metal in an ion state from the hydrogel by putting the hydrogel on which the valuable metal is adsorbed into a valuable metal separation solution; And a dissolution step of separating the valuable metal in the reduced state by putting the hydrogel in a dissolving solution.

Hydrogel according to the present invention can improve the metal recovery performance by containing a metal reducing material, it is also possible to selectively recover a specific valuable metal.

In addition, the method according to the present invention can simplify the process compared to the conventional wet smelting method because the solid-liquid separation in the valuable metal recovery, it can be more environmentally friendly to operate the process because no secondary sludge occurs. Further, since valuable metals can be selectively recovered using the characteristics of metal reducing materials, it is possible to efficiently separate and recover valuable metals that are difficult to separate in an aqueous system.

1 is an electron micrograph of Example 1 and Comparative Example 1.
2 is a graph showing the metal (gold, palladium) recovery performance of Example 1 and Comparative Example 1.
Figure 3 is a graph measuring the metal concentration of the primary and secondary desorption solution using inductively coupled plasma (ICP).

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

One embodiment of the present invention relates to a method for preparing a hydrogel by injecting a polymer solution into a mixed solution of a metal reducing material and a coagulant.

The injection step includes the step of containing the metal reducing material inside or on the surface of the hydrogel while the dissolved polymer solidifies.

The hydrogel prepared by the present invention contains a metal reducing material inside or on the surface thereof, where the expression "containing" means that the metal reducing material is supported or contained inside the hydrogel, and also on the surface of the hydrogel. It may represent that the metal reducing material is coated by being precipitated or adsorbed. Furthermore, the expression "containing" does not exclude that the metal reducing material forms the outer layer (shell) of the hydrogel together with the polymer or is supported in the outer layer.

In the present invention, a polymer solution is injected into a mixed solution of a metal reducing material and a coagulant.

The polymer is chitosan, alginate, alginate, alginic acid, dextran, oxidized dextran, heparan, heparin, healin, hyaluronic acid, agarose, agarose, Carageenan, amylopectin, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate, Dermatan sulfate, keratan sulfate, pectins, xanthan gum can be used.

The solvent is water, alcohol, ether, ketone, ionic liquid, N, N-dimethylacrylamide Methyl acylate, methyl acrylate, methacrylonitrile ), Methyl methacrylate, styrene, vinyl acetate, vinyl chloride, 4-vinylpyridine, 4-vinylpyridine, n-vinylpyrrolidone ), Dimethylformamide, dimethylsulfoxide, diphenylamine, ethylene carbonate, iron (III) chloride, magnesium perchlorate, sulfur dioxide (Sulfur dioxide), Triethylamine, Trimethylamine, Tripropylamine, Zinc chloride, Acrylamide and Acrylonitrile 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 metal reducing material reduces the valuable metal ions present in the solution mainly in anionic complex form to the zero-valent metal. The metal-reducing substance is at least one selected from natural antioxidants such as tocopherols, flavone derivatives, phyllozurcins, gallic acid derivatives, catechin, nordihydroguaiaretic acid, gossypol, lignan glycosides, plant extracts and metal-reducing substances. Glutaraldehyde, Sodium borohydride (NaBH ₄ ), Hydrazine (N ₂ H ₄ ), Borohydride, Dimethylamine borane [(CH ₃ ) ₂ NH.HBH ₃ ], Formaldehyde [CH ₂ O], Sodium dithionite [Na ₂ S ₂ O ₄ ] , Ascorbic acid [C ₆ H ₈ O ₆ ], Ethylene glycol, Sodium alkoxide, Hydroquinone (C ₆ H ₆ O ₂ ), Sodium oxalate (Na ₂ C ₂ H ₂ O ₄ ), Formic acid, Dimethylamine borane, Dithiothreitol, Tris (2-carboxyethyl) phosphine and the like.

In the present invention, the coagulant may vary depending on the polymer, and the coagulant may be sodium polyphosphate, calcium chloride, ethanol, water, caustic soda solution.

The concentration of the polymer solution is 0.01 to 50% (w / v), and in contrast to the polymer solution, 0.01-25% (w / v) of the metal reducing material and 0.01 to 20% (w / v) of the coagulant are used. Can be.

In the case of the polymer, it is possible to prepare a hydrogel such as beads or fibers through a solidification process after dissolution. In the present invention, the metal reducing material may be injected to solidify the dissolved polymer so that the metal reducing material may be simply coated or contained on the surface or the inside of the hydrogel.

The method may further include a highly viscous material as necessary in the mixed solution of the metal reducing material and the coagulant.

Highly viscous materials include Carboxymethyl Cellulose, Hydroxyethyl Cellulose, XanthanGum, Hycel, Carbomer, Gelatin, Pectin, Guar Guargum, Sodium Alginate, Calcium Glycerophosphate, Carrageenan, Tragacanth gum, Propylene Glycol Alginate, Methylethylcellulose ), Potassium alginate (Potassium Alginate) and carboxymethyl cellulose (Calcium Carboxymethylcellulose) may be one or more selected from the group consisting of.

When the metal reducing material is contained or contained in the hydrogel, the metal reducing material may be released to the outside of the hydrogel, so it may be difficult to achieve the expected effect. In the present invention, however, the metal reducing material and the highly viscous material are mixed to form an emulsion having a predetermined viscosity, so that the metal reducing material can be stably included in the hydrogel.

In more detail, the highly viscous material, the metal reducing material and the coagulant may be physically mixed into an emulsion state through a stirring process, and then the mixture of the emulsion state may be added to the polymer solution. In this case, the compatible polymer may be contained by externally coating the mixture of the metal reducing material and the high viscosity material by the coagulant, and the metal reducing material may be granulated by the high viscosity material and exist inside the hydrogel. have.

The high viscosity material may be added 0.01 to 50 parts by weight, preferably 1 to 20 parts by weight based on 100 parts by weight of the metal reducing material. If it is less than 0.01 part by weight, it is difficult to block the granulation of the metal reducing material and eluting to the outside of the hydrogel, and when it exceeds 50 parts by weight, it is difficult to spin the solution when preparing the material due to excessive viscosity.

The high viscosity material may have a viscosity of 2 to 10000 mPa · s, preferably 10 to 5000 mPa · s. When the viscosity is less than 2 mPa · s, the viscosity is small, and the metal reducing agent may not be effectively granulated. When the viscosity is 10000 mPa · s or more, the spinning of the mixed solution becomes difficult.

In another aspect, the present invention comprises the steps of preparing a polymer solution having a molecular weight of 10,000 to 1,000,000, a metal reducing material in a solvent and a mixed solution of a polymer solution and a metal reducing material having a polyvalent cation of 0.1 to 10 wt%; And it relates to a method for producing a hydrogel comprising the step of injecting a drop of the mixed solution to the coagulant solution dropwise.

In the injecting step, as the coagulant is diffused into the mixed solution beads, cationic polymer chains existing therein are moved and solidified to the surface of the beads by electrostatic attraction to form a shell of bubbles, and the metal reducing material is bubbled. It includes the steps carried therein.

The polymer is chitosan having a degree of deacetylation of 90% or more, prepared by deacetylation of chitin, and preferably 95% or more. When the degree of deacetylation of chitosan is less than 90%, it is in the form of a full bead and does not have a space for supporting a metal reducing material therein.

Chitosan that can be used in the present invention may have a molecular weight of 10,000 ~ 1,000,000 range, preferably 30,000 or more and 500,000 or less, more preferably 50,000 or more and 250,000 or less Can be used.

The polymer solution of the present invention may prepare a polymer solution having a polyvalent cation having a molecular weight of 10,000 to 1,000,000 in the solvent to more than 0.1 seconds and less than 10 wt%, preferably more than 2 seconds and less than 10 wt%. A metal solution may be put in the polymer solution to prepare a mixed solution.

In the present invention, the shape of the hydrogel bubble varies according to the molecular weight of the polymer used and the weight (wt)% after mixing in the solvent, and the presence or absence of the formation of the bubble may be determined.

For example, when the molecular weight of chitosan is 50,000, hollow bubbles may be formed when the chitosan solution is in a range of 6 wt% or more and less than 10 wt%. That is, in the case of 6wt%, although bubbles are formed, the thickness of the shell (shell) is not constant, and the inside may be in a mesh form. In addition, the 10 wt% chitosan solution has a high viscosity and cannot be added to the gelling solution, making it difficult to form chitosan bubbles.

In addition, when the molecular weight of the chitosan is 250,000, hollow bubbles may be formed when the chitosan solution is more than 2wt% and less than 6wt%. That is, when less than 2wt%, bubbles may not be formed or beads may be recessed without being formed into circular bubbles. In addition, the 6 wt% chitosan solution does not form hollow bubbles.

In the present invention, by controlling the molecular weight of the polymer and wt% of the polymer solution, it is possible to control the shape of the hydrogel bubble or whether the bubble exists. That is, it is preferable that the wt% of the chitosan solution is lowered as the molecular weight of the chitosan increases.

More specifically, when the molecular weight of chitosan is 50,000, a chitosan solution in a range of 6 wt% or more and less than 10 wt% is preferable, and when chitosan has a molecular weight of 250,000, a chitosan solution in a range of more than 2 wt% and less than 6 wt% is preferable. When the amount is increased from 50,000 to 250,000, it is preferable to gradually reduce the wt% of the chitosan solution from 6-10 wt% to 2-6 wt%.

The present invention includes the step of dropping the beads of the mixed solution to the coagulant solution and injecting.

The coagulant may include sodium polyphosphate, polyacrylic acid, polyimide, and the like, preferably sodium polyphosphate.

The injection step is a step in which the polymer solution of the polyvalent cation and the coagulant existing as the polyvalent anion form a hollow spherical bubble with electrostatic attraction and at the same time a metal reducing material is contained in the bubble.

In the hydrogel manufacturing method, the above-described contents may be referred to for the metal reducing material.

In another aspect, the present invention relates to a method for the selective recovery of valuable metals. The selective recovery method of the valuable metal of the present invention includes an adsorption step and a recovery step, and the recovery step may include desorbing the adsorbed metal ions and dissolving the reduced metal.

The adsorption step is a step of adsorbing the valuable metal by adding a hydrogel containing a metal reducing material in accordance with the production method in a solution containing a variety of valuable metals.

The valuable metal-containing solution mainly catalyzes the valuable metal in a chemical process

For example, industrial waste liquid generated in the industry and the electrical and electronics industry.

The desorption step is a step in which the hydrogel to which the valuable metal is adsorbed is placed in the valuable metal separation solution to separate the valuable metal in the ion state from the hydrogel, and the separation solution may be an electrolyte solution causing an ion exchange reaction.

The dissolving step is a step of separating and then reducing the valuable metal present on the surface of the hydrogel into a solution by reacting for a predetermined time. The dissolving solution is a solution capable of dissolving valuable metals. For example, as a separation solution, thiourea, aqua regia, and sodium cyanide (NaCN) may be used.

Valuable metal recovery method according to the present invention can selectively recover a specific valuable metal. In addition, the method according to the present invention can be separated by solid-liquid separation in valuable metal recovery, it can 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.

Example  One

9 g chitosan was added to 5% (w / w) acetic acid to prepare a 9 wt% chitosan solution. Subsequently, 485 ml of 1 wt% sodium polyphosphate (TPP) and 15 ml Glutaraldehyde (GA: glutaraldehyde) were mixed to prepare a mixed solution. The pH of the spinning solution was adjusted using 1M NaOH while spinning the chitosan solution into the mixed solution. Subsequently, ₁₅ ml of 1 M H ₂ SO _{4 was} added, followed by stirring for 1 hour to obtain a hydrogel containing 3% GA, which was washed with distilled water.

Example  2

100 mL (emulsion) of the mixed solution was prepared by adding 1.5% (w / v) calcium chloride, 1.5% (w / v) carboxymethyl cellulose (CMC) and 0.1 M Gallic acid. The emulsion mixture was spun into 0.6% (w / v) alginate solution dissolved in water and stirred at room temperature for 5 minutes. Then, the gelled alginate gel was washed several times with deionized water, and then poured into 500 mL of 2% (w / v) calcium chloride and stirred at room temperature for 30 minutes. After the reaction was completed several times with deionized water to remove the remaining coagulant to prepare a hydrogel.

Comparative example  One

9 g chitosan was added to 5% (w / w) acetic acid to prepare a 9 wt% chitosan solution. Subsequently, 1 M NaOH was used to adjust the pH of the spinning solution while spinning in 500 ml of 1 wt% sodium polyphosphate (TPP). Subsequently, ₁₅ ml of 1 M H ₂ SO _{4 was} added, followed by stirring for 1 hour to obtain a 0% GA-containing hydrogel, which was washed with distilled water.

1 is an electron micrograph of Example 1 and Comparative Example 1. Referring to Figure 1, Example 1 containing GA and Comparative Example 1 does not contain GA is significantly different in color, Example 1 was also high in strength.

Test Example  One : Adsorption performance test

Initial metal concentration: 500ppm Au + 500ppm Pd solution (0.1M HCl)

Concentration of adsorbent: 1 ~ 10g / L (0.03 ~ 3g sorbent / 30ml metal solution)

Adsorption time 48h.

2 is a graph showing the metal (gold, palladium) recovery performance of Example 1 and Comparative Example 1. The adsorption amount q represents the amount of valuable metal adsorbed by the adsorption material.

Referring to FIG. 2, the adsorption amount of Example 1 is significantly higher than that of Comparative Example 1, and in particular, gold exhibits 10 times or more adsorption performance.

Test Example  2: metal selectivity test

Initial Metal Concentration: 500ppm Au + 500ppm Pd solution (0.1M HCl)

Experimental condition: adsorbent / solution = 3g / L (0.09g sorbent / 30ml metal solution)

48h

Figure 3 shows the metal selectivity of the hydrogel according to the GA content in the conditions of Test Example 2 shown in Table 1.

(Table 1)

여기서 M_Ⅰ는 Au, M_Ⅱ는 Pd임.

Where M _I is Au and M _II is Pd.

Referring to Table 1, it can be seen that the selectivity to Au is improved as the GA-containing concentration of the hydrogel increases. That is, these results indicate that the metal can be selectively recovered as the metal reducing material is contained in the hydrogel.

Example  3

Adsorption experiment for 48 hours was performed using the 3% GA-containing hydrogel obtained in Example 1 (the conditions of Test Example 2), and the 3% GA-containing hydrogel was separated from the mixed solution using a pole. The separated 3% GA-containing hydrogel was washed with distilled water.

Subsequently, the hydrogel containing 3% GA was added to 30 mL of an acid solution (1M / 5M HCl, 1M / 5M H ₂ SO ₄ ), followed by stirring for 24 hours to perform a desorption experiment. A hydrogel containing 3% GA was separated from the desorption solution using a pole.

Subsequently, the separated 3% GA-containing hydrogel was washed with distilled water, and then placed in 30 mL of 0.5M thiourea (1M HCl solution) solution and reacted for 24 hours. The 3% GA containing hydrogel was isolate | separated from the dissolution liquid after reaction using a pole.

The metal concentrations of the desorption solution and the dissolution solution were shown in FIG. 3 by using ICP.

Referring to FIG. 3, it can be seen that the amount of metal recovered in the desorption process and the amount of metal recovered in the dissolution process are significantly different. That is, when the hydrogel containing the metal reducing material according to the present invention is used, it can be seen that the metal adsorbed in the reduction and the metal adsorbed in the ionic form can be effectively separated and recovered.

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 (14)

Method of producing a hydrogel comprising the step of injecting a polymer solution into a mixed solution of a metal reducing material and a coagulant. The method of claim 1, wherein the injecting step comprises the step of containing the metal reducing material inside or on the surface while the dissolved polymer is solidified. The method of claim 1, wherein the method further comprises a highly viscous material in the mixed solution, wherein the polymer contains the mixture of the metal reducing material and the highly viscous material from the outside by the coagulant, wherein the metal The reducing material is a method for producing a hydrogel, characterized in that granulated by the high viscosity material. According to claim 1, wherein the concentration of the polymer solution is 0.01 to 50% (w / v), the metal reducing material is 0.01 to 25% (w / v) and the coagulant is 0.01 to 20 compared to the polymer solution Method for producing a hydrogel, characterized in that% (w / v). According to claim 1, The metal reducing material is a natural antioxidant tocopherols, flavone derivatives, phyllozurcin, gallic acid derivatives, catechin, nordihydroguaiaretic acid, gossypol, lignan glycosides, plant extracts and polymers with metal reducing power, glutaraldehyde ( Glutaraldehyde), Sodium borohydride (NaBH ₄ ), Hydrazine (N ₂ H ₄ ), Borohydride, Dimethylamine borane [(CH ₃ ) ₂ NH.HBH ₃ ], Formaldehyde [CH ₂ O], Sodium dithionite [Na ₂ S ₂ O ₄ ], Ascorbic acid [C ₆ H ₈ O ₆ ], Ethylene glycol, Sodium alkoxide, Hydroquinone (C ₆ H ₆ O ₂ ), Sodium oxalate (Na ₂ C ₂ H ₂ O ₄ ), Formic acid, Dimethylamine borane, Dithiothreitol, And Tris (2-carboxyethyl) phosphine. The method of claim 1, wherein the polymer is selected from the group consisting of chitosan, alginate, dextran, oxidized dextran, heparan, heparin, hyaluronic acid, but are not limited to, agarose, carageenan, amylopectin, amylose, glycogen, starch, cellulose, chitin, heparan sulfate, chondroitin sulfate, dextran sulfate dextran sulfate, dermatan sulfate, keratan sulfate, pectins, xanthan gum, carboxymethylcellulose, acrylamide alone and copolymers, polyacrylic acid, polyethylene oxide, Selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol-polyvinylacetate copolymer, poly (N-vinylpyrrolidone), polyhydroxyethyl acrylate, polysulfone, and polyurethane Hydrogel method as not less than one. The method of claim 1, wherein the coagulant is sodium polyphosphate, calcium chloride, ethanol, water or caustic soda solution. The method of claim 3, wherein the highly viscous material is carboxymethyl cellulose (Carboxymethyl Cellulose), hydroxyethyl cellulose (Hydroxyethyl Cellulose), Xanthan Gum (Hycel), Carbomer (carbomer), gelatin (gelatin) ), Pectin, Guargum, Sodium Alginate, Calcium Glycerophosphate, Carrageenan, Tragacanth gum, Propylene Glycol Alginate), methyl ethyl cellulose (Methylethylcellulose), potassium alginate (Potassium Alginate) and carboxymethyl cellulose calcium (Calcium Carboxymethylcellulose) method for producing a hydrogel, characterized in that at least one selected from the group consisting of. 4. The method of claim 3, wherein the high viscosity material is 0.01 to 50 parts by weight based on 100 parts by weight of the metal reducing material. The method of claim 3, wherein the high viscosity material has a viscosity of 2 to 10000 mPa s. Preparing a mixed solution of a polymer solution having a molecular weight of 10,000 to 1,000,000 and a polymer reducing material having a polyvalent cation of 0.1 to 10 wt% in a solvent; And injecting beads of the mixed solution dropwise to the polymer coagulant solution,
In the injecting step, as the polymer coagulant is diffused into the mixed solution beads, cationic polymer chains existing therein are moved and solidified on the surface of the beads by electrostatic attraction to form a shell of bubbles, and the metal reducing material is Method for producing a hydrogel, characterized in that it comprises the step of supporting in the bubble. [Claim 12] The hydrogel of claim 11, wherein the biocompatible polymer is prepared by deacetylating chitin, and has a deacetylation degree of 90% or more, and the polymer coagulant is a sodium polyphosphate solution. Manufacturing method. The method of claim 12, wherein the chitosan molecular weight is increased from 50,000 to 250,000, the method for producing a hydrogel, characterized in that the wt% of the chitosan solution is gradually adjusted from 6 to 10wt% to 2 to 6wt%. Adsorbing a valuable metal by adding a hydrogel prepared according to any one of claims 1 to 12 to a solution containing various kinds of valuable metals;
A desorption step of separating the valuable metal in an ion state from the hydrogel by putting the hydrogel on which the valuable metal is adsorbed into a valuable metal separation solution; And
And a dissolving step of separating the valuable metal in a reduced state by putting the hydrogel in a dissolving solution.

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