WO2014129763A1 - Procédé de fabrication de capsule et capsule pour absorbant obtenue à partir dudit procédé - Google Patents

Procédé de fabrication de capsule et capsule pour absorbant obtenue à partir dudit procédé Download PDF

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Publication number
WO2014129763A1
WO2014129763A1 PCT/KR2014/001070 KR2014001070W WO2014129763A1 WO 2014129763 A1 WO2014129763 A1 WO 2014129763A1 KR 2014001070 W KR2014001070 W KR 2014001070W WO 2014129763 A1 WO2014129763 A1 WO 2014129763A1
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WO
WIPO (PCT)
Prior art keywords
capsule
acid
present
solution
sodium
Prior art date
Application number
PCT/KR2014/001070
Other languages
English (en)
Korean (ko)
Inventor
윤영상
원성욱
프라탑코테
Original Assignee
전북대학교산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 전북대학교산학협력단 filed Critical 전북대학교산학협력단
Publication of WO2014129763A1 publication Critical patent/WO2014129763A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/206—Hardening; drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • an uncoagulant eg, chloride
  • the polymers in the solution are cured from the outside to the inside to prepare the beads.
  • 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.
  • 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.
  • One aspect of the present invention comprises the steps of mixing a functional material and a quaternary agent
  • 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.
  • the present invention relates to a cap for adsorbent prepared by the above method.
  • 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.
  • 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.
  • FIG. 1 is a schematic view showing a conventional bead manufacturing method.
  • FIG. 2 shows a schematic view of a capsule for an adsorbent according to the present invention.
  • FIG. 3 is a schematic diagram of an apparatus for making a capsule of the present invention.
  • FIG. 4 illustrates a process of forming a capsule in the capsule former 130.
  • 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.
  • Example 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.
  • 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.
  • a functional substance and an ointment are mixed, and then dropped into a polymer solution to prepare 3 ⁇ 4 slots.
  • the mixed solution is preferably added dropwise to the polymer solution in the form of beads.
  • 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.
  • 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.
  • 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.
  • the manufacturing apparatus of the present invention includes a mixer 110, an injector 120, and a capsule former 130.
  • 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.
  • 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.
  • FIG. 4 illustrates a capsule formation process in the capsule former 130.
  • 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.
  • uncoagulant such as Ca 2+
  • 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.
  • 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.
  • 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 ( ⁇ 2 ⁇ 4 ),
  • Hydroquinone ((3 ⁇ 40 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 ⁇ hydroxyl— 5 ⁇ 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,
  • the chelating agent examples 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 ⁇ phenoxy) ethane-N, ⁇ , ⁇ ' ⁇ '-tetraacetic acid (EGTA), ethylenebis (Oxyethylenenitrilo) tetraacetic acid ( ⁇ ), ⁇ - (hydroxyethyl) -ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), ⁇ -dihydroxyethylglycine (2- HxG), ethylenebis (hydroxyphenyl-glycine) (EHPG), glutamic acid, aspartic acid, glycine, lysine); 1,3—dike
  • nitrilotrimethylenephosphonic acid ethylenediaminetetra- (methylenephosphonic acid), hydroxy to Thylidenediphosphonic acid), melamine L-cystein, Phosphatidylcholone, and alamin.
  • 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.
  • 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 ⁇ 403 ⁇ 4> (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.
  • a capsule may be formed in the form of coating the complex beads from the outside.
  • 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 Carboxymethylcelluloseose calcium (Calcium Carboxymethylcel lulose)
  • Capsule for the adsorbent of the present invention is a functional material melamine, L-cystein, Phosphatidylcholone, dibutyl sulfoxide, LIX
  • 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.
  • 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.
  • the adsorbed metal floats to the top of the desorption process.
  • the valuable metal recovery method according to the present invention a specific valuable metal can be selectively recovered.
  • 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.
  • the capsule obtained above was added to 100 mL of 2% CaC12 solution and stirred for about 30 minutes. After reaction was completed, the 3 ⁇ 4 capsule was washed several times with deionized water.
  • a capsule was prepared in the same manner as in Example 1 except for adding 4 g of L-Cistein instead of melamine.
  • Capsules were prepared in the same manner as in Example 1 except for adding 4 g of Phosphatidylcholone instead of melamine.
  • 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.
  • FIG. 6 shows that the functional material is mixed with the high viscosity material and granulated in an emulsion state.
  • FIG. 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une capsule, qui permet d'améliorer la sélectivité liée à des métaux spécifiques et le rendement de la récupération en métal précieux grâce à l'inclusion de substances fonctionnelles sur sa surface ou à l'intérieur. L'invention porte en outre sur une capsule pour absorbant obtenue par ledit procédé. Ladite capsule pour absorbant est apte à inclure des substances fonctionnelles requises à l'intérieur, contrairement aux perles classiques, et apte à conserver sa forme tout en stockant lesdites substances pendant une longue période. Selon la présente invention, l'utilisation d'une capsule à poids moléculaire élevé dans laquelle des substances fonctionnelles telles qu'un agent d'extraction de métal sont granulées permet d'améliorer le rendement de la récupération en métal et de récupérer des métaux spécifiques de manière sélective. Le procédé de la présente invention permet une séparation solide/liquide pour la récupération de métal précieux, et le procédé peut ainsi être simplifié par rapport à un mode hydrométallurgique classique. Étant donné qu'il n'y a pas de production secondaire de boues, ce procédé peut être réalisé d'une manière respectueuse de l'environnement.
PCT/KR2014/001070 2013-02-19 2014-02-07 Procédé de fabrication de capsule et capsule pour absorbant obtenue à partir dudit procédé WO2014129763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130017272A KR101513792B1 (ko) 2013-02-19 2013-02-19 캡슐 제조방법 및 이에 의한 흡착제용 캡슐
KR10-2013-0017272 2013-02-19

Publications (1)

Publication Number Publication Date
WO2014129763A1 true WO2014129763A1 (fr) 2014-08-28

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Publication number Priority date Publication date Assignee Title
KR102415047B1 (ko) * 2015-03-18 2022-06-30 전북대학교산학협력단 키토산 기반의 코어-쉘 흡착제 및 이의 제조방법
KR102580230B1 (ko) * 2018-04-27 2023-09-19 전북대학교산학협력단 양이온 장벽 흡착제 및 이의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10510008A (ja) * 1994-11-30 1998-09-29 アライドシグナル・インコーポレーテッド 金属を回収するための溶媒含浸架橋マトリックスの使用
JP2003113427A (ja) * 2001-10-09 2003-04-18 Takashi Kobayashi マイクロカプセル型金属抽出剤
JP2007503293A (ja) * 2003-08-22 2007-02-22 ダニスコ エイ／エス マイクロカプセル
JP2011189264A (ja) * 2010-03-15 2011-09-29 Mitsubishi Paper Mills Ltd 金属抽出剤内包磁性カプセル及び水処理方法
KR20130055168A (ko) * 2011-11-18 2013-05-28 전북대학교산학협력단 금속 추출제를 포함하는 고분자겔, 그 제조방법 및 이를 이용한 유가금속의 회수방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10510008A (ja) * 1994-11-30 1998-09-29 アライドシグナル・インコーポレーテッド 金属を回収するための溶媒含浸架橋マトリックスの使用
JP2003113427A (ja) * 2001-10-09 2003-04-18 Takashi Kobayashi マイクロカプセル型金属抽出剤
JP2007503293A (ja) * 2003-08-22 2007-02-22 ダニスコ エイ／エス マイクロカプセル
JP2011189264A (ja) * 2010-03-15 2011-09-29 Mitsubishi Paper Mills Ltd 金属抽出剤内包磁性カプセル及び水処理方法
KR20130055168A (ko) * 2011-11-18 2013-05-28 전북대학교산학협력단 금속 추출제를 포함하는 고분자겔, 그 제조방법 및 이를 이용한 유가금속의 회수방법

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KR101513792B1 (ko) 2015-04-21

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