KR102651225B1 - regeneration method of waste ytterbium oxide using precipitation and reduction - Google Patents
regeneration method of waste ytterbium oxide using precipitation and reduction Download PDFInfo
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- KR102651225B1 KR102651225B1 KR1020230132696A KR20230132696A KR102651225B1 KR 102651225 B1 KR102651225 B1 KR 102651225B1 KR 1020230132696 A KR1020230132696 A KR 1020230132696A KR 20230132696 A KR20230132696 A KR 20230132696A KR 102651225 B1 KR102651225 B1 KR 102651225B1
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- ytterbium
- precipitate
- oxide
- recovering
- ytterbium oxide
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- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940075624 ytterbium oxide Drugs 0.000 title claims abstract description 35
- 229910003454 ytterbium oxide Inorganic materials 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 238000001556 precipitation Methods 0.000 title abstract description 6
- 238000011069 regeneration method Methods 0.000 title description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- SJHMKWQYVBZNLZ-UHFFFAOYSA-K ytterbium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Yb+3] SJHMKWQYVBZNLZ-UHFFFAOYSA-K 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
- 150000003747 ytterbium compounds Chemical class 0.000 description 1
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 description 1
- NVEKVESLPDZKSN-UHFFFAOYSA-N ytterbium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Yb+3].[Yb+3] NVEKVESLPDZKSN-UHFFFAOYSA-N 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
Abstract
본 발명은 폐 산화이터븀을 산 용해, 침전 및 환원과정을 거쳐 비교적 쉽게 재생시켜 고순도의 이터븀으로 재생할 수 있는 방법에 관한 것이다. 산화이터븀을 산에 용해시킨 후 침전제를 사용하여 침전물을 형성시킨 다음 이를 다시 환원시켜 정제된 이터븀을 제조하는 방법은 특별한 장비가 필요하지 않고 안전한 방법이며 종래의 기술들에 비해 용이하게 진행할 수 있다.
본 발명을 통해 OLED 제작공정에서 버려지는 희토류 금속인 산화이터븀을 재생시켜 이터븀으로 재사용할 수 있다.The present invention relates to a method by which waste ytterbium oxide can be relatively easily regenerated into high-purity ytterbium through acid dissolution, precipitation, and reduction processes. The method of dissolving ytterbium oxide in acid, forming a precipitate using a precipitant, and then reducing it again to produce purified ytterbium is a safe method that does not require special equipment and can be carried out more easily than conventional techniques. there is.
Through the present invention, ytterbium oxide, a rare earth metal discarded in the OLED manufacturing process, can be recycled and reused as ytterbium.
Description
본 발명은 폐 산화이터븀을 정제하고 재생하는 방법에 관한 것으로, 보다 상세하게는 폐 산화이터븀을 산성 수용액에 용해시킨 후 침전 및 환원반응을 이용해 고순도 이터븀으로 정제하고 재생하는 방법에 관한 것이다.The present invention relates to a method of purifying and regenerating waste ytterbium oxide, and more specifically, to a method of dissolving waste ytterbium oxide in an acidic aqueous solution and then purifying and regenerating it into high-purity ytterbium using precipitation and reduction reactions. .
이터븀(Yb)은 복합산화물 형태로 지각에 함유되어 있는 희토류 금속 중 하나로서 현재 중국에서 주로 채굴되고 매장량은 대략 1백만톤으로 추정되고 있다.Ytterbium (Yb) is one of the rare earth metals contained in the earth's crust in the form of a complex oxide. It is currently mainly mined in China, and its reserves are estimated to be approximately 1 million tons.
이터븀의 특징은 증기압이 높아 정제가 쉬운 물질은 아니며, 불순물로서 휘발성 원소 등이 다량 함유되어 있기 때문에 일반의 금속 정련과 같이 진공 중에서 정제하는 공정은 채택할 수 없어 다루기가 용이한 광물은 아니다.The characteristic of ytterbium is that it has a high vapor pressure, so it is not an easy material to purify. Since it contains a large amount of volatile elements as impurities, it cannot be purified in a vacuum like general metal refining, so it is not an easy mineral to handle.
이터븀은 20세기 후반까지만 해도 사실상 상업적 용도가 없는 희토류 원소로 여겨졌으나, 최근에는 강철합금 첨가제, 레이저 등에 첨가되어 사용되고 있으며, 이터븀 화합물들이 특수 유리와 도자기 유약의 채색제, 유기반응의 촉매로 활용방향을 넓히고 있다.Ytterbium was considered a rare earth element with virtually no commercial use until the late 20th century, but recently it has been used as an additive to steel alloys and lasers, and ytterbium compounds have been used as colorants for special glass and ceramic glazes and as catalysts for organic reactions. The direction of use is expanding.
그외 OLED 내의 전자주입층(EIL; Electron Injection Layer)에 사용되고 있고, 그 사용량이 점차 증가하고 있어 이에 따라 중국으로부터 수입량도 늘고 있는 추세이다.In addition, it is used in the electron injection layer (EIL) in OLED, and its usage is gradually increasing, leading to an increase in imports from China.
그런데 최근 미국과 중국 사이의 관계 악화로 인해 중국에서 채굴되는 희토류 금속에 대한 자원리스크가 부각되고 있어 국내외 디스플레이 회사에서는 사용하고 남은 산화이터븀의 재활용에 대한 연구개발을 활발히 진행하고 있다.However, due to the recent deterioration of relations between the United States and China, resource risks related to rare earth metals mined in China have been highlighted, and domestic and foreign display companies are actively conducting research and development on recycling leftover ytterbium oxide.
추가적으로 폐 산화이터븀을 폐기하는 대신 재사용하게 되면 ESG 경영 측면에도 부합할 수 있다는 장점이 있다.Additionally, reusing waste ytterbium oxide instead of disposing of it has the advantage of being compatible with ESG management aspects.
이러한 산화이터븀의 재생방법으로는 용매추출법이나 열처리 환원법이 알려져 있으나, 용매추출법의 경우에는 공정이 복잡하고 다량의 폐액발생 문제가 있고, 열처리 환원법의 경우에는 상대적으로 낮은 순도와 효율 문제로 인해 산업적으로 사용하기에는 어려움이 있다.Solvent extraction and heat reduction methods are known as methods for regenerating ytterbium oxide. However, in the case of the solvent extraction method, the process is complicated and there is a problem of generating a large amount of waste liquid, and in the case of the heat treatment reduction method, there are problems with relatively low purity and efficiency, making it difficult to use industrially. It is difficult to use.
따라서 기존의 폐 산화이터븀의 재생공정보다 간단하면서도 고순도의 이터븀으로 재생이 가능한 방법의 개발이 절실히 요구되고 있다.Therefore, there is an urgent need to develop a method that is simpler than the existing recycling process of waste ytterbium oxide and can regenerate high purity ytterbium.
따라서 본 발명이 해결하고자 하는 과제는 폐 산화이터븀으로부터 고순도의 이터븀을 재생하는 방법을 제공하고자 하며, 특히 침전-환원 반응의 상대적으로 단순하고 안전한 방식을 통해 종래의 기술보다 순도가 높은 이터븀을 생산하는 데 있다.Therefore, the problem to be solved by the present invention is to provide a method of regenerating high-purity ytterbium from waste ytterbium oxide, and in particular, to produce ytterbium with higher purity than conventional techniques through a relatively simple and safe method of precipitation-reduction reaction. is to produce.
상기 과제를 해결하기 위하여 본 발명은 하기와 같은 단계를 포함하는 폐 산화이터븀(Yb2O3)으로부터 이터븀(Yb)을 재생하는 방법을 제공한다. 1) 디스플레이 제작공정에서 사용된 폐 산화이터븀을 산성 수용액에 용해시키는 단계(S100), 2) 산화이터븀이 용해된 용액에 침전제를 공급하여 이터븀 침전물을 형성시키는 단계(S200), 3) 필터를 이용해 이터븀 침전물을 여과시키는 단계(S300), 4) 이터븀 침전물을 수산화나트륨 수용액에 용해시키는 단계(S400), 5) 이터븀 침전물이 용해된 용액에 환원제를 공급하여 이터븀을 환원시키는 단계(S500); 및 6) 환원된 이터븀을 회수하는 단계(S600).In order to solve the above problems, the present invention provides a method for recovering ytterbium (Yb) from spent ytterbium oxide (Yb 2 O 3 ) including the following steps. 1) Step of dissolving waste ytterbium oxide used in the display manufacturing process in an acidic aqueous solution (S100), 2) Step of supplying a precipitant to the solution in which ytterbium oxide is dissolved to form a ytterbium precipitate (S200), 3) Step of filtering the ytterbium precipitate using a filter (S300), 4) Dissolving the ytterbium precipitate in an aqueous solution of sodium hydroxide (S400), 5) Reducing ytterbium by supplying a reducing agent to the solution in which the ytterbium precipitate is dissolved. Step (S500); and 6) recovering the reduced ytterbium (S600).
본 발명의 일 실시예에 따르면, 상기 산성 수용액은 질산, 염산 또는 인산 중 어느 하나인 것을 특징으로 한다.According to one embodiment of the present invention, the acidic aqueous solution is characterized in that it is any one of nitric acid, hydrochloric acid, or phosphoric acid.
본 발명의 일 실시예에 따르면, 상기 산성 수용액의 농도는 5~20 vol%인 것을 특징으로 한다.According to one embodiment of the present invention, the concentration of the acidic aqueous solution is 5 to 20 vol%.
본 발명의 일 실시예에 따르면, 상기 침전제는 H2SO4, NaF, Na2S 중 어느 하나이며, 상기 침전제의 첨가량은 이터븀이 용해된 혼합액 100 중량부 대비 5~30 중량부인 것을 특징으로 한다.According to one embodiment of the present invention, the precipitant is any one of H 2 SO 4 , NaF, and Na 2 S, and the amount of the precipitant added is 5 to 30 parts by weight based on 100 parts by weight of the mixed solution in which ytterbium is dissolved. do.
본 발명의 일 실시예에 따르면, 상기 필터의 기공크기는 0.1~10 ㎛ 인 것을 특징으로 한다.According to one embodiment of the present invention, the pore size of the filter is 0.1 to 10 ㎛.
본 발명의 일 실시예에 따르면, 상기 수산화나트륨 수용액의 농도는 0.1~1.0 M 인 것을 특징으로 한다.According to one embodiment of the present invention, the concentration of the sodium hydroxide aqueous solution is 0.1 to 1.0 M.
본 발명의 일 실시예에 따르면, 상기 환원제는 아스코르브산, 하이드라진, 소듐 하이드로포스페이트, 글루코스, 탄닌산, 디메틸포름아미드, 테트라부틸암모늄 보로하이드라이드, 소듐보로하이드라이드로 이루어진 군에서 선택되는 1종 이상이며, 상기 환원제의 공급량은 이터븀 침전물의 당량과 동일하게 조절하는 것을 특징으로 한다.According to one embodiment of the present invention, the reducing agent is one or more selected from the group consisting of ascorbic acid, hydrazine, sodium hydrophosphate, glucose, tannic acid, dimethylformamide, tetrabutylammonium borohydride, and sodium borohydride. The supply amount of the reducing agent is characterized in that it is adjusted to be equal to the equivalent weight of the ytterbium precipitate.
본 발명에 의하면, 폐 산화이터븀으로부터 고순도의 이터븀을 효율적으로 생산해 낼 수 있게 된다. 또한 본 발명의 효과는 이상에서 언급된 것들에 한정되지 않으며, 언급되지 아니한 다른 효과들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.According to the present invention, it is possible to efficiently produce high purity ytterbium from waste ytterbium oxide. Additionally, the effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.
도 1은 본 발명의 일 실시예에 따라 폐 산화이터븀의 재생방법을 예시한다.1 illustrates a method for recycling spent ytterbium oxide according to an embodiment of the present invention.
본 발명에 관한 설명은 구조적 내지 기능적 설명을 위한 실시예에 불과하므로, 본 발명의 권리범위는 본문에 설명된 실시예에 의하여 제한되는 것으로 해석되어서는 아니 된다. 즉, 실시예는 다양한 변경이 가능하고 여러 가지 형태를 가질 수 있으므로 본 발명의 권리범위는 기술적 사상을 실현할 수 있는 균등물들을 포함하는 것으로 이해되어야 한다. Since the description of the present invention is only an example for structural or functional explanation, the scope of the present invention should not be construed as limited by the examples described in the text. In other words, since the embodiments can be modified in various ways and can have various forms, the scope of rights of the present invention should be understood to include equivalents that can realize the technical idea.
또한, 본 발명에서 제시된 목적 또는 효과는 특정 실시예가 이를 전부 포함하여야 한다거나 그러한 효과만을 포함하여야 한다는 의미는 아니므로, 본 발명의 권리범위는 이에 의하여 제한되는 것으로 이해되어서는 아니 될 것이다.In addition, the purpose or effect presented in the present invention does not mean that a specific embodiment must include all or only such effects, so the scope of the present invention should not be understood as limited thereby.
이하에서는 첨부된 도면을 참조하여 본 발명을 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail with reference to the attached drawings.
도 1은 본 발명의 일 실시예에 따라 폐 산화이터븀의 재생방법을 예시한다.1 illustrates a method for recycling spent ytterbium oxide according to an embodiment of the present invention.
도 1에 따르면, 본 발명의 첫번째 단계는 디스플레이 제작 공정에서 사용하고 남은 폐 산화이터븀(Ytterbium oxide, Yb2O3)을 준비한 다음 이를 산성 수용액에 용해시키는 단계(S100)이다.According to FIG. 1, the first step of the present invention is to prepare waste ytterbium oxide (Yb 2 O 3 ) remaining after use in the display manufacturing process and then dissolve it in an acidic aqueous solution (S100).
앞서 설명한 바와 같이 이터븀은 OLED의 전자주입층에 사용되며, 사용 후에는 산화이터븀으로 전환된다. 그런데 OLED 제작공정에서 투입된 이터븀은 약 30% 정도만 사용되고 나머지는 폐 산화이터븀의 형태로 버려지고 있다.As explained earlier, ytterbium is used in the electron injection layer of OLED, and after use, it is converted to ytterbium oxide. However, only about 30% of the ytterbium used in the OLED production process is used, and the rest is discarded in the form of waste ytterbium oxide.
상기 산성 수용액으로는 폐 산화이터븀을 용해시킬 수 있는 질산(HNO3), 염산(HCl), 인산(H3PO4) 수용액을 사용할 수 있으나, 이에 제한되지는 않는다. 다만 동일한 농도의 황산(H2SO4) 수용액을 사용하는 경우는 산화이터븀이 전부 용해되는 데 걸리는 시간이 오래 걸려 후속 공정 진행이 어렵다는 단점이 있다.The acidic aqueous solution may include, but is not limited to, nitric acid (HNO 3 ), hydrochloric acid (HCl), and phosphoric acid (H 3 PO 4 ) aqueous solutions that can dissolve waste ytterbium oxide. However, when using an aqueous solution of sulfuric acid (H 2 SO 4 ) of the same concentration, there is a disadvantage that it takes a long time for all the ytterbium oxide to dissolve, making subsequent processes difficult.
산성 수용액의 농도는 5~20 vol%가 사용될 수 있드며, 바람직하게는 5~10 vol%가 적당한다. 5 vol% 미만일 경우에는 폐 산화이터븀의 용해속도가 매우 느려 공정을 진행하는데 시간이 오래 소요된다.The concentration of the acidic aqueous solution can be 5 to 20 vol%, and is preferably 5 to 10 vol%. If it is less than 5 vol%, the dissolution rate of waste ytterbium oxide is very slow, so it takes a long time to proceed with the process.
한편, 20 vol%를 초과할 경우에는 폐 산화이터븀과 산성 수용액 사이의 반응이 격렬하게 진행되어 폭발 및 발화의 위험이 커지게 된다.On the other hand, if it exceeds 20 vol%, the reaction between the spent ytterbium oxide and the acidic aqueous solution proceeds violently, increasing the risk of explosion and ignition.
다음 단계는 산화이터븀이 전부 용해된 용액에 침전제를 첨가하여 이터븀 침전물을 형성시키는 단계(S200)이다.The next step is to form a ytterbium precipitate by adding a precipitant to the solution in which all the ytterbium oxide is dissolved (S200).
본 단계에 사용될 수 있는 침전제로는 황산(H2SO4), 불화나트륨(NaF), 황화나트륨(Na2S)중 어느 하나가 사용될 수 있으며 침전 반응을 통해 각각 이터븀 설페이트(Yb2(SO4)3), 이터븀 플루오라이드(YbF3), 이터븀 설파이드(YbS)의 침전물이 형성된다.As a precipitant that can be used in this step, any one of sulfuric acid (H 2 SO 4 ), sodium fluoride (NaF), and sodium sulfide (Na 2 S) can be used, and through precipitation reaction, ytterbium sulfate (Yb 2 (SO 4 ) 3 ), ytterbium fluoride (YbF 3 ), and ytterbium sulfide (YbS) precipitates are formed.
침전제는 이터븀이 용해된 용액 100 중량부를 기준으로 5~30 중량부를 첨가하는 것이 바람직하다. It is preferable to add 5 to 30 parts by weight of the precipitant based on 100 parts by weight of the solution in which ytterbium is dissolved.
첨가되는 침전제의 양이 5 중량부 미만일 경우에는 이터븀 침전물의 형성이 어렵다는 단점이 있다. 반대로 침전제의 양이 30 중량부를 초과할 경우에는 침전물을 만드는 데 사용되고 남은 침전제들이 불순물로 존재하여 이터븀 재생의 과정을 방해하고 순도가 낮아지는 문제가 있다.If the amount of precipitant added is less than 5 parts by weight, there is a disadvantage in that it is difficult to form a ytterbium precipitate. On the other hand, if the amount of the precipitant exceeds 30 parts by weight, the remaining precipitant used to make the precipitate exists as an impurity, which interferes with the ytterbium regeneration process and lowers the purity.
침전 반응이 완료된 후 다음 단계는 필터를 이용해 이터븀 침전물을 여과시키는 단계(S300)이다.After the precipitation reaction is completed, the next step is to filter the ytterbium precipitate using a filter (S300).
본 단계에서 사용하는 필터는 내산성을 갖는 폴리프로필렌(PP), PVDF(Polyvinylidene fluoride), PTFE(Polytetrafluoroethylene) 재질의 필터가 적합하며, 필터의 기공크기는 0.1~10㎛이 적당하다. The filter used in this step is suitable for acid-resistant polypropylene (PP), PVDF (Polyvinylidene fluoride), and PTFE (Polytetrafluoroethylene), and the pore size of the filter is 0.1 to 10㎛.
만약 0.1㎛ 미만의 기공크기를 갖는 필터는 작은 기공크기로 인해 필터가 쉽게 막혀서 필터의 잦은 교체 및 공정 중단 등의 문제를 갖는다.If a filter has a pore size of less than 0.1㎛, the filter is easily clogged due to the small pore size, causing problems such as frequent replacement of the filter and process interruption.
만약 10㎛보다 큰 기공크기를 갖는 필터를 사용하게 되면 이터븀 침전물과 환원된 이터븀 분말에 대한 여과력이 낮아 결과적으로는 재생 수율이 떨어지게 되는 문제가 있다.If a filter with a pore size larger than 10㎛ is used, there is a problem in that the filtration power for ytterbium precipitates and reduced ytterbium powder is low, resulting in a decrease in regeneration yield.
여과를 통해 걸러진 이터븀 침전물을 다음 단계의 용해를 위해 건조하거나 분쇄할 수 있다.The ytterbium precipitate filtered out can be dried or ground for dissolution in the next step.
다음 단계는 여과를 통해 수득된 이터븀 침전물을 수산화나트륨(NaOH) 수용액에 용해시키는 단계(S400)이다.The next step is dissolving the ytterbium precipitate obtained through filtration in an aqueous sodium hydroxide (NaOH) solution (S400).
이 단계에서 사용하는 수산화나트륨 수용액의 농도는 0.1~1.0M이 적당하다. 만약 0.1 M 미만의 농도를 갖는 수산화나트륨 수용액을 사용하게 되면 이터븀 침전물의 용해가 잘 이루어지지 않기 때문에 반응을 종료시키는 시간이 길어지게 된다. The appropriate concentration of the sodium hydroxide aqueous solution used in this step is 0.1~1.0M. If an aqueous solution of sodium hydroxide with a concentration of less than 0.1 M is used, the time to complete the reaction becomes longer because the ytterbium precipitate is not easily dissolved.
만약 1.0M 농도를 초과하는 수산화나트륨 수용액을 사용하게 되면 과량의 수산화나트륨이 불순물로 작용할 수 있다는 문제점이 있다.If an aqueous sodium hydroxide solution exceeding 1.0M concentration is used, there is a problem in that excess sodium hydroxide may act as an impurity.
이 단계를 거치게 되면 이터븀 침전물은 수산화나트륨 수용액 상에서 Ytterbium hydroxide(Yb(OH)3) 형태가 된다.After this step, the ytterbium precipitate becomes Ytterbium hydroxide (Yb(OH) 3 ) in an aqueous sodium hydroxide solution.
다음 단계는 Ytterbium hydroxide(Yb(OH)3)를 환원제를 공급하여 이터븀으로 환원시키는 단계(S500)이다.The next step is to reduce Ytterbium hydroxide (Yb(OH) 3 ) to ytterbium by supplying a reducing agent (S500).
앞서 만들어진 Ytterbium hydroxide(Yb(OH)3)를 환원시키기 위한 환원제로는 아스코르브산(ascorbic acid), 하이드라진(N2H4), 소듐 하이드로포스페이트, 글루코스, 탄닌산, 디메틸포름아미드, 테트라부틸암모늄 보로하이드라이드, 소듐보로하이드라이드(NaBH4) 중의 1종이 사용될 수 있으며, 바람직하게는 약환원제인 아스코르브산이 적당하다.Reducing agents for reducing Ytterbium hydroxide (Yb(OH) 3 ) prepared previously include ascorbic acid, hydrazine (N 2 H 4 ), sodium hydrophosphate, glucose, tannic acid, dimethylformamide, and tetrabutylammonium borohydride. One of sodium borohydride (NaBH 4 ) may be used, and ascorbic acid, a weak reducing agent, is preferred.
환원제의 양은 앞서 만들어졌던 이터븀 침전물(Yb2(SO4)3, YbF3, YbS)의 당량과 동일한 양이 공급되도록 조절하는 것이 바람직하다. 만약 이터븀 침전물의 당량보다 적은 양이 공급되면 순수한 이터븀의 재생 효율이 낮아지게 된다. 만약 이터븀 침전물의 당량보다 환원제가 과량으로 공급되면 반응하지 않은 미반응한 환원제가 존재하여 수율이 낮아지는 문제가 있다. It is desirable to adjust the amount of the reducing agent to supply the same amount as the equivalent of the ytterbium precipitate (Yb 2 (SO 4 ) 3 , YbF 3 , YbS) previously prepared. If an amount less than the equivalent of ytterbium precipitate is supplied, the regeneration efficiency of pure ytterbium is lowered. If the reducing agent is supplied in excess of the equivalent weight of the ytterbium precipitate, there is a problem of low yield due to the presence of unreacted reducing agent.
마지막 단계는 필터를 이용해 고순도의 이터븀을 회수하는 단계(600)이다. 이 때 사용될 수 있는 필터로는 앞서와 마찬가지로 폴리프로필렌, PVDF, PTFE 재질의 필터가 적합하며, 필터의 기공크기는 마찬가지로 0.1~10㎛가 적당하다. The final step is to recover high purity ytterbium using a filter (600). As before, the filters that can be used at this time are suitable for filters made of polypropylene, PVDF, and PTFE, and the pore size of the filter is similarly 0.1 to 10㎛.
이하에서는 실시예를 통해 본 발명을 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail through examples.
<실시예 1> <Example 1>
폐 산화이터븀을 용해시키기 위해 산성 수용액으로 10 vol% 질산을 사용하였다. 사용한 산성 수용액의 양은 1L이고 폐 산화이터븀의 공급량은 산성 수용액 100 중량부 대비 10 중량부의 산화이터븀을 공급하였다. 상온에서 폐 산화이터븀이 전부 용해될 때까지 천천히 교반하였다.To dissolve the spent ytterbium oxide, 10 vol% nitric acid was used as an acidic aqueous solution. The amount of acidic aqueous solution used was 1L, and the amount of waste ytterbium oxide supplied was 10 parts by weight based on 100 parts by weight of the acidic aqueous solution. It was stirred slowly at room temperature until all of the spent ytterbium oxide was dissolved.
이터븀 침전물을 형성시키기 위한 침전제로는 산화이터븀이 용해된 용액 100중량부 대비 20 중량부의 황산(H2SO4)을 사용하였으며, 침전 반응이 완료될 때까지 상온에서 천천히 교반하였다. As a precipitant to form the ytterbium precipitate, 20 parts by weight of sulfuric acid (H 2 SO 4 ) was used based on 100 parts by weight of the solution in which ytterbium oxide was dissolved, and the solution was slowly stirred at room temperature until the precipitation reaction was completed.
생성된 이터븀 침전물을 여과시키기 위해 1㎛ PVDF 필터를 사용하여 여과하였다. 여과된 침전물을 다시 용해시키기 위해 0.1M NaOH 수용액을 사용하였고, 상온에서 교반과 함께 모두 용해시켰다. The resulting ytterbium precipitate was filtered using a 1㎛ PVDF filter. A 0.1M NaOH aqueous solution was used to re-dissolve the filtered precipitate, and it was all dissolved with stirring at room temperature.
용해된 이터븀을 환원시키기 위한 환원제로 아스코르브산을 사용하였으며, 이터븀 침전물(Yb2(SO4)3)의 당량과 동일하게 조절하여 공급하였다(44.7g 아스코르브산). Ascorbic acid was used as a reducing agent to reduce dissolved ytterbium, and was adjusted to equal the equivalent weight of ytterbium precipitate (Yb 2 (SO 4 ) 3 ) and supplied (44.7 g ascorbic acid).
상온에서 교반과 함께 반응을 완료하였으며, 마지막으로 0.5㎛ PVDF 필터를 이용하여 이터븀을 회수하였다. 회수된 이터븀의 순도를 ICP-OES를 이용하여 분석하였다.The reaction was completed with stirring at room temperature, and finally ytterbium was recovered using a 0.5㎛ PVDF filter. The purity of the recovered ytterbium was analyzed using ICP-OES.
<실시예 2> <Example 2>
산성 수용액으로 10 vol% 염산을 사용한다는 점을 제외하고, 실시예 1과 동일하게 진행하였다.The procedure was the same as Example 1, except that 10 vol% hydrochloric acid was used as the acidic aqueous solution.
<실시예 3> <Example 3>
산성 수용액으로 10 vol% 인산을 사용한다는 점을 제외하고, 실시예 1과 동일하게 진행하였다.The procedure was the same as in Example 1, except that 10 vol% phosphoric acid was used as the acidic aqueous solution.
<실시예 4> <Example 4>
침전제로 NaF를 사용한다는 점을 제외하고, 실시예 1과 동일하게 진행하였다.The procedure was the same as in Example 1, except that NaF was used as a precipitant.
<실시예 5> <Example 5>
침전제로 Na2S를 사용한다는 점을 제외하고, 실시예 1과 동일하게 진행하였다.The procedure was the same as in Example 1, except that Na 2 S was used as a precipitant.
표 1은 실시예 1 내지 5의 공정조건과 이를 통해 수득한 이터븀(Yb)의 순도를 나타내는 표이다. 실험 결과 산성 수용액으로 질산을 사용하고, 침전제로 황산을 사용한 실시예 1의 경우 수득한 이터븀이 가장 좋은 순도를 나타내고 있음을 확인하였다.Table 1 is a table showing the process conditions of Examples 1 to 5 and the purity of ytterbium (Yb) obtained therefrom. As a result of the experiment, it was confirmed that the ytterbium obtained in Example 1, which used nitric acid as an acidic aqueous solution and sulfuric acid as a precipitant, showed the best purity.
(vol %)(vol%)
(M)(M)
상기에서는 본 발명의 일 실시예를 참조하여 설명하였지만, 해당 기술 분야에서 통상의 지식을 가진 자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the present invention has been described above with reference to an embodiment of the present invention, those skilled in the art can modify the present invention in various ways without departing from the spirit and scope of the present invention as set forth in the claims below. and that it can be changed.
S100: 폐 산화이터븀을 산성 수용액에 용해시키는 단계
S200: 이터븀 침전물을 형성시키는 단계
S300: 이터븀 침전물을 여과시키는 단계
S400: 이터븀 침전물을 수산화나트륨 수용액에 용해시키는 단계
S500: 이터븀을 환원시키는 단계
S600: 이터븀을 회수하는 단계S100: Dissolving spent ytterbium oxide in acidic aqueous solution
S200: forming ytterbium precipitate
S300: Filtering the ytterbium precipitate
S400: Dissolving ytterbium precipitate in aqueous sodium hydroxide solution
S500: Step to reduce ytterbium
S600: Steps to recover ytterbium
Claims (7)
ⅰ) 디스플레이 제작 공정에서 사용된 폐 산화이터븀을 상온에서 질산(HNO3) 또는 염산(HCl) 수용액에 용해시키는 단계(S100);
ⅱ) 상기 산화이터븀이 용해된 용액에 침전제인 황산(H2SO4)을 공급하여 이터븀 침전물을 형성시키는 단계(S200);
ⅲ) 필터를 이용해 상기 이터븀 침전물을 여과시키는 단계(S300);
ⅳ) 여과된 상기 이터븀 침전물을 수산화나트륨(NaOH) 수용액에 용해시키는 단계(S400);
ⅴ) 상기 이터븀 침전물이 용해된 용액에 환원제인 아스코르브산을 공급하여 이터븀으로 환원시키는 단계(S500); 및
ⅵ) 상기 환원된 이터븀을 회수하는 단계(S600).A method for recovering ytterbium (Yb) from spent ytterbium oxide (Yb 2 O 3 ) comprising the following steps.
i) dissolving the waste ytterbium oxide used in the display manufacturing process in an aqueous solution of nitric acid (HNO 3 ) or hydrochloric acid (HCl) at room temperature (S100);
ii) forming a ytterbium precipitate by supplying sulfuric acid (H 2 SO 4 ), a precipitant, to the solution in which the ytterbium oxide is dissolved (S200);
iii) filtering the ytterbium precipitate using a filter (S300);
iv) dissolving the filtered ytterbium precipitate in an aqueous sodium hydroxide (NaOH) solution (S400);
v) supplying ascorbic acid, a reducing agent, to the solution in which the ytterbium precipitate is dissolved to reduce it to ytterbium (S500); and
vi) Recovering the reduced ytterbium (S600).
상기 질산 또는 염산 수용액의 농도는 5~20 vol%인 것을 특징으로 하는
폐 산화이터븀으로부터 이터븀을 재생하는 방법.According to paragraph 1,
The concentration of the nitric acid or hydrochloric acid aqueous solution is 5 to 20 vol%.
Method for recovering ytterbium from spent ytterbium oxide.
상기 침전제의 첨가량은 이터븀 침전물이 용해된 혼합액 100 중량부 대비 5~30 중량부인 것을 특징으로 하는
폐 산화이터븀으로부터 이터븀을 재생하는 방법.According to paragraph 1,
The amount of the precipitant added is 5 to 30 parts by weight based on 100 parts by weight of the mixed solution in which the ytterbium precipitate is dissolved.
Method for recovering ytterbium from spent ytterbium oxide.
상기 필터의 기공크기는 0.1~10 ㎛ 인 것을 특징으로 하는
폐 산화이터븀으로부터 이터븀을 재생하는 방법.According to paragraph 1,
The pore size of the filter is 0.1 to 10 ㎛.
Method for recovering ytterbium from spent ytterbium oxide.
상기 수산화나트륨 수용액의 농도는 0.1~1.0 M 인 것을 특징으로 하는
폐 산화이터븀으로부터 이터븀을 재생하는 방법.According to paragraph 1,
The concentration of the sodium hydroxide aqueous solution is 0.1 to 1.0 M.
Method for recovering ytterbium from spent ytterbium oxide.
상기 환원제의 공급량은 이터븀 침전물의 당량과 동일하게 조절하는 것을 특징으로 하는
폐 산화이터븀으로부터 이터븀을 재생하는 방법.According to paragraph 1,
The supply amount of the reducing agent is adjusted to be equal to the equivalent amount of ytterbium precipitate.
Method for recovering ytterbium from spent ytterbium oxide.
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