WO2014069699A1 - Absorbent ball particle for recovering porous lithium by carbonization, and method for preparing same - Google Patents
Absorbent ball particle for recovering porous lithium by carbonization, and method for preparing same Download PDFInfo
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- WO2014069699A1 WO2014069699A1 PCT/KR2012/009193 KR2012009193W WO2014069699A1 WO 2014069699 A1 WO2014069699 A1 WO 2014069699A1 KR 2012009193 W KR2012009193 W KR 2012009193W WO 2014069699 A1 WO2014069699 A1 WO 2014069699A1
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- WIPO (PCT)
- Prior art keywords
- adsorption ball
- lithium
- ball particles
- adsorption
- particles
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 148
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000003763 carbonization Methods 0.000 title claims description 19
- 230000002745 absorbent Effects 0.000 title abstract 6
- 239000002250 absorbent Substances 0.000 title abstract 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229920003987 resole Polymers 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 142
- 238000011084 recovery Methods 0.000 claims description 70
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 16
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 9
- -1 hydroquino Chemical compound 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001755 resorcinol Drugs 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910009343 Li1.33 Mn1.67 O4 Inorganic materials 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- FDSMXFUYVWTYQJ-UHFFFAOYSA-N nitromethanetriol Chemical compound OC([N+](=O)[O-])(O)O FDSMXFUYVWTYQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000013535 sea water Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 6
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
Definitions
- the present invention relates to adsorption ball particles for lithium recovery having a spherical porous structure with excellent recovery of lithium, and a method of manufacturing the same.
- seawater which accounts for about 70% of the world, includes manganese (2.7 billion tons), molybdenum (14 billion tons), cobalt (140 million tons), and tungsten (140 million tons) ), Titanium (1.4 billion tonnes), lithium (200 billion tonnes), magnesium (1840 trillion tonnes), indium (272 billion tonnes), rare earths (4.2 billion tonnes), chromium (68 million tonnes) and vanadium (2.7 billion tonnes)
- About 80 kinds of metals such as tons), germanium (80 million tons) and bismuth (20 million tons) are dissolved in low concentrations of ions.
- magnesium (1840 trillion tons), lithium (200 billion tons), molybdenum (14 billion tons), and uranium (4.1 billion tons) are likely to be commercialized. Therefore, many efforts have been made to selectively separate and recover valuable metal ions such as lithium and uranium having low concentrations from seawater.
- Lithium separation technology currently used is largely used for organic material adsorption and inorganic adsorption methods such as lithium manganese metal oxide (LiMnO 4 ).
- the organic adsorption method there is mainly a method using a lithium selective ion exchange resin, but these methods have a small lithium ion radius, so the selectivity and efficiency for lithium in the mixed solution is very low, and in the case of a lithium manganese metal oxide-based adsorption method, an imprinting method As a result, it has excellent adsorption rate of lithium ions, but the material is difficult to handle in the form of powder, and it is very difficult to apply the process.In addition, it has a secondary wastewater by using acidic solution such as hydrochloric acid when recovering lithium ions. There are many problems to apply to the development of new materials that can selectively adsorb lithium ions and the development of chemical free desorption process.
- lithium recovery methods are known to reduce lithium ions by electrochemical methods, or to reduce lithium oxide with magnesium or aluminum metal, and another method is to use an adsorbent that selectively adsorbs lithium ions. To recover lithium, and the like.
- the main interest of these studies using lithium adsorbents is to develop high performance adsorbents with high selectivity for lithium ions and excellent adsorption / desorption performance.
- the present invention is to solve the above problems, it is an object of the present invention to provide a spherical porous lithium recovery adsorption ball particles and a method of manufacturing the composite metal oxide is adsorbed or dispersed. More specifically, the purpose of the present invention is to efficiently recover lithium from seawater and wastewater solutions, and to provide adsorption ball particles for lithium recovery with improved durability and a method of manufacturing the same.
- the phenolic monomer of step a) is any one or two or more selected from phenol, pehydroxybenzene-based, pyrocatechin (catechol), resorcinol (resorcin), hydroquino, pyrogallol ,
- the formaldehyde-based monomer relates to a method for producing the adsorption ball particles for lithium recovery of any one or two or more selected from aliphatic or aromatic formaldehyde.
- the present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the catalyst of step a) is an alkaline catalyst.
- the present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the catalyst contains 1 to 2 parts by weight based on 100 parts by weight of the phenolic monomer.
- the present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the molar ratio of the phenolic monomer and the formaldehyde monomer is 1: 1 to 4.
- the present invention relates to a method for producing the adsorption ball particles for lithium recovery, wherein the composite metal oxide of step b) is any one selected from the following Chemical Formulas 1 to 2.
- M is one element selected from Co, Ni, Mn,
- M ' is one element selected from Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge,
- M ′′ is at least one element selected from Mg, Ca, B, and Ga.
- the present invention relates to a method for producing the adsorption ball particles for lithium recovery, wherein the composite metal oxide is of the general formula (3).
- the present invention relates to a method for producing adsorption ball particles for lithium recovery of the size of the composite metal oxide is 50 ⁇ 100nm.
- the curing agent of step b) is one or two or more mixtures selected from hexamethylenetetraamine, trishydroxynitromethane, paraformaldehyde, dimethylamine, ammonia, ethylenediamine and formaldehyde, triethylenediamine It relates to a method for producing the adsorption ball particles for phosphorus lithium recovery.
- the present invention relates to a method for producing the adsorption ball particles for lithium recovery for 2 to 4 hours at a temperature of 800 ⁇ 1000 °C during the carbonization of step c).
- the adsorption ball particles produced by the method for producing lithium adsorption ball particles are related to the lithium adsorption ball particles having a spherical porous structure.
- the present invention also relates to a lithium recovery adsorption ball particles having a size of 20 ⁇ 1000 ⁇ m the adsorption ball particles for lithium recovery.
- the present invention also relates to a lithium recovery adsorption ball particle having a spinel structure of the composite metal oxide of the lithium recovery adsorption ball particle.
- the adsorption ball particle for lithium recovery according to the present invention is a structure in which a composite metal oxide is dispersed and adsorbed in a resol resin by polymerizing a resol oligomer solution, a composite metal oxide, and a curing agent, so that spherical porous particles can be prepared and handled. Not only easy but also have improved durability of the spherical porous particles, that is, there is an effect capable of producing the adsorption ball particles for lithium recovery to recover the lithium ions. Therefore, lithium ion is adsorbed to the adsorption ball particles by exposing the adsorption ball particles for lithium recovery to seawater and wastewater for a long time, thereby effectively recovering high concentrations of lithium ions by chemical and electrical repetitive desorption methods.
- One aspect of the present invention relates to a method for producing adsorption ball particles for lithium recovery, and to various methods of introducing a composite metal oxide containing metal ions into a polymer support, a polymer polymer alone or a crosslinked polymer support may be used.
- a polymer support After dispersing the metal complex oxide, and heating it appropriately to prepare a particle having a porosity to have a porosity, it is ion-exchanged by acid treatment such as hydrochloric acid to recover the spherical lithium ion of the present invention
- Adsorbent ball particles can be prepared. In the case of complete firing, the adhesion between the composite metal oxides may be weak, and thus the use of the composite metal oxides may be somewhat limited.
- the present invention is not particularly limited as long as it is a conventional suspension polymerization method for producing the particles, and the polymerization monomer is not particularly limited as long as it is a monomer to be employed in conventional suspension polymerization.
- the present invention relates to a method for producing lithium adsorption ball particles having a resol resin as a support and having a spherical porous structure.
- the phenolic monomer of step a) may include any one or two or more selected from phenol, pehydroxybenzene-based, pyrocatechin (catechol), resorcinol (resorcin), hydroquino, pyrogallol,
- phenol may be preferably used.
- the formaldehyde-based monomer of step a) may include any one or two or more selected from aliphatic or aromatic formaldehyde, but is not limited thereto, preferably formaldehyde can be used.
- formaldehyde can be used.
- the use of phenol as a phenol and formaldehyde monomer as the monomer mixture is easy to form a resol resin having excellent alkali solubility.
- the inclusion of the phenolic monomer and formaldehyde-based monomer in the above range is improved durability, physical and chemical properties are It is preferable because it can form a resol resin which is excellent and has excellent alkali solubility.
- the catalyst of step a) is preferably an alkaline catalyst, and specifically, any one selected from ammonia water, triethylamine, and the like may be used, but the present invention is not limited thereto and may be used as a general alkaline catalyst used in the art. Do.
- the catalyst preferably contains 1 to 2 parts by weight with respect to 100 parts by weight of the phenol monomer, and when the catalyst is included in the above range, it is preferable because the preparation of the resol oligomer solution is easy and the reaction time can be shortened. .
- the complex metal oxide of step b) may be any one selected from the following Chemical Formulas 1 to 2, preferably, the Chemical Formula 3.
- M is one element selected from Co, Ni, Mn, M 'is Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In , Si, Ge is one element selected from, M "is at least one element selected from Mg, Ca, B, Ga.
- the composite metal oxide used in the present invention is preferably represented by Chemical Formula 3, which has a high chemical stability of lithium manganese oxide in the above structure, and when formed into an ionic body, has a adsorption range for selectively adsorbing lithium ions. Because it can provide.
- the size of the composite metal oxide is preferably 50 ⁇ 100nm, because it has the effect of improving the durability when it has a range of the size of the above.
- the curing agent of step b) may be used that is one or two or more mixtures selected from hexamethylenetetraamine, trishydroxynitromethane, paraformaldehyde, dimethylamine, ammonia, ethylenediamine and formaldehyde, triethylenediamine,
- the curing agent is used to increase the crosslinking density inside the spherical resol oligomer solution.
- hexamethylene teraamine is used in terms of durability.
- the carbonization of step c) is preferably performed for 2 to 4 hours at a temperature of 800 to 1,000 ° C., and when the carbonization is performed for the above time in the above temperature range, adhesion between the composite metal oxides may be improved and durability may be improved.
- carbonization in the above range is the basis for producing a porous ball adsorption ball particles having a pore size of 0.1 ⁇ 10 ⁇ m, because the pore size of 0.1 ⁇ 10 ⁇ m is excellent in physical and chemical durability.
- the step d) is an acid treatment step of the adsorption ball particles carbonized in the step c),
- the acid solution that can be used for the acid treatment is not particularly limited, inorganic acid solutions such as hydrochloric acid, sulfuric acid, etc. may be used, Preferably, hydrochloric acid is used. This is because the use of the acidic solution is preferable for maximizing the generation of lithium holes for more effective reversible reaction of lithium ions and hydrogen ions, and preventing the elution of manganese ions.
- the present invention may polymerize and carbonize the resol oligomer solution, the composite metal oxide, and a curing agent to produce particles having a spherical porous structure.
- Particles having a spherical porous structure that is, adsorption ball particles for lithium recovery, are resol resins.
- the composite metal oxide is dispersed and adsorbed in the form. Accordingly, the durability of the adsorption ball particle for lithium recovery is improved, and since it is used in the form of spherical particles, it is easy to apply to the lithium adsorption process, and it is possible to improve the disadvantages of difficult handling of the existing powder form, thereby making it easy to apply various processes. There is one advantage.
- the present invention relates to an adsorption ball particle manufactured by the method of preparing the adsorption ball particle for lithium recovery, wherein the manufactured lithium recovery adsorption ball particle has a spherical porous structure.
- the adsorption ball particles for lithium recovery manufactured according to the present invention are manufactured in a spherical shape, the handling is easy and durability can be improved due to the porous structure.
- the spherical porous structure produced in the present invention is preferably a suction ball particles for recovering lithium is 20 ⁇ 1000 ⁇ m size, the particles of the size is preferable to recover the lithium ions, may have a high fire resistance, physical And because the chemical durability is excellent. In addition, it can provide an adsorption surface that can be selectively adsorbed only lithium ions, and can compensate for the disadvantages of powdered lithium adsorbent.
- the powder form means that the particle size is less than 1 ⁇ m.
- the structure of the composite metal oxide of the spherical porous structure for collecting lithium adsorption ball particles is a spinel structure, and the result obtained by phase eluting lithium ions in the compound having a spinel structure is contained in the target solution. This is because it shows excellent selectivity for lithium ions and can efficiently adsorb and recover lithium ions.
- the adsorption ball particles for lithium recovery according to the present invention are made of particles having a spherical porous structure, which can compensate for the disadvantages of the lithium adsorbent in the form of powder, which is easy to handle and adsorbs the composite metal oxide to the resol oligomer resin. And according to the dispersed form there is an effect that can be produced for the absorption ball particles for improved lithium recovery. Therefore, lithium ion is adsorbed to the adsorption ball particles by exposing the adsorption ball particles for lithium recovery to seawater and waste water for a long time, and thus, high concentration of lithium ions can be effectively recovered by chemical and electrical repetitive desorption methods.
- Example 1 is an SEM image of the adsorption ball particles for lithium recovery before carbonization prepared in Example 1 of the present invention.
- Example 2 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 1 of the present invention.
- Example 3 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 2 of the present invention.
- Example 4 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 3 of the present invention.
- Example 5 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 1 of the present invention.
- Figure 6 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 2 of the present invention.
- Example 7 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 3 of the present invention.
- Example 8 is a graph illustrating the experiments of the durability of the adsorption ball particles for lithium recovery prepared in Example 1 of the present invention.
- the crystal structure of the adsorption ball particle prepared according to the present invention was measured by X-ray diffraction pattern (Multipurpose X-ray Diffractometer), the X-ray diffraction pattern analysis was carried out in the range of 10 ⁇ 90 It was.
- EDS Errgy Dispersive Spectroscopy
- Artificial seawater (Li + 21.0 ppm, Na + 9.3 ⁇ 10 -3 ppm, Mg + 1.3 ⁇ 10 -3 ppm, K + 3.4 using lithium adsorption ball particles prepared in Examples and Comparative Examples according to the present invention) Lithium adsorption amount was measured at (x10 2 ppm, Ca 2+ 3.5 x 10 2 ppm, Sr 2+ 9.3 ppm, Rb 2+ 1.3 x 10 -1 ppm, Fe 0.1 x 10 -1 ppm). Artificial seawater was prepared by dissolving 37.3 g of marine reef salt in 1 L of distilled water to measure lithium adsorption performance. The pH of the prepared artificial seawater was prepared to be pH 8 similar to that of seawater. 1 g of lithium ion adsorption ball particles were added to the prepared artificial seawater 40 ml, and the adsorption of lithium was performed for 70 hours while stirring at a speed of 100 rpm.
- samples were collected at intervals of 1 hour, 6 hours, 12 hours, 24 hours, 48 hours, and 72 hours to measure the amount of lithium adsorbed through ICP analysis.
- 10 g of the lithium adsorption ball particles prepared to analyze the durability of the adsorption ball particles for recovering lithium prepared in Examples and Comparative Examples according to the present invention are Li + 21.0 ppm, Na + 9.3 ⁇ 10 -3 ppm, Mg + 1.3 Prepared with a composition of 10 x 3 ppm, K + 3.4 x 10 2 ppm, Ca 2+ 3.5 x 10 2 ppm, Sr 2+ 9.3 ppm, Rb 2+ 1.3 x 10 -1 ppm, Fe 0.1 x 10 -1 ppm After 72 hours of adsorption in the artificial seawater of pH 8, the adsorption ball particles were dried three times after elution of Li adsorbed at intervals of 24 hours in 5M HCl solution.
- Equation 1 The adsorption and desorption and drying process was repeated 10 times to determine the occurrence of weight loss according to whether the adsorption ball particles were broken and calculated as shown in Equation 1 below.
- Li 1.33 Mn 1.67 O 4 (average particle diameter: 50 nm) was added to 100 parts by weight of the phenolic monomer as a composite metal oxide having lithium ions in 150 g of the resol oligomer solution, followed by stirring at a speed of 450 rpm to sufficiently disperse the composite A resol oligomer solution containing a metal oxide was prepared.
- 1.0 part by weight of polyvinyl alcohol (Poly (vinyl alcohol), 99.0%) was dissolved in 250 ml of distilled water based on 100 parts by weight of phenol monomer, and then added to the prepared resol oligomer solution containing the composite metal oxide.
- 3.0 parts by weight of hexamethylene terramine (HMTA) as a curing agent was added thereto, followed by a hardening reaction for 15 hours with vigorous stirring to prepare adsorption ball particles.
- the size of the prepared adsorption ball particles was an average of 300 ⁇ m.
- the spherical adsorption ball particles prepared by the curing reaction were washed with distilled water and carbonized using a tube furnace at a temperature of 1000 ° C. in a nitrogen atmosphere in which oxygen was blocked under the conditions shown in Table 1 below.
- the adsorption ball particles of the secondary Li ion were washed with distilled water, dried in an oven at 70 ° C. for 3 hours, and then stirred for 3 hours at 500 rpm in 500 ml of 5M hydrochloric acid for 3 hours.
- EDS Energy Dispersive Spectroscopy
- Resol oligomer solution was prepared in the same manner as in Step 1 of Example 1.
- the experiment was carried out in the same manner as in the second step of Example 1, and only the temperature was changed at the time of carbonization. At this time, the size of the prepared adsorption ball particles was 310 ⁇ m average.
- Resol oligomer solution was prepared in the same manner as in Step 1 of Example 1.
- the experiment was carried out in the same manner as in the second step of Example 1, the experiment was carried out by changing only the temperature at the time of carbonization, the size of the prepared adsorption ball particles was an average 310 ⁇ m.
- styrene oligomer solution including the composite metal oxide prepared above, and then stirred vigorously and additionally dispersed for 30 minutes using ultrasonic waves.
- the solution was slowly added dropwise to distilled water, followed by vigorous stirring to proceed suspension polymerization. In order to proceed with a smooth polymerization, it maintained 80 degreeC, and reacted for 6 hours.
- the resulting composite was slowly dried in an oven at 80 ° C. for 12 hours. In order to completely remove the unreacted material and moisture, it was calcined at 300 ° C. in an electric furnace for 2 hours.
- Examples 1 to 3 are experiments by changing the carbonization temperature during the production of the adsorption ball particles for lithium recovery, the maximum 21 per 1 g of the adsorption ball particles for lithium recovery when the carbonization temperature is 800 °C to 1000 °C It was found that the adsorption amount was ppm.
- the spherical lithium ion adsorption ball particles according to the present invention not only shows excellent adsorption efficiency from lithium ions, but also durability Its excellent and spherical bead shape makes it easy to handle and is expected to be used as an effective material for lithium recovery by applying it to various types of adsorption systems.
- Example 1 is a SEM image of the adsorption ball particles for lithium recovery before carbonization prepared in Example 1
- Figure 2 is a SEM image of the adsorption ball particles for lithium recovery after carbonization, looking at Figure 2, the adsorption ball after carbonization It can be confirmed that pores are formed on the surface of the particles.
- the average size of the adsorption ball particles prepared in Example 1 was confirmed that the 300 ⁇ m.
- Figure 3 is a SEM photograph of the adsorption ball particles for lithium recovery after carbonization prepared in Example 2, it could be confirmed that the average size of the particles is 310 ⁇ m.
- Figure 4 is a SEM photograph of the adsorption ball particles for lithium recovery after carbonization prepared in Example 3, it could be confirmed that the average size of the particles is 310 ⁇ m.
- the shape of the adsorption ball particles for lithium recovery prepared in Examples 1 to 3 has a spherical porous structure, and thus, it was confirmed that it had a large surface area.
- the crystal structure of the adsorption ball particle prepared in Example 1 is shown in Figure 5 the result of measuring the crystal structure through an X-ray diffraction pattern (Multipurpose X-ray Diffractometer).
- X-ray diffraction pattern analysis of the crystal structure of the spherical adsorption ball particles thus prepared as shown in FIG. 5, it can be seen that the diffraction pattern of the spinel crystal structure appears.
- X-ray diffraction patterns of the adsorption ball particles prepared in Examples 2 to 3 are shown in FIGS. 6 to 7 below.
- the adsorption ball particles prepared in Example 1 showed the same pattern as the adsorption ball particles prepared in Example 1.
Abstract
The present invention relates to a method for preparing an absorbent ball particle for recovering porous lithium, comprising: a) a step of performing a condensation reaction between a monomer mixture and a catalyst so as to prepare a resol oligomer solution; b) a step of polymerizing the resol oligomer solution, a composite metal oxide, and a hardening agent so as to prepare an absorbent ball particle; c) a step of carbonizing the absorbent ball particle that was prepared in step b); and d) a step of acidifying the carbonized absorbent ball particle. The present invention also relates to an absorbent ball particle for recovering porous lithium prepared by the above-described method.
Description
본 발명은 리튬의 회수율이 우수한 구형의 다공성 구조의 리튬회수용 흡착볼 입자 및 그의 제조방법에 관한 것이다.The present invention relates to adsorption ball particles for lithium recovery having a spherical porous structure with excellent recovery of lithium, and a method of manufacturing the same.
지구의 약 70%를 차지하는 해수에는 우라늄 (41억 톤)외에 우리나라 10대 전략 희소 금속인 망간(27억 톤), 몰리브덴(140억 톤), 코발트(1억 4000톤), 텅스텐(1억 4000톤), 티타늄(14억 톤), 리튬(2천억 톤), 마그네슘(1840조 톤), 인듐(272억 톤), 희토류(42억 톤), 크롬(6천 8백만 톤)과 바나듐(27억 톤), 게르마늄(8천만 톤), 비스무스(2천만 톤)등의 약 80여종의 금속이 저농도의 이온형태로 용존되어 있다. 특히 마그네슘(1,840조 톤), 리튬(2천억 톤), 몰리브덴(140억 톤), 우라늄(41억 톤) 등은 상업화 가능성이 크다. 그러므로, 해수로부터 농도가 극히 낮은 리튬, 우라늄과 같은 유가금속 이온을 선택적으로 분리 회수하여 자원화하기 위한 노력들이 많이 이루어지고 있다. In addition to uranium (4.1 billion tons), seawater, which accounts for about 70% of the world, includes manganese (2.7 billion tons), molybdenum (14 billion tons), cobalt (140 million tons), and tungsten (140 million tons) ), Titanium (1.4 billion tonnes), lithium (200 billion tonnes), magnesium (1840 trillion tonnes), indium (272 billion tonnes), rare earths (4.2 billion tonnes), chromium (68 million tonnes) and vanadium (2.7 billion tonnes) About 80 kinds of metals such as tons), germanium (80 million tons) and bismuth (20 million tons) are dissolved in low concentrations of ions. In particular, magnesium (1840 trillion tons), lithium (200 billion tons), molybdenum (14 billion tons), and uranium (4.1 billion tons) are likely to be commercialized. Therefore, many efforts have been made to selectively separate and recover valuable metal ions such as lithium and uranium having low concentrations from seawater.
현재 사용되고 있는 리튬분리기술은 크게 유기소재 흡착 및 리튬망간 금속산화물(LiMnO4)과 같은 무기흡착법이 사용되고 있다. 유기흡착법의 경우 주로 리튬 선택성 이온교환 수지를 이용한 방법이 있으나 이들 방법은 리튬 이온반경이 작아 혼합용액 중에서 리튬에 대한 선택성과 효율이 매우 낮고, 리튬망간 금속산화물계 흡착방법의 경우 각인(imprinting) 방법으로 리튬이온 흡착율은 우수하나 소재가 분말 형태로 취급이 어렵고 공정의 적용이 매우 까다로우며, 리튬이온 회수시 염산과 같은 산성용액의 사용으로 2차 폐수의 발생이 있어 친환경 방식을 주장하는 자원 보유국에 적용하기 에는 많은 문제점이 있어 리튬이온을 선택적으로 흡착할 수 있는 새로운 소재의 개발 및 chemical free한 탈착 공정의 개발이 필요한 실정이다.Lithium separation technology currently used is largely used for organic material adsorption and inorganic adsorption methods such as lithium manganese metal oxide (LiMnO 4 ). In the case of the organic adsorption method, there is mainly a method using a lithium selective ion exchange resin, but these methods have a small lithium ion radius, so the selectivity and efficiency for lithium in the mixed solution is very low, and in the case of a lithium manganese metal oxide-based adsorption method, an imprinting method As a result, it has excellent adsorption rate of lithium ions, but the material is difficult to handle in the form of powder, and it is very difficult to apply the process.In addition, it has a secondary wastewater by using acidic solution such as hydrochloric acid when recovering lithium ions. There are many problems to apply to the development of new materials that can selectively adsorb lithium ions and the development of chemical free desorption process.
또한 종래의 리튬 회수 방법으로는 전기화학적 방법에 의해 리튬 이온을 환원시키거나 마그네슘 또는 알루미늄 금속으로 리튬 산화물을 환원시키는 것 등이 알려져 있으며, 또 다른 방법으로는 리튬 이온을 선택적으로 흡착하는 흡착제를 이용하여 리튬을 회수하는 방법 등이 연구되고 있다. 리튬 흡착제를 이용하는 이러한 연구들의 주된 관심은 리튬 이온에 대한 높은 선택성과 흡착/탈착 성능이 우수한 고성능 흡착제를 개발하는 것이다.In addition, conventional lithium recovery methods are known to reduce lithium ions by electrochemical methods, or to reduce lithium oxide with magnesium or aluminum metal, and another method is to use an adsorbent that selectively adsorbs lithium ions. To recover lithium, and the like. The main interest of these studies using lithium adsorbents is to develop high performance adsorbents with high selectivity for lithium ions and excellent adsorption / desorption performance.
그러한 연구들의 결실로서 망간 산화물을 재료로 하여 고상 반응법 또는 겔 공법으로 리튬의 흡/탈착이 용이한 분말을 제조하는 방법이 공지되어 있고, 그러한 방법으로 제조한 분말은 리튬 2차 전지용 양극 재료, 리튬 흡착제의 재료 등으로 이용되어왔다. 그러나 분말 상태의 리튬 흡착제를 사용하는 것은 취급상 불편이 따르기 때문에 이를 성형하여 이용할 필요가 있다. As a result of such studies, a method is known in which a powder which facilitates adsorption / desorption of lithium by a solid phase reaction method or a gel method using manganese oxide as a material is known, and the powder prepared by such a method is a cathode material for a lithium secondary battery, It has been used as a material for lithium adsorbents. However, since the use of powdered lithium adsorbent is inconvenient in handling, it is necessary to mold and use it.
예를 들면, 대한민국 특허공개 제10-2003-9509호에 개시된 바와 같이, 분말을 알루미나 파우더와 혼합한 후, PVC와 같은 공극 형성제를 사용하여 상기 분말 및 알루미나 파우더의 혼합물을 덩어리지게 함으로써 구슬 형태로 흡착제를 제조하는 방법을 응용하여 성형할 수 있다.For example, as disclosed in Korean Patent Publication No. 10-2003-9509, after mixing a powder with alumina powder, a pore-forming agent such as PVC is used to agglomerate the mixture of the powder and alumina powder to form a bead. It can be molded by applying a method for producing an adsorbent.
그러나 상기와 같은 종래의 PVC 첨가법을 이용하여 구슬 형태로 흡착제를 제조할 경우에는, 취급은 용이한 반면, 리튬의 흡/탈착을 위한 흡착 자리가 분말 흡착제에 비해 약 30% 이상 저하되는 것으로 보고되어 있기 때문에, 리튬 흡착제로서 사용 시에 리튬 회수능이 떨어진다는 문제점이 지적되었다.However, in the case of preparing the adsorbent in the form of beads using the conventional PVC addition method as described above, while the handling is easy, the adsorption site for the adsorption / desorption of lithium is reported to be reduced by about 30% or more compared to the powder adsorbent As a result, it has been pointed out that the lithium recovery ability is poor when used as a lithium adsorbent.
본 발명은 상기의 문제점을 해결하기 위한 것으로, 복합금속산화물이 흡착 또는 분산되어 있는 구형의 다공성 리튬 회수용 흡착볼 입자 및 그의 제조방법을 제공하는데 그 목적이 있다. 더욱 구체적으로, 해수 및 폐수 용액에서 리튬을 효과적으로 회수할 수 있으며, 내구성이 향상된 리튬 회수용 흡착볼 입자 및 그의 제조방법을 제공하는데 그 목적이 있다.The present invention is to solve the above problems, it is an object of the present invention to provide a spherical porous lithium recovery adsorption ball particles and a method of manufacturing the composite metal oxide is adsorbed or dispersed. More specifically, the purpose of the present invention is to efficiently recover lithium from seawater and wastewater solutions, and to provide adsorption ball particles for lithium recovery with improved durability and a method of manufacturing the same.
상기의 목적을 달성하기 위한 본 발명의 일 양태로는,In one aspect of the present invention for achieving the above object,
a) 페놀계 단량체, 포름알데히드계 단량체 및 촉매를 축합반응시켜 레졸 올리고머용액을 제조하는 단계;a) preparing a resol oligomer solution by condensing a phenol monomer, a formaldehyde monomer and a catalyst;
b) 상기 레졸 올리고머 용액, 복합금속산화물 및 경화제를 중합시켜 흡착볼입자를 제조하는 단계;b) preparing adsorption ball particles by polymerizing the resol oligomer solution, a composite metal oxide, and a curing agent;
c) 상기 b)단계에서 제조된 흡착볼 입자를 탄화하는 단계; 및c) carbonizing the adsorption ball particles prepared in step b); And
d) 상기 탄화된 흡착볼 입자를 산처리하는 단계; 를 포함하는 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.d) acid treating the carbonized adsorption ball particles; It relates to a method for producing lithium adsorption ball particles comprising a.
또한 본 발명은 상기 a) 단계의 페놀계 단량체는 페놀, 페히드록시벤젠계, 피로카테킨(카테콜), 레조르시놀(레조르신), 히드로퀴노, 피로갈롤에서 선택되는 어느 하나 또는 둘 이상이며, 상기 포름알데히드계 단량체는 지방족 또는 방향족 포름알데히드에서 선택되는 어느 하나 또는 둘 이상인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In the present invention, the phenolic monomer of step a) is any one or two or more selected from phenol, pehydroxybenzene-based, pyrocatechin (catechol), resorcinol (resorcin), hydroquino, pyrogallol , The formaldehyde-based monomer relates to a method for producing the adsorption ball particles for lithium recovery of any one or two or more selected from aliphatic or aromatic formaldehyde.
또한 본 발명은 상기 a)단계의 촉매가 알칼리성 촉매인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.The present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the catalyst of step a) is an alkaline catalyst.
또한 본 발명은 상기 촉매가 페놀계 단량체 100중량부에 대하여 1 ~ 2 중량부 포함하는 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.The present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the catalyst contains 1 to 2 parts by weight based on 100 parts by weight of the phenolic monomer.
또한 본 발명은 상기 페놀계 단량체와 포름알데히드계 단량체의 몰비가 1: 1 ~ 4인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.The present invention also relates to a method for producing adsorption ball particles for lithium recovery, wherein the molar ratio of the phenolic monomer and the formaldehyde monomer is 1: 1 to 4.
또한 본 발명은 상기 b)단계의 복합금속산화물이 하기 화학식 1 내지 2에서 선택되는 어느 하나인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In another aspect, the present invention relates to a method for producing the adsorption ball particles for lithium recovery, wherein the composite metal oxide of step b) is any one selected from the following Chemical Formulas 1 to 2.
[화학식 1][Formula 1]
LimM2-nO4
LimM 2-n O 4
[화학식 2][Formula 2]
LimMxM'yM"zO2
Li m M x M ' y M " z O 2
(상기기 화학식 1에서,(In Chemical Formula 1,
M은 Co, Ni, Mn으로부터 선택되는 1종의 원소이고, M is one element selected from Co, Ni, Mn,
M'는 Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge으로부터 선택되는 1종의 원소이고, M 'is one element selected from Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge,
M"는 Mg, Ca, B, Ga으로부터 선택되는 적어도 1종의 원소이다. M ″ is at least one element selected from Mg, Ca, B, and Ga.
또한, 0.5 ≤ m 이고, 0 ≤ n ≤ 0.33 이고, 0.9 ≤ X < 1이고, 0.001 ≤ y≤ 0.5이고, 0 ≤ z ≤ 0.5이다.) And 0.5 ≦ m, 0 ≦ n ≦ 0.33, 0.9 ≦ X <1, 0.001 ≦ y ≦ 0.5, and 0 ≦ z ≦ 0.5.)
또한 본 발명은 상기 복합금속산화물이 하기 화학식 3인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In addition, the present invention relates to a method for producing the adsorption ball particles for lithium recovery, wherein the composite metal oxide is of the general formula (3).
[화학식 3][Formula 3]
Li1.33Mn1.67O4
Li 1.33 Mn 1.67 O 4
또한 본 발명은 상기 복합금속산화물의 크기가 50 ~ 100nm인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In addition, the present invention relates to a method for producing adsorption ball particles for lithium recovery of the size of the composite metal oxide is 50 ~ 100nm.
또한 본 발명은 상기 b)단계의 경화제가 헥사메틸렌테트라아민, 트리스하이드록실니트로메탄, 파라포름알데히드, 디메틸아민, 암모니아, 에틸렌디아민 및 포름알데히드, 트리에틸렌디아민에서 선택되는 하나 또는 둘 이상의 혼합물인 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In addition, the present invention is that the curing agent of step b) is one or two or more mixtures selected from hexamethylenetetraamine, trishydroxynitromethane, paraformaldehyde, dimethylamine, ammonia, ethylenediamine and formaldehyde, triethylenediamine It relates to a method for producing the adsorption ball particles for phosphorus lithium recovery.
또한 본 발명은 상기 c)단계의 탄화시 온도 800 ~ 1000℃에서 2 ~ 4시간하는 것인 리튬 회수용 흡착볼 입자의 제조방법에 관한 것이다.In addition, the present invention relates to a method for producing the adsorption ball particles for lithium recovery for 2 to 4 hours at a temperature of 800 ~ 1000 ℃ during the carbonization of step c).
본 발명의 다른 양태로는, 상기 리튬 회수용 흡착볼 입자의 제조방법에 의해 제조된 흡착볼 입자는 구형의 다공성구조인 것인 리튬 회수용 흡착볼 입자에 관한 것이다.In another aspect of the present invention, the adsorption ball particles produced by the method for producing lithium adsorption ball particles are related to the lithium adsorption ball particles having a spherical porous structure.
또한 본 발명은 상기 리튬 회수용 흡착볼 입자의 크기가 20 ~ 1000㎛인 것인 리튬 회수용 흡착볼 입자에 관한 것이다.The present invention also relates to a lithium recovery adsorption ball particles having a size of 20 ~ 1000㎛ the adsorption ball particles for lithium recovery.
또한 본 발명은 상기 리튬 회수용 흡착볼 입자의 복합금속산화물의 구조가 스피넬구조인 것인 리튬 회수용 흡착볼 입자에 관한 것이다.The present invention also relates to a lithium recovery adsorption ball particle having a spinel structure of the composite metal oxide of the lithium recovery adsorption ball particle.
본 발명에 따른 리튬 회수용 흡착볼 입자는 레졸 올리고머 용액, 복합금속산화물 및 경화제를 중합시켜 레졸수지에 복합금속산화물이 분산 및 흡착되어 있는 구조로써, 구형의 다공성 입자를 제조 할 수 있어, 취급이 용이할 뿐만 아니라 내구성이 향상된 구형의 다공성 입자, 즉, 리튬이온을 회수할 수 있는 리튬회수용 흡착볼 입자를 제조할 수 있는 효과가 있다. 따라서 장시간 해수 및 폐수 등에 리튬 회수용 흡착볼 입자를 노출시켜 흡착볼 입자에 리튬이온을 흡착시켜 화학적, 전기적인 반복적인 탈착방법에 의해 고농도의 리튬이온을 효과적으로 회수 할 수 있는 효과가 있다.The adsorption ball particle for lithium recovery according to the present invention is a structure in which a composite metal oxide is dispersed and adsorbed in a resol resin by polymerizing a resol oligomer solution, a composite metal oxide, and a curing agent, so that spherical porous particles can be prepared and handled. Not only easy but also have improved durability of the spherical porous particles, that is, there is an effect capable of producing the adsorption ball particles for lithium recovery to recover the lithium ions. Therefore, lithium ion is adsorbed to the adsorption ball particles by exposing the adsorption ball particles for lithium recovery to seawater and wastewater for a long time, thereby effectively recovering high concentrations of lithium ions by chemical and electrical repetitive desorption methods.
이하 본 발명의 각 구성에 대하여 구체적으로 설명한다.Hereinafter, each configuration of the present invention will be described in detail.
본 발명의 일 양태로는, 리튬 회수용 흡착볼 입자의 제조방법에 관한 것으로, 금속이온을 함유하는 복합금속산화물을 고분자 지지체에 도입하는 여러 방법으로는, 고분자 중합체 단독이나 또는 가교고분자 지지체를 사용할 수 있다. 고분자 지지체의 경우에는 금속복합 산화물을 분산한 후, 이를 적절히 가열함으로써, 부분 소성하여 다공성을 가지도록 하는 입자를 제조하고, 이를 염산등의 산 처리하여 이온 교환시켜 본 발명의 구형의 리튬 이온 회수용 흡착볼 입자를 제조할 수 있다. 완전 소성하는 경우에는 복합금속산화물간 접착력이 약하여 장기 사용이 다소 제한되는 점이 있을 수 있지만, 복합금속산화물이 서로 잘 연결되어 강한 강도를 가지는 경우라면 제한되지 않는다.One aspect of the present invention relates to a method for producing adsorption ball particles for lithium recovery, and to various methods of introducing a composite metal oxide containing metal ions into a polymer support, a polymer polymer alone or a crosslinked polymer support may be used. Can be. In the case of the polymer support, after dispersing the metal complex oxide, and heating it appropriately to prepare a particle having a porosity to have a porosity, it is ion-exchanged by acid treatment such as hydrochloric acid to recover the spherical lithium ion of the present invention Adsorbent ball particles can be prepared. In the case of complete firing, the adhesion between the composite metal oxides may be weak, and thus the use of the composite metal oxides may be somewhat limited.
본 발명은 입자를 제조하는 방법으로는 통상적인 현탁중합법이라면 크게 제한 받지 않으며, 또한 중합단량체 또한 통상의 현탁중합에 채택하는 단량체라면 크게 제한되지 않는다. The present invention is not particularly limited as long as it is a conventional suspension polymerization method for producing the particles, and the polymerization monomer is not particularly limited as long as it is a monomer to be employed in conventional suspension polymerization.
본 발명은, 레졸수지를 지지체로 하며, 구형의 다공성 구조를 가지는 리튬 회수용 흡착볼 입자의 제조방법에 관한 것으로,The present invention relates to a method for producing lithium adsorption ball particles having a resol resin as a support and having a spherical porous structure.
a) 페놀계 단량체, 포름알데히드계 단량체 및 촉매를 축합반응시켜 레졸 올리고머용액을 제조하는 단계;a) preparing a resol oligomer solution by condensing a phenol monomer, a formaldehyde monomer and a catalyst;
b) 상기 레졸 올리고머 용액, 복합금속산화물 및 경화제를 중합시켜 흡착볼입자를 제조하는 단계;b) preparing adsorption ball particles by polymerizing the resol oligomer solution, a composite metal oxide, and a curing agent;
c) 상기 b)단계에서 제조된 흡착볼 입자를 탄화하는 단계; 및c) carbonizing the adsorption ball particles prepared in step b); And
d) 상기 탄화된 흡착볼 입자를 산 처리하는 단계; 를 포함한다. d) acid treating the carbonized adsorption ball particles; It includes.
상기 a) 단계의 페놀계 단량체는 페놀, 페히드록시벤젠계, 피로카테킨(카테콜), 레조르시놀(레조르신), 히드로퀴노, 피로갈롤에서 선택되는 어느 하나 또는 둘 이상을 포함할 수 있으나, 이에 제한되지는 않으며, 바람직하게는 페놀을 사용할 수 있다. The phenolic monomer of step a) may include any one or two or more selected from phenol, pehydroxybenzene-based, pyrocatechin (catechol), resorcinol (resorcin), hydroquino, pyrogallol, However, the present invention is not limited thereto, and phenol may be preferably used.
또한 상기 a)단계의 포름알데히드계 단량체는 지방족 또는 방향족 포름알데히드에서 선택되는 어느 하나 또는 둘 이상을 포함할 수 있으나, 이에 제한되지는 않으며, 바람직하게는 포름알데히드를 사용할 수 있다. 상기 단량체 혼합물이 폐놀계 단량체로 페놀, 포름알데히드계 단량체로 알데히드를 사용하는 것은 알칼리 용해도가 우수한 레졸 수지를 형성하는데 용이하기 때문이다.In addition, the formaldehyde-based monomer of step a) may include any one or two or more selected from aliphatic or aromatic formaldehyde, but is not limited thereto, preferably formaldehyde can be used. The use of phenol as a phenol and formaldehyde monomer as the monomer mixture is easy to form a resol resin having excellent alkali solubility.
또한 상기 페놀계 단량체와 포름알데히드계 단량체의 몰비를 1: 1 ~ 4으로 혼합하는 것이 바람직하며, 상기의 범위로 페놀계 단량체와 포름알데히드계 단량체를 포함하는 것이 내구성이 향상되고, 물리적 화학적 특성이 우수하며 알칼리 용해도가 우수한 레졸 수지를 형성할 수 있기 때문에 바람직하다. In addition, it is preferable to mix the molar ratio of the phenolic monomer and the formaldehyde-based monomer 1: 1 to 4, the inclusion of the phenolic monomer and formaldehyde-based monomer in the above range is improved durability, physical and chemical properties are It is preferable because it can form a resol resin which is excellent and has excellent alkali solubility.
상기 a)단계의 촉매는 알칼리성 촉매를 사용한 것이 바람직하며, 구체적으로암모니아수, 트리에틸아민 등에서 선택되는 어느 하나를 사용할 수 있지만, 이에 한정되지 않고 이 기술 분야에 사용되는 통상의 알칼리성 촉매라면 사용이 가능하다. 또한 상기 촉매는 페놀 단량체 100중량부에 대하여 1 ~ 2 중량부 포함하는 것이 바람직하며, 촉매를 상기의 범위로 포함하였을 경우, 레졸 올리고머 용액의 제조가 용이하고, 반응 시간을 단축할 수 있기 때문에 좋다.The catalyst of step a) is preferably an alkaline catalyst, and specifically, any one selected from ammonia water, triethylamine, and the like may be used, but the present invention is not limited thereto and may be used as a general alkaline catalyst used in the art. Do. In addition, the catalyst preferably contains 1 to 2 parts by weight with respect to 100 parts by weight of the phenol monomer, and when the catalyst is included in the above range, it is preferable because the preparation of the resol oligomer solution is easy and the reaction time can be shortened. .
상기 b)단계의 복합금속산화물은 하기 화학식 1 내지 2에서 선택되는 어느 하나일 수 있으며, 바람직하게는 하기 화학식 3일 수 있다. The complex metal oxide of step b) may be any one selected from the following Chemical Formulas 1 to 2, preferably, the Chemical Formula 3.
[화학식 1][Formula 1]
LimM2-nO4
LimM 2-n O 4
[화학식 2][Formula 2]
LimMxM'yM"zO2
Li m M x M ' y M " z O 2
[화학식 3][Formula 3]
Li1.33Mn1.67O4
Li 1.33 Mn 1.67 O 4
(상기 화학식 1에서, M은 Co, Ni, Mn으로부터 선택되는 1종의 원소이고, M'는 Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge으로부터 선택되는 1종의 원소이고, M"는 Mg, Ca, B, Ga으로부터 선택되는 적어도 1종의 원소이다. (In Formula 1, M is one element selected from Co, Ni, Mn, M 'is Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In , Si, Ge is one element selected from, M "is at least one element selected from Mg, Ca, B, Ga.
또한, 0.5 ≤ m 이고, 0 ≤ n ≤ 0.33 이고, 0.9 ≤ X < 1이고, 0.001 ≤ y≤ 0.5이고, 0 ≤ z ≤ 0.5이다.)And 0.5 ≦ m, 0 ≦ n ≦ 0.33, 0.9 ≦ X <1, 0.001 ≦ y ≦ 0.5, and 0 ≦ z ≦ 0.5.)
본 발명에서 사용되는 복합금속산화물은 상기 화학식 3인 것이 바람직한데, 이는 상기의 구조일 경우 리튬 망간 산화물이 높은 화학적 안정성을 가지며, 이온체로 형성할 경우 리튬이온을 선택적으로 흡착할 수 있는 흡착 범위를 제공할 수 있기 때문이다.The composite metal oxide used in the present invention is preferably represented by Chemical Formula 3, which has a high chemical stability of lithium manganese oxide in the above structure, and when formed into an ionic body, has a adsorption range for selectively adsorbing lithium ions. Because it can provide.
또한 상기 복합금속산화물의 크기가 50 ~ 100nm인 것이 바람직한데, 이는 상기의 크기의 범위를 가질 경우 내구성이 향상되는 효과가 있기 때문이다.In addition, the size of the composite metal oxide is preferably 50 ~ 100nm, because it has the effect of improving the durability when it has a range of the size of the above.
상기 b)단계의 경화제는 헥사메틸렌테트라아민, 트리스하이드록실니트로메탄, 파라포름알데히드, 디메틸아민, 암모니아, 에틸렌디아민 및 포름알데히드, 트리에틸렌디아민등에서 선택되는 하나 또는 둘 이상의 혼합물인 것을 사용할 수 있으며, 경화제는 구형 레졸 올리고머 용액 내부의 가교밀도를 높이기 위해 사용하는 것으로, 바람직하게는 헥사메틸렌테르라아민을 사용하는 것이 내구성면에서 좋다. The curing agent of step b) may be used that is one or two or more mixtures selected from hexamethylenetetraamine, trishydroxynitromethane, paraformaldehyde, dimethylamine, ammonia, ethylenediamine and formaldehyde, triethylenediamine, The curing agent is used to increase the crosslinking density inside the spherical resol oligomer solution. Preferably, hexamethylene teraamine is used in terms of durability.
상기 c)단계의 탄화는 온도 800 ~ 1,000℃에서 2 ~ 4시간하는 것이 바람직하며, 상기의 온도범위에서 상기의 시간만큼 탄화를 수행할 경우 복합금속산화물간의 접착력이 향상되어 내구성이 좋아질 수 있다. 또한 상기의 범위에서 탄화하는 것이 기공크기 0.1 ~ 10 ㎛인 다공성 구조의 흡착볼 입자를 제조할 수 있는 기반이 되며, 상기 기공크기가 0.1 ~ 10㎛인 것이 물리적 및 화학적 내구성이 우수하기 때문이다. The carbonization of step c) is preferably performed for 2 to 4 hours at a temperature of 800 to 1,000 ° C., and when the carbonization is performed for the above time in the above temperature range, adhesion between the composite metal oxides may be improved and durability may be improved. In addition, carbonization in the above range is the basis for producing a porous ball adsorption ball particles having a pore size of 0.1 ~ 10 ㎛, because the pore size of 0.1 ~ 10 ㎛ is excellent in physical and chemical durability.
상기 d)단계는 상기 c)단계에서 탄화된 흡착볼 입자를 산 처리하는 단계로, 산 처리에 이용될 수 있는 산성 용액은 특별히 제한되지는 않지만, 염산, 황산 등의 무기산용액을 사용할 수 있으며, 바람직하게는 염산을 사용하는 것이 좋다. 상기의 산성 용액을 사용하는 것이 리튬이온과 수소이온의 보다 효과적인 가역 반응을 위한 리튬홀의 생성을 최대화하고, 망간 이온의 용출을 방지하는데 바람직하기 때문이다.The step d) is an acid treatment step of the adsorption ball particles carbonized in the step c), the acid solution that can be used for the acid treatment is not particularly limited, inorganic acid solutions such as hydrochloric acid, sulfuric acid, etc. may be used, Preferably, hydrochloric acid is used. This is because the use of the acidic solution is preferable for maximizing the generation of lithium holes for more effective reversible reaction of lithium ions and hydrogen ions, and preventing the elution of manganese ions.
본 발명은 상기 레졸 올리고머 용액, 복합금속산화물 및 경화제를 중합시키고, 탄화하여 구형의 다공성구조를 가지는 입자를 제조할 수 있으며, 구형의 다공성구조를 가지는 입자, 즉 리튬 회수용 흡착볼 입자는 레졸수지에 복합금속산화물이 분산 및 흡착되어 있는 형태를 가지게 된다. 이에 따라, 리튬 회수용 흡착볼 입자의 내구성이 향상되고, 구형입자의 형태로 사용되기 때문에 리튬흡착 공정에 적용이 간편하고, 기존 분말형태의 취급이 어려운 단점을 개선할 수 있어 다양한 공정 적용이 용이한 장점이 있다.The present invention may polymerize and carbonize the resol oligomer solution, the composite metal oxide, and a curing agent to produce particles having a spherical porous structure. Particles having a spherical porous structure, that is, adsorption ball particles for lithium recovery, are resol resins. The composite metal oxide is dispersed and adsorbed in the form. Accordingly, the durability of the adsorption ball particle for lithium recovery is improved, and since it is used in the form of spherical particles, it is easy to apply to the lithium adsorption process, and it is possible to improve the disadvantages of difficult handling of the existing powder form, thereby making it easy to apply various processes. There is one advantage.
본 발명은 다른 또 양태로는 상기 리튬 회수용 흡착볼 입자의 제조방법에 의해 제조된 흡착볼 입자에 관한 것으로, 제조된 리튬 회수용 흡착볼 입자는 구형의 다공성구조를 가지는 것을 특징으로 한다.In still another aspect, the present invention relates to an adsorption ball particle manufactured by the method of preparing the adsorption ball particle for lithium recovery, wherein the manufactured lithium recovery adsorption ball particle has a spherical porous structure.
본 발명에 따라 제조되는 리튬 회수용 흡착볼 입자가 구형으로 제조됨에 따라 취급이 용이하고, 다공성 구조로 인해 내구성이 향상 될 수 있는 것이다.As the adsorption ball particles for lithium recovery manufactured according to the present invention are manufactured in a spherical shape, the handling is easy and durability can be improved due to the porous structure.
본 발명에서 제조되는 구형의 다공성 구조의 리튬 회수용 흡착볼 입자는 크기가 20 ~ 1000㎛인 것이 바람직하며, 상기의 크기의 입자는 리튬이온을 회수하는데 바람직하고, 높은 내화도를 가질 수 있으며, 물리적 및 화학적 내구성이 우수하기 때문이다. 또한 리튬 이온만을 선택적으로 흡착 될 수 있는 흡착면을 제공할 수 있으며, 분말형태 리튬 흡착체의 단점을 보완할 수 있다.The spherical porous structure produced in the present invention is preferably a suction ball particles for recovering lithium is 20 ~ 1000㎛ size, the particles of the size is preferable to recover the lithium ions, may have a high fire resistance, physical And because the chemical durability is excellent. In addition, it can provide an adsorption surface that can be selectively adsorbed only lithium ions, and can compensate for the disadvantages of powdered lithium adsorbent.
본 발명에서 분말형태란, 입자의 크기가 1 ㎛미만 크기를 의미한다.In the present invention, the powder form means that the particle size is less than 1 ㎛.
또한 상기 제조되는 구형의 다공성 구조의 리튬 회수용 흡착볼 입자의 복합금속산화물의 구조가 스피넬구조인 것이 바람직하며, 스피넬 구조를 가짐으로 해서 화합물 내의 리튬 이온을 위상 용출시켜 수득된 결과물이 대상 용액 내에서 리튬 이온에 대한 뛰어난 선택성을 나타 낼 수 있으며, 효율적으로 리튬이온을 흡착 및 회수할 수 있기 때문이다.In addition, it is preferable that the structure of the composite metal oxide of the spherical porous structure for collecting lithium adsorption ball particles is a spinel structure, and the result obtained by phase eluting lithium ions in the compound having a spinel structure is contained in the target solution. This is because it shows excellent selectivity for lithium ions and can efficiently adsorb and recover lithium ions.
본 발명에 따른 리튬 회수용 흡착볼 입자는 구형의 다공성구조의 입자로 제조되어, 분말형태의 리튬흡착제의 단점을 보완할 수 있으며, 이에 취급이 용이할 뿐만 아니라 레졸 올리고머 수지에 복합금속산화물이 흡착 및 분산된 형태임에 따라 내구성이 향상된 리튬회수용 흡착볼 입자를 제조할 수 있는 효과가 있다. 따라서 장시간 해수 및 폐수 등에 리튬 회수용 흡착볼 입자를 노출시켜 흡착볼 입자에 리튬이온을 흡착시켜 화학적, 전기적인 반복적인 탈착방법에 의해 고농도의 리튬이온을 효과적으로 회수 할 수 있다.The adsorption ball particles for lithium recovery according to the present invention are made of particles having a spherical porous structure, which can compensate for the disadvantages of the lithium adsorbent in the form of powder, which is easy to handle and adsorbs the composite metal oxide to the resol oligomer resin. And according to the dispersed form there is an effect that can be produced for the absorption ball particles for improved lithium recovery. Therefore, lithium ion is adsorbed to the adsorption ball particles by exposing the adsorption ball particles for lithium recovery to seawater and waste water for a long time, and thus, high concentration of lithium ions can be effectively recovered by chemical and electrical repetitive desorption methods.
도 1은 본 발명의 실시예 1에서 제조한 탄화전의 리튬 회수용 흡착볼 입자의 SEM 이미지이다.1 is an SEM image of the adsorption ball particles for lithium recovery before carbonization prepared in Example 1 of the present invention.
도 2는 본 발명의 실시예 1에서 제조한 탄화후의 리튬 회수용 흡착볼 입자의 SEM 이미지이다.2 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 1 of the present invention.
도 3는 본 발명의 실시예 2에서 제조한 탄화후의 리튬 회수용 흡착볼 입자의 SEM 이미지이다.3 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 2 of the present invention.
도 4는 본 발명의 실시예 3에서 제조한 탄화후의 리튬 회수용 흡착볼 입자의 SEM 이미지이다.4 is an SEM image of the adsorption ball particles for lithium recovery after carbonization prepared in Example 3 of the present invention.
도 5는 본 발명의 실시예 1에서 제조한 리튬 회수용 흡착볼 입자의 XRD 패턴이다.5 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 1 of the present invention.
도 6는 본 발명의 실시예 2에서 제조한 리튬 회수용 흡착볼 입자의 XRD 패턴이다.Figure 6 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 2 of the present invention.
도 7는 본 발명의 실시예 3에서 제조한 리튬 회수용 흡착볼 입자의 XRD 패턴이다.7 is an XRD pattern of the adsorption ball particles for lithium recovery prepared in Example 3 of the present invention.
도 8은 본 발명의 실시예 1에서 제조한 리튬 회수용 흡착볼 입자의 내구성을 실험하여 나타낸 그래프이다.8 is a graph illustrating the experiments of the durability of the adsorption ball particles for lithium recovery prepared in Example 1 of the present invention.
이하, 본 발명을 실시 예에 의해 상세히 설명한다. 단, 하기 실시 예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 내용이 하기 실시 예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.
이하 물성은 다음과 같은 방법으로 측정하였다.Below physical properties were measured by the following method.
1. 리튬 회수용 흡착볼 입자의 표면구조 측정1. Measurement of surface structure of adsorption ball particle for lithium recovery
냉전계 전자주사현미경(Cold type Field Emission Scanning Electron Microscope)을 통하여 관찰하였다.Cold field electron scanning microscope (Cold type Field Emission Scanning Electron Microscope) was observed.
2. 리튬 회수용 흡착볼 입자의 결정구조 측정2. Measurement of crystal structure of adsorption ball particle for lithium recovery
본 발명에 따라 제조된 흡착볼 입자의 결정 구조는 X-선 회절 패턴(Multipurpose X-ray Diffractometer)을 통하여 결정구조를 측정하였으며, 상기 X-선 회절 패턴 분석은 10 ~ 90 의 θ의 범위에서 실시하였다.The crystal structure of the adsorption ball particle prepared according to the present invention was measured by X-ray diffraction pattern (Multipurpose X-ray Diffractometer), the X-ray diffraction pattern analysis was carried out in the range of 10 ~ 90 It was.
3. EDS(Energy Dispersive Spectroscopy) 측정3. Energy Dispersive Spectroscopy (EDS) Measurement
본 발명에 따라 제조된 리튬 회수용 흡착볼 입자 내의 리튬망간산화물의 함유를 확인하기 위하여 EDS(Energy Dispersive Spectroscopy)를 측정하였다.EDS (Energy Dispersive Spectroscopy) was measured to confirm the content of lithium manganese oxide in the adsorption ball particles for lithium recovery according to the present invention.
4. 제조된 리튬 회수용 흡착볼 입자를 이용한 리튬이온의 흡착량 측정 4. Measurement of the adsorption amount of lithium ions using the prepared adsorption ball particles for lithium recovery
본 발명에 따른 실시예 및 비교예에서 제조한 리튬 회수용 흡착볼 입자를 이용하여 인공해수 (Li+ 21.0 ppm, Na+ 9.3×10-3 ppm, Mg+ 1.3×10-3 ppm, K+ 3.4×102 ppm, Ca2+ 3.5×102 ppm, Sr2+ 9.3 ppm, Rb2+ 1.3×10-1 ppm, Fe 0.1×10-1 ppm) 에서 리튬 흡착량을 측정하였다. 리튬 흡착성능을 측정하기 위하여 인공해수는 인공해수염(Marine reef salt) 37.3 g 을 증류수 1 L에서 용해시켜 제조하였다. 제조된 인공해수의 pH는 해수와 비슷한 pH 8이 되도록 제조하였다. 제조된 인공해수 40 ml 에 리튬 이온 흡착볼 입자 1 g 을 넣고 100 rpm의 속도로 교반해 주면서 70 시간 동안 리튬의 흡착을 진행 하였다. Artificial seawater (Li + 21.0 ppm, Na + 9.3 × 10 -3 ppm, Mg + 1.3 × 10 -3 ppm, K + 3.4 using lithium adsorption ball particles prepared in Examples and Comparative Examples according to the present invention) Lithium adsorption amount was measured at (x10 2 ppm, Ca 2+ 3.5 x 10 2 ppm, Sr 2+ 9.3 ppm, Rb 2+ 1.3 x 10 -1 ppm, Fe 0.1 x 10 -1 ppm). Artificial seawater was prepared by dissolving 37.3 g of marine reef salt in 1 L of distilled water to measure lithium adsorption performance. The pH of the prepared artificial seawater was prepared to be pH 8 similar to that of seawater. 1 g of lithium ion adsorption ball particles were added to the prepared artificial seawater 40 ml, and the adsorption of lithium was performed for 70 hours while stirring at a speed of 100 rpm.
리튬 흡착의 성능측정을 위해 1시간, 6시간, 12시간, 24시간, 48시간, 72시간 간격으로 시료를 분취하여 ICP 분석을 통해 흡착된 리튬의 양을 측정하였다. In order to measure the performance of lithium adsorption, samples were collected at intervals of 1 hour, 6 hours, 12 hours, 24 hours, 48 hours, and 72 hours to measure the amount of lithium adsorbed through ICP analysis.
5. 리튬 회수용 흡착볼 입자의 내구성 시험 5. Durability test of adsorption ball particle for lithium recovery
본 발명에 따른 실시예 및 비교예에서 제조한 리튬 회수용 흡착볼 입자의 내구성을 분석하기 위해 제조된 리튬 흡착볼 입자10 g 을 Li+ 21.0 ppm, Na+ 9.3×10-3 ppm, Mg+ 1.3×10-3 ppm, K+ 3.4×102 ppm, Ca2+ 3.5×102 ppm, Sr2+ 9.3 ppm, Rb2+ 1.3×10-1 ppm, Fe 0.1×10-1 ppm의 조성으로 제조된 pH 8의 인공해수에서 72시간 흡착을 진행한 후, 흡착볼 입자를 5M HCl용액에서 24시간 간격으로 흡착된 Li용출 3회를 진행한 후 건조하였다.10 g of the lithium adsorption ball particles prepared to analyze the durability of the adsorption ball particles for recovering lithium prepared in Examples and Comparative Examples according to the present invention are Li + 21.0 ppm, Na + 9.3 × 10 -3 ppm, Mg + 1.3 Prepared with a composition of 10 x 3 ppm, K + 3.4 x 10 2 ppm, Ca 2+ 3.5 x 10 2 ppm, Sr 2+ 9.3 ppm, Rb 2+ 1.3 x 10 -1 ppm, Fe 0.1 x 10 -1 ppm After 72 hours of adsorption in the artificial seawater of pH 8, the adsorption ball particles were dried three times after elution of Li adsorbed at intervals of 24 hours in 5M HCl solution.
상기 흡탈착 및 건조 과정을 10회 반복 진행하야 흡착볼 입자의 파손여부에 따른 무게감소의 발생여부를 측정하여 하기 식 1과 같이 계산하여, 그 결과를 하기 표 4에 기재하였다. The adsorption and desorption and drying process was repeated 10 times to determine the occurrence of weight loss according to whether the adsorption ball particles were broken and calculated as shown in Equation 1 below.
[실시예 1] Example 1
1단계; 레졸 올리고머 용액의 제조Stage 1; Preparation of Resol Oligomeric Solution
페놀(Phenol, SAMCHUN, 99.0%) 95.06g과 포름알데히드(Formaldehyde solution, SAMCHUN, 35.0%)85.77g(몰비 1:1)를 충분히 혼합되도록 교반하였다. 그리고 페놀 100중량부에 대하여 암모니아수(Ammonia solution, SAMCHUN, 30.0%)1.25 중량부를 첨가하여 촉매로 사용하였으며, 85℃의 온도에서 8시간 동안 축합반응을 통해 레졸 올리고머 용액을 제조하였다. 레졸 올리고머 용액의 합성 여부는 투명한 용액이 불투명하게 변화되는 것으로 확인 하였다. 95.06 g of phenol (Phenol, SAMCHUN, 99.0%) and 85.77 g (molar ratio 1: 1) of formaldehyde (Formaldehyde solution, SAMCHUN, 35.0%) were stirred to be sufficiently mixed. Then, 1.25 parts by weight of ammonia water (Ammonia solution, SAMCHUN, 30.0%) was used as a catalyst based on 100 parts by weight of phenol, and a resol oligomer solution was prepared through a condensation reaction at a temperature of 85 ° C. for 8 hours. Synthesis of the resol oligomer solution was confirmed that the transparent solution is changed opaque.
2 단계; 흡착볼 입자의 제조Two steps; Preparation of Suction Ball Particles
상기 레졸 올리고머 용액 150g 에 리튬이온을 가지는 복합금속산화물로 Li1.33Mn1.67O4(평균입경 50nm)를 페놀계 단량체 100중량부에 대하여 40중량부 첨가한 후 450rpm의 속도로 교반하여 충분히 분산시켜 복합금속산화물이 포함된 레졸 올리고머 용액을 제조하였다.Li 1.33 Mn 1.67 O 4 (average particle diameter: 50 nm) was added to 100 parts by weight of the phenolic monomer as a composite metal oxide having lithium ions in 150 g of the resol oligomer solution, followed by stirring at a speed of 450 rpm to sufficiently disperse the composite A resol oligomer solution containing a metal oxide was prepared.
그리고, 페놀 단량체 100중량부에 대하여 폴리비닐알콜(Poly(vinyl alcohol), 99.0%) 1.0중량부를 증류수 250 ml 에 녹인 후, 상기 제조된 복합금속산화물이 포함된 레졸 올리고머 용액에 첨가하였다. 또한 경화제로 헥사메틸렌테르라아민(HMTA;hexamethylenetetramine) 3.0 중량부를 투입한 후 강력하게 교반하면서 15시간 동안 경화반응을 진행하여 흡착볼 입자를 제조하였다. 이때 제조된 흡착볼 입자의 크기는 평균 300 ㎛이었다. Then, 1.0 part by weight of polyvinyl alcohol (Poly (vinyl alcohol), 99.0%) was dissolved in 250 ml of distilled water based on 100 parts by weight of phenol monomer, and then added to the prepared resol oligomer solution containing the composite metal oxide. In addition, 3.0 parts by weight of hexamethylene terramine (HMTA) as a curing agent was added thereto, followed by a hardening reaction for 15 hours with vigorous stirring to prepare adsorption ball particles. At this time, the size of the prepared adsorption ball particles was an average of 300 ㎛.
그리고 경화반응을 통해 제조된 구형의 흡착볼 입자를 증류수로 세척한 후 튜브 퍼니스를 이용하여 하기 표 1의 조건으로 산소가 차단된 질소분위기에서 1000℃의 온도로 탄화를 실시하였다.The spherical adsorption ball particles prepared by the curing reaction were washed with distilled water and carbonized using a tube furnace at a temperature of 1000 ° C. in a nitrogen atmosphere in which oxygen was blocked under the conditions shown in Table 1 below.
3 단계; 탄화된 흡착볼 입자의 산처리(흡착볼 입자의 활성화)Three steps; Acid treatment of carbonized adsorption ball particles (activation of adsorption ball particles)
상기 2단계에서 제조한 탄화된 흡착볼 입자를 활성화하기 위하여 상기 탄화된 흡착볼 입자 100g 을 증류수로 세척 후 65℃의 오븐에서 3시간 동안 건조 하였다. 그리고, 5M 염산 500ml에서 24시간동안 100rpm의 속도로 교반하며 1차 Li 용출을 진행하였다. 1차 Li 이온의 용출이 끝난 흡착볼 입자를 증류수로 세척 후 65℃의 오븐에서 3시간 동안 건조한 후 5M 염산 500ml에서 24시간동안 100rpm의 속도로 교반하며 2차 Li용출을 진행하였다. 2차 Li 이온의 용출이 끝난 흡착볼 입자는 증류수로 세척 후 70℃의 오븐에서 3시간 동안 건조한 후 5M 염산 500ml에서 24시간동안 100rpm의 속도로 교반하며 3차 Li용출을 진행하였으며, 이때 리튬 회수용 흡착볼 입자 내의 리튬망간산화물의 함유를 확인하기 위하여 EDS(Energy Dispersive Spectroscopy)를 측정하였으며, 그 결과는 하기 표 3에 나타내었다. In order to activate the carbonized adsorption ball particles prepared in step 2, 100g of the carbonized adsorption ball particles were washed with distilled water and dried in an oven at 65 ° C. for 3 hours. In addition, primary Li elution was performed while stirring at 500 rpm of 5 M hydrochloric acid at a rate of 100 rpm for 24 hours. The adsorption ball particles of the primary Li ions eluted were washed with distilled water, dried in an oven at 65 ° C. for 3 hours, and stirred for 2 hours at 500 rpm in 5M hydrochloric acid at a rate of 100 rpm for 2 hours. The adsorption ball particles of the secondary Li ion were washed with distilled water, dried in an oven at 70 ° C. for 3 hours, and then stirred for 3 hours at 500 rpm in 500 ml of 5M hydrochloric acid for 3 hours. EDS (Energy Dispersive Spectroscopy) was measured in order to confirm the content of lithium manganese oxide in the water adsorption ball particles, and the results are shown in Table 3 below.
[실시예 2] Example 2
1단계; 레졸 올리고머 용액의 제조Stage 1; Preparation of Resol Oligomeric Solution
상기 실시예 1의 단계 1과 동일한 방법으로 레졸 올리고머 용액을 제조하였다.Resol oligomer solution was prepared in the same manner as in Step 1 of Example 1.
2 단계; 흡착볼 입자의 제조Two steps; Preparation of Suction Ball Particles
상기 실시예 1의 2단계와 동일한 방법으로 실시하였으며, 탄화시 온도만을 변화하여 실험하였으며, 각 실험조건은 하기 표 1에 나타내었다. 이때 제조된 흡착볼 입자의 크기는 평균 310 ㎛이었다.The experiment was carried out in the same manner as in the second step of Example 1, and only the temperature was changed at the time of carbonization. At this time, the size of the prepared adsorption ball particles was 310 ㎛ average.
3 단계; 탄화된 흡착볼 입자의 산처리(흡착볼 입자의 활성화)Three steps; Acid treatment of carbonized adsorption ball particles (activation of adsorption ball particles)
상기 실시예 1의 단계 3과 동일한 방법으로 실시하였으며, 이때 리튬 회수용 흡착볼 입자내의 리튬망간산화물의 함유를 확인하기 위하여 EDS(Energy Dispersive Spectroscopy)를 측정하였으며. 그 결과는 하기 표 3에 나타내었다. In the same manner as in Step 3 of Example 1, at this time, EDS (Energy Dispersive Spectroscopy) was measured to determine the content of lithium manganese oxide in the adsorption ball particles for lithium recovery. The results are shown in Table 3 below.
[실시예 3] Example 3
1단계; 레졸 올리고머 용액의 제조Stage 1; Preparation of Resol Oligomeric Solution
상기 실시예 1의 단계 1과 동일한 방법으로 레졸 올리고머 용액을 제조하였다.Resol oligomer solution was prepared in the same manner as in Step 1 of Example 1.
2 단계; 흡착볼 입자의 제조Two steps; Preparation of Suction Ball Particles
상기 실시예 1의 2단계와 동일한 방법으로 실시하였으며, 탄화시 온도만을 변화하여 실험하였고, 이때 제조된 흡착볼 입자의 크기는 평균 310 ㎛이었다. The experiment was carried out in the same manner as in the second step of Example 1, the experiment was carried out by changing only the temperature at the time of carbonization, the size of the prepared adsorption ball particles was an average 310 ㎛.
각 실험조건은 하기 표 1에 나타내었다.Each experimental condition is shown in Table 1 below.
3 단계; 탄화된 흡착볼 입자의 산처리(흡착볼 입자의 활성화)Three steps; Acid treatment of carbonized adsorption ball particles (activation of adsorption ball particles)
상기 실시예 1의 단계 3과 동일한 방법으로 실시하였으며, 이때 리튬 회수용 흡착볼 입자내의 리튬망간산화물의 함유를 확인하기 위하여 EDS(Energy Dispersive Spectroscopy)를 측정하였으며, 그 결과는 하기 표 3에 나타내었다. In the same manner as in Step 3 of Example 1, at this time, EDS (Energy Dispersive Spectroscopy) was measured to confirm the content of lithium manganese oxide in the adsorption ball particles for lithium recovery, and the results are shown in Table 3 below. .
[표 1]TABLE 1
[비교예 1] Comparative Example 1
스틸렌(styrene, 분자량 104.15 g/mol) 5g 과 디비닐벤젠 (divinyl benzene, 분자량 130.19 g/mol) 15g 을 충분히 혼합되도록 교반한 후, 리튬이온을 가지는 복합금속산화물로 Li1.33Mn1.67O4(평균입경 60nm)를 스틸렌 단량체 100중량부에 대하여 40중량부, 폴리비닐알콜(Poly(vinyl alcohol), 99%검화도) 0.1중량부를 첨가하였다. 그리고 450rpm의 속도로 80℃의 온도에서 충분히 혼합되도록 교반하여 복합금속산화물을 포함한 스틸렌 올리고머 용액을 제조하였다.5 g of styrene (molecular weight: 104.15 g / mol) and 15 g of divinyl benzene (molecular weight: 130.19 g / mol) were stirred to be sufficiently mixed, and then Li 1.33 Mn 1.67 O 4 (average) A particle size of 60 nm) was added 40 parts by weight of 100 parts by weight of styrene monomer, and 0.1 parts by weight of poly (vinyl alcohol, 99% saponification). Then, the mixture was stirred at a temperature of 80 ° C. at a speed of 450 rpm to prepare a styrene oligomer solution including a composite metal oxide.
상기 제조된 복합금속산화물을 포함하는 스틸렌 올리고머 용액에 스틸렌 단량체 100중량부에 대하여 벤조펄옥사이드 0.1중량부와 톨루엔 10중량부를 첨가하여 강하게 교반하고 추가적으로 초음파를 이용해 30분간 분산시켰다. 그리고 상기 용액을 증류수에 천천히 적하시키면서 강력하게 교반하여 현탁중합을 진행하였다. 원활한 중합을 진행하기 위해 80℃를 유지하고 6시간 반응을 진행하였다. 수득한 합성물은 80℃의 오븐에서 12시간 동안 서서히 건조하였다. 미반응 물질과 수분을 완전히 제거하기 위해 전기로에서 300℃의 온도로 2시간 소성하였다.0.1 parts by weight of benzopearl oxide and 10 parts by weight of toluene were added to the styrene oligomer solution including the composite metal oxide prepared above, and then stirred vigorously and additionally dispersed for 30 minutes using ultrasonic waves. The solution was slowly added dropwise to distilled water, followed by vigorous stirring to proceed suspension polymerization. In order to proceed with a smooth polymerization, it maintained 80 degreeC, and reacted for 6 hours. The resulting composite was slowly dried in an oven at 80 ° C. for 12 hours. In order to completely remove the unreacted material and moisture, it was calcined at 300 ° C. in an electric furnace for 2 hours.
이어서, 상기 제조된 흡착제를 하기 표 2의 조건으로 탄화하였다.Subsequently, the prepared adsorbent was carbonized under the conditions shown in Table 2 below.
이어서, 상기 제조한 흡착볼 입자를 활성화하기 위하여 산 처리 하였다. 산 처리는 0.1몰의 HCl 용액 500 ml 에서 100 rpm의 속도로 교반 하는 상태로 24시간 동안 진행하였다. 1회 활성화한 구상 흡착제는 60℃ 오븐에서 4시간 건조한 후 0.1몰의 HCl 용액 500 ml 에서 1회 반응과 같은 속도로 교반하며 24시간동안 2차 활성화 하였다. 2회 활성화한 구상 흡착체는 전과 마찬가지로 60℃ 오븐에서 4시간 건조하고 이어서 다시 0.1몰의 HCl 용액 500 ml 을 이용하여 3회 리튬 이온의 탈착과정을 통하여 구상 흡착볼 입자를 활성화 하였다. 이때 리튬 회수용 흡착볼 입자 내의 리튬망간산화물의 함유를 확인하기 위하여 EDS(Energy Dispersive Spectroscopy)를 측정하였으며, 그 결과는 하기 표 3에 나타내었다. Subsequently, acid treatment was performed to activate the prepared adsorption ball particles. The acid treatment was performed for 24 hours with stirring at 500 rpm of 0.1 mol of HCl solution at 500 rpm. Once activated spherical adsorbent was dried for 4 hours in an oven at 60 ℃, and stirred for 2 hours for 24 hours with stirring at 500 ml of 0.1 mol of HCl solution at the same speed. The activated spherical adsorbent twice was dried in an oven at 60 ° C. for 4 hours and then activated by spherical adsorption ball particles three times using 500 ml of 0.1 mol of HCl solution. At this time, EDS (Energy Dispersive Spectroscopy) was measured to confirm the content of lithium manganese oxide in the adsorption ball particle for lithium recovery, and the results are shown in Table 3 below.
[표 2]TABLE 2
[표 3]TABLE 3
[표 4]TABLE 4
상기 표 3를 살펴보면, 실시예 1 내지 3 에서 제조한 리튬 회수용 흡착볼 입자는 리튬이온이 모두 용출되어 존재 하지 않음을 알 수 확인할 수 있었다. Looking at the Table 3, it can be seen that the lithium recovery adsorption ball particles prepared in Examples 1 to 3 are not present because all the lithium ions are eluted.
상기 표 4를 살펴보면, 실시예 1 내지 3은 리튬 회수용 흡착볼 입자 제조시 탄화온도를 변화하여 실험한 것으로, 탄화온도가 800℃ 내지 1000℃인 경우 리튬 회수용 흡착볼 입자 1 g 당 최대 21 ppm의 흡착량을 나타냄을 알 수 있었다. Referring to Table 4, Examples 1 to 3 are experiments by changing the carbonization temperature during the production of the adsorption ball particles for lithium recovery, the maximum 21 per 1 g of the adsorption ball particles for lithium recovery when the carbonization temperature is 800 ℃ to 1000 ℃ It was found that the adsorption amount was ppm.
또한 상기 실시예 1 내지 3에서 제조한 리튬 회수용 흡착볼 입자의 리튬 이온의 흡착율을 측정한 결과로부터, 본 발명에 따른 구형 리튬 이온 흡착볼 입자는 리튬이온으로부터 우수한 흡착효율을 나타낼 뿐만 아니라, 내구성이 뛰어나며 구형의 비드형태를 갖고 있어 취급이 용이하여 여러 형태의 흡착 시스템에 적용하여 리튬회수에 대한 효과적인 소재로 이용될 수 있을 것으로 기대된다.In addition, from the results of measuring the adsorption rate of lithium ions of the lithium recovery adsorption ball particles prepared in Examples 1 to 3, the spherical lithium ion adsorption ball particles according to the present invention not only shows excellent adsorption efficiency from lithium ions, but also durability Its excellent and spherical bead shape makes it easy to handle and is expected to be used as an effective material for lithium recovery by applying it to various types of adsorption systems.
상기 실시예 1을 통하여 제조한 구형의 흡착볼 입자의 표면 구조를 냉전계 전자주사현미경(Cold type Field Emission Scanning Electron Microscope)을 통하여 관찰한 SEM사진을 도 1 내지 2에 나타내었다. SEM pictures of the surface structure of the spherical adsorption ball particles prepared in Example 1 using a Cold Type Field Emission Scanning Electron Microscope are shown in FIGS.
도 1은 실시예 1에서 제조한 탄화전의 리튬 회수용 흡착볼 입자의 SEM사진을 나타내며, 도 2는 탄화후의 리튬 회수용 흡착볼 입자의 SEM이미지를 나타내는 것으로, 도 2를 살펴보면, 탄화 후 흡착볼 입자의 표면에 기공이 생성되었음을 확인 할 수 있다. 또한 상기 실시예 1 에서 제조한 흡착볼 입자의 평균크기가 300㎛인 것을 확인 할 수 있었다. 1 is a SEM image of the adsorption ball particles for lithium recovery before carbonization prepared in Example 1, Figure 2 is a SEM image of the adsorption ball particles for lithium recovery after carbonization, looking at Figure 2, the adsorption ball after carbonization It can be confirmed that pores are formed on the surface of the particles. In addition, the average size of the adsorption ball particles prepared in Example 1 was confirmed that the 300㎛.
도 3은 실시예 2에서 제조한 탄화후의 리튬 회수용 흡착볼 입자의 SEM사진으로, 입자의 평균크기가 310㎛임을 확인 할 수 있었다.Figure 3 is a SEM photograph of the adsorption ball particles for lithium recovery after carbonization prepared in Example 2, it could be confirmed that the average size of the particles is 310㎛.
도 4는 실시예 3에서 제조한 탄화후의 리튬 회수용 흡착볼 입자의 SEM사진으로, 입자의 평균크기는 310㎛임을 확인 할 수 있었다. Figure 4 is a SEM photograph of the adsorption ball particles for lithium recovery after carbonization prepared in Example 3, it could be confirmed that the average size of the particles is 310㎛.
또한 실시예 1 내지 3에서 제조한 리튬 회수용 흡착볼 입자의 형태가 구형의 다공성구조를 지니고 있어 넓은 표면적을 가지고 있음을 확인 할 수 있었다.In addition, the shape of the adsorption ball particles for lithium recovery prepared in Examples 1 to 3 has a spherical porous structure, and thus, it was confirmed that it had a large surface area.
상기 실시예 1에서 제조한 흡착볼 입자의 결정 구조는 X-선 회절 패턴(Multipurpose X-ray Diffractometer)을 통하여 결정구조를 측정한 결과를 도 5에 나타내었다. 이와 같이 제조된 구형 흡착볼 입자의 결정구조를 하기 도 5에서와 같이 X-선 회절 패턴 분석을 실시한 결과 스피넬(spinel) 결정구조의 회절 패턴이 나타남을 알 수 있다. 또한 상기 실시예 2 내지 3에서 제조한 흡착볼 입자를 X-선 회절 패턴을 하기 도 6 내지 7에 나타내었으며, 이를 분석한 결과, 실시예 1에서 제조한 흡착볼 입자와 같은 패턴을 나타냄을 확인 할 수 있었다. The crystal structure of the adsorption ball particle prepared in Example 1 is shown in Figure 5 the result of measuring the crystal structure through an X-ray diffraction pattern (Multipurpose X-ray Diffractometer). As a result of X-ray diffraction pattern analysis of the crystal structure of the spherical adsorption ball particles thus prepared, as shown in FIG. 5, it can be seen that the diffraction pattern of the spinel crystal structure appears. In addition, X-ray diffraction patterns of the adsorption ball particles prepared in Examples 2 to 3 are shown in FIGS. 6 to 7 below. As a result, the adsorption ball particles prepared in Example 1 showed the same pattern as the adsorption ball particles prepared in Example 1. Could.
Claims (13)
- a) 페놀계 단량체, 포름알데히드계 단량체 및 촉매를 축합반응시켜 레졸 올리고머용액을 제조하는 단계;a) preparing a resol oligomer solution by condensing a phenol monomer, a formaldehyde monomer and a catalyst;b) 상기 레졸 올리고머 용액, 복합금속산화물 및 경화제를 중합시켜 흡착볼 입자를 제조하는 단계;b) preparing adsorption ball particles by polymerizing the resol oligomer solution, a composite metal oxide, and a curing agent;c) 상기 b)단계에서 제조된 흡착볼 입자를 탄화하는 단계; 및c) carbonizing the adsorption ball particles prepared in step b); Andd) 상기 탄화된 흡착볼 입자를 산 처리하는 단계; 를 포함하는 리튬 회수용 흡착볼 입자의 제조방법. d) acid treating the carbonized adsorption ball particles; Method for producing a lithium recovery adsorption ball particles comprising a.
- 제 1항에 있어서,The method of claim 1,상기 a) 단계의 페놀계 단량체는 페놀, 페히드록시벤젠계, 피로카테킨(카테콜), 레조르시놀(레조르신), 히드로퀴노, 피로갈롤에서 선택되는 어느 하나 또는 둘 이상이며, 상기 포름알데히드계 단량체는 포름알데히드, 디메틸아크릴 아미드, 하이드록시에틸메타크릴레이트에서 선택되는 어느 하나 또는 둘 이상인 것인 리튬 회수용 흡착볼 입자의 제조방법. The phenolic monomer of step a) is any one or two or more selected from phenol, pehydroxybenzene-based, pyrocatechin (catechol), resorcinol (resorcin), hydroquino, pyrogallol, the formaldehyde The monomer is a method of producing the adsorption ball particles for lithium recovery is one or two or more selected from formaldehyde, dimethyl acrylamide, hydroxyethyl methacrylate.
- 제 1항에 있어서,The method of claim 1,상기 a)단계의 촉매는 알칼리성 촉매인 것인 리튬 회수용 흡착볼 입자의 제조방법.The catalyst of step a) is an alkaline catalyst is a method for producing adsorption ball particles for lithium recovery.
- 제 3항에 있어서,The method of claim 3, wherein상기 촉매는 페놀계 단량체 100중량부에 대하여 1 ~ 2 중량부 포함하는 것인 리튬 회수용 흡착볼 입자의 제조방법.The catalyst is a manufacturing method of the adsorption ball particles for lithium recovery containing 1 to 2 parts by weight based on 100 parts by weight of the phenolic monomer.
- 제 2항에 있어서, The method of claim 2,상기 페놀계 단량체와 포름알데히드계 단량체의 몰비가 1: 1 ~ 4인 것인 리튬 회수용 흡착볼 입자의 제조방법.The molar ratio of the phenolic monomer and the formaldehyde-based monomer is 1: 1 to 4, the manufacturing method of the adsorption ball particles for lithium recovery.
- 제 1항에 있어서,The method of claim 1,상기 b)단계의 복합금속산화물은 하기 화학식 1 내지 2에서 선택되는 어느 하나인 것인 리튬 회수용 흡착볼 입자의 제조방법.The composite metal oxide of step b) is a method for producing the adsorption ball particles for lithium recovery is any one selected from the following formula (1).[화학식 1][Formula 1]LimM2-nO4 LimM 2-n O 4[화학식 2][Formula 2]LimMxM'yM"zO2 Li m M x M ' y M " z O 2(상기 화학식 1에서,(In Formula 1,M은 Co, Ni, Mn으로부터 선택되는 1종의 원소이고, M is one element selected from Co, Ni, Mn,M'는 Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge으로부터 선택되는 1종의 원소이고, M 'is one element selected from Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si, Ge,M"는 Mg, Ca, B, Ga으로부터 선택되는 적어도 1종의 원소이다. M ″ is at least one element selected from Mg, Ca, B, and Ga.또한, 0.5 ≤ m 이고, 0 ≤ n ≤ 0.33 이고, 0.9 ≤ X < 1이고, 0.001 ≤ y≤ 0.5이고, 0 ≤ z ≤ 0.5이다.) And 0.5 ≦ m, 0 ≦ n ≦ 0.33, 0.9 ≦ X <1, 0.001 ≦ y ≦ 0.5, and 0 ≦ z ≦ 0.5.)
- 제 6항에 있어서,The method of claim 6,상기 복합금속산화물은 하기 화학식 3인 것인 리튬 회수용 흡착볼 입자의 제조방법.The composite metal oxide is a manufacturing method of the adsorption ball particles for lithium recovery of the formula (3).[화학식 3][Formula 3]Li1.33Mn1.67O4 Li 1.33 Mn 1.67 O 4
- 제 6항에 있어서,The method of claim 6,상기 복합금속산화물의 크기가 50 ~ 100nm인 것인 리튬 회수용 흡착볼 입자의 제조방법.Method for producing a lithium adsorption ball particles that the size of the composite metal oxide is 50 ~ 100nm.
- 제 1항에 있어서,The method of claim 1,상기 b)단계의 경화제는 헥사메틸렌테트라아민, 트리스하이드록실니트로메탄, 파라포름알데히드, 디메틸아민, 암모니아, 에틸렌디아민 및 포름알데히드, 트리에틸렌디아민에서 선택되는 하나 또는 둘 이상의 혼합물인 것인 리튬 회수용 흡착볼 입자의 제조방법.The curing agent of step b) is hexamethylenetetraamine, trishydroxynitromethane, paraformaldehyde, dimethylamine, ammonia, ethylenediamine and formaldehyde, triethylenediamine for recovery of lithium Method for producing adsorption ball particles.
- 제 1항에 있어서,The method of claim 1,상기 c)단계의 탄화는 온도 800 ~ 1000℃에서 2 ~ 4시간하는 것인 리튬 회수용 흡착볼 입자의 제조방법.The carbonization of step c) is a method for producing adsorption ball particles for lithium recovery 2 to 4 hours at a temperature of 800 ~ 1000 ℃.
- 제 1항의 리튬 회수용 흡착볼 입자의 제조방법에 의해 제조된 흡착볼 입자는 구형의 다공성구조인 것인 리튬 회수용 흡착볼 입자.Adsorption ball particles prepared by the method for producing lithium adsorption ball particles of claim 1 is a spherical porous structure of lithium adsorption ball particles.
- 제 11항에 있어서,The method of claim 11,상기 리튬 회수용 흡착볼 입자의 크기가 20 ~ 1000㎛인 것인 리튬 회수용 흡착볼 입자.Adsorption ball particles for lithium recovery that the size of the adsorption ball particles for lithium recovery is 20 ~ 1000㎛.
- 제 11항에 있어서,The method of claim 11,상기 리튬 회수용 흡착볼 입자의 복합금속산화물의 구조가 스피넬구조인 것인 리튬 회수용 흡착볼 입자.Adsorbent ball particles for lithium recovery that the structure of the composite metal oxide of the adsorption ball particles for lithium recovery is a spinel structure.
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| KR101182271B1 (en) * | 2011-04-28 | 2012-09-12 | 한국지질자원연구원 | Porous manganese oxide absorbent for Lithium having spinel type structure and a method of manufacturing the same |
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