JP2012055881A - Method for recovering lithium, and lithium recovering apparatus - Google Patents
Method for recovering lithium, and lithium recovering apparatus Download PDFInfo
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- JP2012055881A JP2012055881A JP2011169342A JP2011169342A JP2012055881A JP 2012055881 A JP2012055881 A JP 2012055881A JP 2011169342 A JP2011169342 A JP 2011169342A JP 2011169342 A JP2011169342 A JP 2011169342A JP 2012055881 A JP2012055881 A JP 2012055881A
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- lithium
- lithium ion
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 198
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 238000000034 method Methods 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 233
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 233
- 239000012528 membrane Substances 0.000 claims abstract description 198
- 238000011084 recovery Methods 0.000 claims abstract description 156
- 239000002608 ionic liquid Substances 0.000 claims abstract description 79
- 238000000909 electrodialysis Methods 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 239000013535 sea water Substances 0.000 claims abstract description 32
- 239000012466 permeate Substances 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 29
- 230000001681 protective effect Effects 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000001223 reverse osmosis Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 229920000544 Gore-Tex Polymers 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 6
- -1 chloride ions Chemical class 0.000 description 5
- 150000002641 lithium Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- OIDIRWZVUWCCCO-UHFFFAOYSA-N 1-ethylpyridin-1-ium Chemical compound CC[N+]1=CC=CC=C1 OIDIRWZVUWCCCO-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
本発明は、リチウムの回収方法およびリチウムの回収装置に関する。 The present invention relates to a lithium recovery method and a lithium recovery apparatus.
温暖化緩和に向けた低炭素化社会には、電気自動車、家庭用蓄電池等の大型リチウムイオン電池が必須であり、その電池製造には、ノートパソコン等の小型リチウムイオン電池の１０００倍のリチウム原料が必要である。また、核融合エネルギーの燃料の製造には、リチウムの同位体である６リチウム（６Ｌｉ）が大量に必要である。我が国にはレアメタルであるリチウムの鉱物資源がなく輸入に頼っているのが現状であり、資源の確保が望まれている。６リチウム（６Ｌｉ）はより希少であり海外からの輸入も困難であるため、資源の確保の要望はより強い。 Large-sized lithium-ion batteries such as electric vehicles and household storage batteries are indispensable for a low-carbon society to mitigate global warming. is required. In addition, the production of nuclear fusion energy fuel requires a large amount of 6 lithium ( 6 Li), which is an isotope of lithium. In Japan, there is no rare mineral of lithium, which is a rare metal, and we are relying on imports. 6 Lithium ( 6 Li) is more scarce and difficult to import from abroad, so the demand for securing resources is stronger.
一方、海水中には微量なリチウムが含まれており、リチウムを含む海水などの低濃度の溶液からリチウムを効率よく回収する技術の確立が求められている。特許文献１では、β−ジケトン、中性有機リン化合物および環状構造を有するビニルモノマーを原料として製造した吸着剤を用いてリチウムを回収する方法が提案されている。 On the other hand, seawater contains a small amount of lithium, and establishment of a technique for efficiently recovering lithium from a low-concentration solution such as seawater containing lithium is required. Patent Document 1 proposes a method of recovering lithium using an adsorbent produced using a β-diketone, a neutral organic phosphorus compound, and a vinyl monomer having a cyclic structure as raw materials.
特許文献１に記載の吸着剤は、吸着速度および吸着容量が大きい。しかしながら、吸着剤を用いたリチウムの回収方法には、吸着剤の寿命の限界、リチウム吸脱着プロセスが複雑、リチウム以外の元素も吸着する等、工業化のために改善すべき課題が依然として残されている。 The adsorbent described in Patent Document 1 has a large adsorption rate and adsorption capacity. However, lithium recovery methods using adsorbents still have problems to be improved for industrialization, such as the limit of the life of adsorbents, complicated lithium adsorption / desorption processes, and adsorption of elements other than lithium. Yes.
本発明は、以上の通りの事情に鑑みてなされたものであり、従来技術よりも工業化が容易であって、リチウムを含む海水などの低濃度の溶液からリチウムを選択的に効率よく回収できるリチウムの回収方法およびリチウムの回収装置を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and is easier to industrialize than the prior art, and can selectively recover lithium from a low-concentration solution such as seawater containing lithium. It is an object of the present invention to provide a recovery method and a lithium recovery device.
上記の課題を解決するために、本発明のリチウムの回収方法は、リチウムイオンを含む溶液中からリチウムイオンを選択的に分離回収するリチウムの回収方法であって、アノード電極とカソード電極との間にリチウムイオン選択性を有するイオン液体を含有するリチウムイオン選択的透過膜を配置することで電気透析槽を分画して前記アノード電極側にリチウム溶液セル、前記カソード電極側にリチウムイオン分離回収セルを形成し、前記リチウム溶液セルに前記溶液を供給し、電気透析法によって前記リチウムイオン選択的透過膜を透過して前記リチウムイオン分離回収セルに透析されるリチウムイオンを回収することを特徴とする。 In order to solve the above-described problems, the lithium recovery method of the present invention is a lithium recovery method for selectively separating and recovering lithium ions from a solution containing lithium ions, between the anode electrode and the cathode electrode. A lithium ion selective permeable membrane containing an ionic liquid having lithium ion selectivity is arranged on the electrodialysis tank to separate the lithium solution cell on the anode electrode side and the lithium ion separation and recovery cell on the cathode electrode side Forming the solution, supplying the solution to the lithium solution cell, and collecting lithium ions permeated through the lithium ion selective permeable membrane by electrodialysis to be dialyzed into the lithium ion separation and recovery cell. .
また、本発明の別のリチウムの回収方法は、リチウムイオンを含む溶液中からリチウムイオンを選択的に分離回収するリチウムの回収方法であって、アノード電極とカソード電極との間にリチウムイオン選択性を有するイオン液体を含有する複数のリチウムイオン選択的透過膜を配置することで電気透析槽を分画するとともに、隣り合う前記リチウムイオン選択的透過膜相互の間を陰イオン透過膜の配置で分画して、前記リチウムイオン選択的透過膜を挟んで前記アノード電極側にリチウム溶液セル、前記カソード電極側にリチウムイオン分離回収セルを形成し、前記リチウム溶液セルに前記溶液を供給し、電気透析法によって前記リチウムイオン選択的透過膜を透過して前記リチウムイオン分離回収セルに透析されるリチウムイオンを回収することを特徴とする。 Another lithium recovery method of the present invention is a lithium recovery method for selectively separating and recovering lithium ions from a solution containing lithium ions, wherein the lithium ion selectivity is provided between an anode electrode and a cathode electrode. The electrodialysis tank is fractionated by arranging a plurality of lithium ion selective permeable membranes containing an ionic liquid having ionic liquid, and the anion permeable membrane is divided between adjacent lithium ion selective permeable membranes. Forming a lithium solution cell on the anode electrode side and a lithium ion separation / recovery cell on the cathode electrode side by sandwiching the lithium ion selective permeable membrane, supplying the solution to the lithium solution cell, and performing electrodialysis Lithium ions permeated through the lithium ion selective permeable membrane by the method and dialyzed into the lithium ion separation and recovery cell are recovered. And wherein the Rukoto.
また、このリチウムの回収方法においては、前記リチウムイオン選択的透過膜は、イオン液体を膜に含浸させたものであることや、そのアノード電極側およびカソード電極側の一方または各々に陽イオン透過膜を配置した保護膜付リチウムイオン選択的透過膜であること、さらには、前記イオン液体を含浸させた膜と陽イオン透過膜との間にはイオン液体セルが介在されていることがその形態として好ましく考慮される。 Further, in this lithium recovery method, the lithium ion selective permeable membrane is obtained by impregnating a membrane with an ionic liquid, or a cation permeable membrane on one or each of the anode electrode side and the cathode electrode side. As a form, the lithium ion selective permeation membrane with a protective film is arranged, and further, an ionic liquid cell is interposed between the membrane impregnated with the ionic liquid and the cation permeation membrane. Considered preferably.
また、前記リチウムイオン選択的透過膜は、イオン液体セルのアノード電極側およびカソード電極側の各々に陽イオン透過膜を配置した保護膜付リチウムイオン選択的透過膜であることもその形態として考慮される。イオン液体が脱離することを低減もしくは防止するため、前記のように、陽イオン透過膜を配置することが好ましい。イオン液体が脱離することを低減もしくは防止するためには、イオン液体をゲル化する手法も効果的である。 In addition, the lithium ion selective permeable membrane may be a lithium ion selective permeable membrane with a protective film in which a cation permeable membrane is disposed on each of the anode electrode side and the cathode electrode side of the ionic liquid cell. The In order to reduce or prevent the ionic liquid from desorbing, it is preferable to dispose a cation permeable membrane as described above. In order to reduce or prevent the ionic liquid from desorbing, a method of gelling the ionic liquid is also effective.
そして、本発明のリチウムの回収方法においては、前記イオン液体が、（ＣＦ３ＳＯ２）２Ｎ−または（ＦＳＯ２）２Ｎ−を有するイオン液体であることが好ましい。 In the lithium recovery method of the present invention, the ionic liquid is preferably an ionic liquid having (CF 3 SO 2 ) 2 N — or (FSO 2 ) 2 N — .
海水等の低濃度のリチウムイオンを含む前記リチウムイオンを含む溶液から、本発明のリチウムの回収方法にてリチウムイオンを含む回収液を得た場合、回収液のリチウム濃度は低い。そこで、回収液のリチウム濃度を高くするために、逆浸透膜を用いた逆浸透法、または電気透析法により濃度調整を行うことが好ましい。 When a recovery liquid containing lithium ions is obtained from a solution containing lithium ions containing low concentration lithium ions such as seawater by the lithium recovery method of the present invention, the lithium concentration of the recovery liquid is low. Therefore, in order to increase the lithium concentration of the recovered liquid, it is preferable to adjust the concentration by a reverse osmosis method using a reverse osmosis membrane or an electrodialysis method.
更に、本発明のリチウムの回収方法において、前記リチウムイオン分離回収セルから回収したリチウムイオンを含む回収液中には塩化物イオン等のマイナスイオンを含む場合があるため、電解透析してマイナスイオンを除去し、前記回収液からリチウムを回収した後、乾燥処理により水酸化リチウム(ＬｉＯＨ)や炭酸リチウム(Ｌｉ２ＣＯ３)等のリチウム原料が得られる。 Furthermore, in the lithium recovery method of the present invention, the recovery solution containing lithium ions recovered from the lithium ion separation and recovery cell may contain negative ions such as chloride ions. After removing and recovering lithium from the recovery solution, a lithium raw material such as lithium hydroxide (LiOH) or lithium carbonate (Li 2 CO 3 ) is obtained by a drying treatment.
また、本発明のリチウムの回収方法は、前記リチウムイオンを含む溶液が、リチウムを含む海水などの低濃度の溶液からリチウムを回収できることが大きな特徴である。 The lithium recovery method of the present invention is characterized in that the lithium ion-containing solution can recover lithium from a low-concentration solution such as seawater containing lithium.
さらにまた、このリチウムの回収方法において、低電圧にて電気透析を行った場合は前記リチウムイオンを含む溶液に含まれるリチウムイオンが６リチウム（６Ｌｉ）同位体を多く含み、前記溶液中から前記６リチウム同位体を濃縮することも可能である。 Furthermore, in this lithium recovery method, when electrodialysis is performed at a low voltage, the lithium ions contained in the lithium ion-containing solution contain a large amount of 6 lithium ( 6 Li) isotopes, and It is also possible to concentrate 6 lithium isotopes.
本発明のリチウムの回収装置は、以上の方法を実現可能とするものである。 The lithium recovery apparatus of the present invention makes it possible to implement the above method.
すなわち、リチウムイオンを含む溶液中からリチウムイオンを選択的に分離回収するリチウムの回収装置であって、アノード電極とカソード電極とを有する電気透析槽と、この電気透析槽内に設けられ、前記アノード電極と前記カソード電極との間を分画して前記アノード電極側にリチウム溶液セル、前記カソード電極側にリチウムイオン分離回収セルを形成する、リチウムイオン選択性を有するイオン液体を含有するリチウムイオン選択的透過膜と、前記リチウム溶液セルにリチウムイオンを含む溶液を供給するリチウム供給手段と、前記リチウムイオン分離回収セルからリチウムイオンを含む溶液を回収するリチウム回収手段と、を備えていることを特徴とする。 That is, a lithium recovery device that selectively separates and recovers lithium ions from a solution containing lithium ions, an electrodialysis tank having an anode electrode and a cathode electrode, and provided in the electrodialysis tank, the anode Lithium ion selection containing an ionic liquid having lithium ion selectivity, forming a lithium solution cell on the anode electrode side and a lithium ion separation and recovery cell on the cathode electrode side by dividing between the electrode and the cathode electrode A lithium permeation membrane, a lithium supply means for supplying a solution containing lithium ions to the lithium solution cell, and a lithium recovery means for recovering a solution containing lithium ions from the lithium ion separation and recovery cell. And
また、本発明の別のリチウムの回収装置は、リチウムイオンを含む溶液中からリチウムイオンを選択的に分離回収するリチウムの回収装置であって、アノード電極とカソード電極とを有する電気透析槽と、この電気透析槽内に設けられ、前記アノード電極と前記カソード電極との間を分画する、リチウムイオン選択性を有するイオン液体を含有する複数のリチウムイオン選択的透過膜と、隣り合う前記リチウムイオン選択的透過膜相互の間に設けられ、前記リチウムイオン選択的透過膜を挟んで前記アノード電極側にリチウム溶液セル、前記カソード電極側にリチウムイオン分離回収セルを形成する陰イオン透過膜と、前記リチウム溶液セルにリチウムイオンを含む溶液を供給するリチウム供給手段と、前記リチウムイオン分離回収セルからリチウムイオンを含む溶液を回収するリチウム回収手段と、を備えていることを特徴とする。 Another lithium recovery apparatus of the present invention is a lithium recovery apparatus that selectively separates and recovers lithium ions from a solution containing lithium ions, an electrodialysis tank having an anode electrode and a cathode electrode, A plurality of lithium ion selective permeable membranes, which are provided in this electrodialysis tank and which contain an ionic liquid having lithium ion selectivity, which separates between the anode electrode and the cathode electrode, and the adjacent lithium ions An anion permeable membrane provided between the selectively permeable membranes and forming a lithium solution cell on the anode electrode side and a lithium ion separation and recovery cell on the cathode electrode side with the lithium ion selective permeable membrane interposed therebetween; Lithium supply means for supplying a solution containing lithium ions to the lithium solution cell, and the lithium ion separation and recovery cell Characterized in that it comprises a lithium recovery means for recovering the solution containing lithium ion, a.
このリチウムの回収装置においては、前記リチウムイオン選択的透過膜は、イオン液体を膜に含浸させたものであることや、そのアノード電極側およびカソード電極側の一方または各々に陽イオン透過膜を配置した保護膜付リチウムイオン選択的透過膜であること、さらには、前記イオン液体を含浸させた膜と陽イオン透過膜との間にはイオン液体セルが介在されていることがその形態として好ましく考慮される。 In this lithium recovery apparatus, the lithium ion selective permeable membrane is obtained by impregnating a membrane with an ionic liquid, or a cation permeable membrane is disposed on one or each of the anode electrode side and the cathode electrode side. Preferably, it is a lithium ion selective permeation membrane with a protective film, and that an ionic liquid cell is interposed between the membrane impregnated with the ionic liquid and the cation permeation membrane. Is done.
また、前記リチウムイオン選択的透過膜は、イオン液体セルのアノード電極側およびカソード電極側の各々に陽イオン透過膜を配置した保護膜付リチウムイオン選択的透過膜であることもその形態として考慮される。イオン液体が脱離することを低減もしくは防止するため、前記のように、陽イオン透過膜が配置されていることが好ましい。イオン液体が脱離することを低減もしくは防止するためには、イオン液体がゲル化されていることも効果的である。 In addition, the lithium ion selective permeable membrane may be a lithium ion selective permeable membrane with a protective film in which a cation permeable membrane is disposed on each of the anode electrode side and the cathode electrode side of the ionic liquid cell. The In order to reduce or prevent the ionic liquid from desorbing, it is preferable that the cation permeable membrane is disposed as described above. In order to reduce or prevent the ionic liquid from desorbing, it is also effective that the ionic liquid is gelled.
また、このリチウムの回収装置において、前記イオン液体が、（ＣＦ３ＳＯ２）２Ｎ−または（ＦＳＯ２）２Ｎ−を有するイオン液体であることが好ましい。 In this lithium recovery apparatus, the ionic liquid is preferably an ionic liquid having (CF 3 SO 2 ) 2 N − or (FSO 2 ) 2 N − .
さらには、前記リチウムイオン分離回収セルから回収したリチウムイオンを含む回収液を、逆浸透膜を使用した逆浸透膜法または電気透析法により濃度調整する濃度調整手段を備えていることや、前記リチウムイオン分離回収セルから回収したリチウムイオン回収液を電気透析してリチウム原料を回収する回収手段を備えていることも考慮される。 Further, the lithium ion separation and recovery cell is provided with a concentration adjusting means for adjusting the concentration of the recovered liquid containing lithium ions by a reverse osmosis membrane method using a reverse osmosis membrane or an electrodialysis method, It is also considered that a recovery means for recovering the lithium raw material by electrodialyzing the lithium ion recovery liquid recovered from the ion separation recovery cell is considered.
本発明によれば、工業化が容易な電気透析法を採用して、リチウムを含む海水などの低濃度の溶液からリチウムを選択的に効率よく回収することができる。 ADVANTAGE OF THE INVENTION According to this invention, the electrodialysis method with easy industrialization is employ | adopted, and lithium can be selectively collect | recovered efficiently from low concentration solutions, such as seawater containing lithium.
以下、本発明の実施形態について図面を参照して説明する。 Embodiments of the present invention will be described below with reference to the drawings.
図１は、リチウムの回収装置の一実施形態を示す模式図である。 FIG. 1 is a schematic view showing an embodiment of a lithium recovery apparatus.
図１（ａ）のリチウムの回収装置１は、電気透析槽２と、リチウムイオン選択的透過膜５と、リチウム供給手段６と、リチウム回収手段７と、を備えている。 The lithium recovery apparatus 1 in FIG. 1A includes an electrodialysis tank 2, a lithium ion selective permeable membrane 5, a lithium supply means 6, and a lithium recovery means 7.
電気透析槽２内の両側には、アノード電極３とカソード電極４とが配置されている。リチウムイオン選択的透過膜５は、アノード電極３とカソード電極４との間に配置され、電気透析槽２を分画しており、このリチウムイオン選択的透過膜５を挟んでアノード電極３側にリチウム溶液セル８が形成され、カソード電極４側にリチウムイオン分離回収セル９が形成されている。リチウム溶液セル８には、海水などリチウムイオンを含む溶液（以下、原液ともいう）が収納されており、リチウム供給手段６を構成する、原液を供給する供給路６ａおよび原液からリチウムイオンが減損したリチウムイオン減損液を排出する排出路６ｂが接続されている。リチウムイオン分離回収セル９には、リチウム溶液セル８から移動したリチウムイオンが収納されており、リチウム回収手段７を構成する、塩酸等を供給する供給路７ａおよびリチウム溶液セル８から移動したリチウムイオンを含む溶液（Ｌｉ回収液）を排出する排出路７ｂが接続されている。 An anode electrode 3 and a cathode electrode 4 are arranged on both sides in the electrodialysis tank 2. The lithium ion selective permeable membrane 5 is disposed between the anode electrode 3 and the cathode electrode 4 and separates the electrodialysis tank 2. The lithium ion selective permeable membrane 5 is disposed on the anode electrode 3 side with the lithium ion selective permeable membrane 5 interposed therebetween. A lithium solution cell 8 is formed, and a lithium ion separation and recovery cell 9 is formed on the cathode electrode 4 side. The lithium solution cell 8 contains a solution containing lithium ions such as seawater (hereinafter also referred to as a stock solution), and lithium ions are depleted from the stock solution supply path 6a constituting the lithium supply means 6 and the stock solution. A discharge path 6b for discharging the lithium ion depleting solution is connected. Lithium ions moved from the lithium solution cell 8 are accommodated in the lithium ion separation and recovery cell 9. The supply path 7 a for supplying hydrochloric acid and the like constituting the lithium recovery means 7 and the lithium ions moved from the lithium solution cell 8 are accommodated. A discharge path 7b for discharging a solution containing Li (Li recovery liquid) is connected.
なお、図１（ａ）の実施形態では、海水が供給路６ａからリチウム溶液セル８に供給され、希塩酸が供給路７ａからリチウムイオン分離回収セル９に供給されている。 In the embodiment of FIG. 1A, seawater is supplied from the supply path 6a to the lithium solution cell 8, and dilute hydrochloric acid is supplied from the supply path 7a to the lithium ion separation and recovery cell 9.
リチウムイオン選択的透過膜５は、リチウムイオン選択性を有するイオン液体を膜に含浸保持させて構成される。 The lithium ion selective permeable membrane 5 is configured by impregnating and holding an ionic liquid having lithium ion selectivity.
リチウムイオン選択性を有するイオン液体の具体例としては、PP13-TFSI（正式化学名：N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl) imide）、TMPA-TFSI（正式化学名：N,N,N-Trimethyl-N-propylammonium bis(trifluoromethanesulfonyl) imide）、P13-TFSI（正式化学名：N-Methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl) imide）やP14-TFSI（正式化学名：N-Methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl) imide）等が挙げらるが、これに限定されず、他のイオン液体であってもよい。他のイオン液体として、例えば、1-Alkyl-3methylimidazoliumをカチオンとしてTFSIアニオン（(CF3SO2)2N-）またはＦＳＩアニオン（（ＦＳＯ２）２Ｎ−）と組み合わせたイオン液体が挙げられる。このようなイオン液体として、1-Ethyl-3methylimidazolium bis(trifluoromethanesulfonyl)imideや、1-Ethyl -2,3methylimidazolium bis(trifluoromethanesulfonyl)imide等のイミダゾリウム系イオン液体、1-Ethylpyridinium bis(trifluoromethanesulfonyl)imideや1-Butylpyridinium bis(trifluoromethanesulfonyl)imide等のピリジニウム系イオン液体、Trimethylphosphonium bis(trifluoromethanesulfonyl)imide、Polyethyleneoxide(PEO) bis(trifluoromethanesulfonyl)imide等のイオン液体等が挙げられる。他にもスルフォン酸型Zwitterion、カルボン酸型Zwitterion、イミド酸型Zwitterion、ボレート型ZwitterionにそれぞれTFSIアニオンまたはＦＳＩアニオンを組み合わせたイオン液体等も挙げられる。上記したイオン液体のなかでもTFSIアニオンまたはＦＳＩアニオンを含むイオン液体が好適であり、良好なリチウムイオン伝導性を有する。 Specific examples of ionic liquids having lithium ion selectivity include PP13-TFSI (official chemical name: N-Methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide), TMPA-TFSI (official chemical name: N, N, N- Trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide), P13-TFSI (official chemical name: N-Methyl-N-propylpyrrolidinium bis) and P14-TFSI (official chemical name: N-Methyl-N-butylpyrrolidinium bis) (trifluoromethanesulfonyl) imide) and the like, but is not limited thereto, and other ionic liquids may be used. Examples of other ionic liquids include ionic liquids in which 1-Alkyl-3methylimidazolium is used as a cation and combined with a TFSI anion ((CF 3 SO 2 ) 2 N − ) or an FSI anion ((FSO 2 ) 2 N − ). Such ionic liquids include imidazolium-based ionic liquids such as 1-Ethyl-3methylimidazolium bis (trifluoromethanesulfonyl) imide and 1-Ethyl-2,3methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-Ethylpyridinium bis (trifluoromethanesulfonyl) imide and 1-Ethylpyridinium bis (trifluoromethanesulfonyl) imide. Examples thereof include pyridinium ionic liquids such as Butylpyridinium bis (trifluoromethanesulfonyl) imide, and ionic liquids such as Trimethylphosphonium bis (trifluoromethanesulfonyl) imide and Polyethyleneoxide (PEO) bis (trifluoromethanesulfonyl) imide. Other examples include sulfonic acid type Zwitterion, carboxylic acid type Zwitterion, imido acid type Zwitterion, borate type Zwitterion, and ionic liquids in which TFSI anion or FSI anion is combined. Among the ionic liquids described above, TFSI anions or ionic liquids containing FSI anions are suitable and have good lithium ion conductivity.
イオン液体を含浸させる膜は、イオン液体を含浸させることができればどのような材質でもよく、特に制限されるものではない。疎水性の材料を採用することもできる。具体例として、有機質の隔膜構造が緻密になっている密構造緻密有機隔膜（商品名、登録商標：ゴアテックス）や、有機質の多孔質隔膜から構成される多孔質有機隔膜（商品名、登録商標：ポアフロン）等が挙げられる。 The membrane impregnated with the ionic liquid may be any material as long as it can be impregnated with the ionic liquid, and is not particularly limited. Hydrophobic materials can also be employed. As a specific example, a dense organic membrane with a dense organic membrane structure (trade name, registered trademark: Gore-Tex) and a porous organic membrane (trade name, registered trademark) composed of an organic porous membrane. : Pore-Flon) and the like.
リチウムイオン選択的透過膜５の両側に、すなわち、アノード電極３側およびカソード電極４側に図２（ａ）のように陽イオン透過膜１０が保護膜として各々配置されていてもよい。陽イオン透過膜１０は、陽イオンの透過性能を有する膜であれば特に制限されるものではなく、例えば、陽イオン交換膜、ナフィオン（登録商標）、膜・電極接合体(MEA)等が挙げられる。 The cation permeable membrane 10 may be disposed on both sides of the lithium ion selective permeable membrane 5, that is, on the anode electrode 3 side and the cathode electrode 4 side, respectively, as a protective membrane as shown in FIG. The cation permeable membrane 10 is not particularly limited as long as it has a cation permeability, and examples thereof include a cation exchange membrane, Nafion (registered trademark), and a membrane / electrode assembly (MEA). It is done.
この態様では、保護膜付リチウムイオン選択的透過膜１１が形成される。また、陽イオン透過膜１０の配置の具体的な態様としては、図２（ｂ）に示すように、イオン液体を収納するイオン液体セル１２を、リチウムイオン選択的透過膜５に隣接して形成し、その外側に陽イオン透過膜１０を配設することもできる。更に、本発明では、リチウムイオン選択性を有するイオン液体を膜に含浸保持せず、図２（ｃ）に示すように、イオン液体を収納するイオン液体セル１２の外側に陽イオン透過膜１０を配設し、保護膜付リチウムイオン選択的透過膜１３が形成することもできる。図１（ｂ）のリチウムの回収装置１は、電気透析槽２と、イオン液体を収納するイオン液体セル１２と、その外側に陽イオン透過膜１０と、リチウム供給手段６と、リチウム回収手段７と、を備えている。このように、リチウムイオン選択性を有するイオン液体を膜に含浸保持しない手法もある。いずれの構成も陽イオン透過膜１０の外側へイオン液体が脱離することを低減もしくは防止できるので、リチウムの回収装置１としてはリチウムイオンの透過性が良好であり、リチウムの回収率を向上させることができる。また、イオン液体をゲル化させ、リチウムイオン選択的透過膜５中に、あるいは図２（ｃ）のイオン液体セル１２中にイオン液体を保持させる手法もある。 In this embodiment, the lithium ion selective permeable membrane 11 with a protective film is formed. Further, as a specific aspect of the arrangement of the cation permeable membrane 10, as shown in FIG. 2B, an ionic liquid cell 12 containing an ionic liquid is formed adjacent to the lithium ion selective permeable membrane 5. In addition, the cation permeable membrane 10 can be disposed on the outside thereof. Furthermore, in the present invention, the ionic liquid having lithium ion selectivity is not impregnated and held in the membrane, and the cation permeable membrane 10 is disposed outside the ionic liquid cell 12 containing the ionic liquid as shown in FIG. The lithium ion selective permeable membrane 13 with a protective film may be formed. The lithium recovery device 1 shown in FIG. 1B includes an electrodialysis tank 2, an ionic liquid cell 12 containing an ionic liquid, a cation permeable membrane 10, a lithium supply means 6, and a lithium recovery means 7 outside thereof. And. As described above, there is also a technique in which the membrane is not impregnated with the ionic liquid having lithium ion selectivity. Since any configuration can reduce or prevent the ionic liquid from desorbing to the outside of the cation permeable membrane 10, the lithium recovery device 1 has good lithium ion permeability and improves the lithium recovery rate. be able to. There is also a technique in which the ionic liquid is gelled and the ionic liquid is held in the lithium ion selective permeable membrane 5 or in the ionic liquid cell 12 of FIG.
本実施形態のリチウムの回収装置１では、電気透析槽２内の両側に設けられたアノード電極３およびカソード電極４に直流電流を印加すると、リチウム溶液セル８内の海水中の陽イオンおよび陰イオンが逆極性の電極側に移動する。 In the lithium recovery apparatus 1 of the present embodiment, when a direct current is applied to the anode electrode 3 and the cathode electrode 4 provided on both sides in the electrodialysis tank 2, cations and anions in seawater in the lithium solution cell 8. Moves to the opposite polarity electrode side.
リチウム溶液セル８内の海水中の陽イオンはカソード電極４側に移動するが、リチウムイオンだけがリチウムイオン選択的透過膜５を通過してリチウムイオン分離回収セル９へ移動し、海水中のナトリウムイオン、マグネシウムイオン、カルシウムイオン、カリウムイオンなど、リチウムイオンを除く他の陽イオンはリチウムイオン選択的透過膜５を通過できずにリチウムイオン減損液として排出路６ｂから排出される。排出された、リチウムイオンが減損した海水（リチウムイオン減損液）は、再度、供給路６ａを通じてリチウム溶液セル８に供給することができる。 The cations in the seawater in the lithium solution cell 8 move to the cathode electrode 4 side, but only the lithium ions pass through the lithium ion selective permeable membrane 5 and move to the lithium ion separation / recovery cell 9, and sodium in the seawater. Other cations other than lithium ions, such as ions, magnesium ions, calcium ions, and potassium ions, cannot pass through the lithium ion selective permeable membrane 5 and are discharged from the discharge path 6b as a lithium ion depleted solution. The discharged seawater (lithium ion-depleted solution) in which lithium ions are impaired can be supplied again to the lithium solution cell 8 through the supply path 6a.
リチウム溶液セル８内の海水中の陰イオン、例えば塩化物イオンはアノード電極３に引き寄せられ、塩素ガス（Ｃｌ２）が生成する。 Anions, such as chloride ions, in the seawater in the lithium solution cell 8 are attracted to the anode electrode 3 to generate chlorine gas (Cl 2 ).
リチウムイオン分離回収セル９では、希塩酸が水素イオンと塩化物イオンに電離される。塩化物イオンはリチウム溶液セル８から移動してきたリチウムイオンと塩を形成しＬｉ回収液として排出路７ｂから排出される。排出されたＬｉ回収液は、再度、供給路７ａを通じてリチウムイオン分離回収セル９に供給することができる。水素イオンはカソード電極４に引き寄せられ、水素ガス（Ｈ２）が生成する。 In the lithium ion separation and recovery cell 9, dilute hydrochloric acid is ionized into hydrogen ions and chloride ions. Chloride ions form a salt with the lithium ions that have moved from the lithium solution cell 8, and are discharged from the discharge path 7b as Li recovery liquid. The discharged Li recovery liquid can be supplied again to the lithium ion separation and recovery cell 9 through the supply path 7a. Hydrogen ions are attracted to the cathode electrode 4 to generate hydrogen gas (H 2 ).
上記した図１のリチウムの回収装置１は、リチウムイオン選択的透過膜５が１枚使用され、リチウム溶液セル８およびリチウムイオン分離回収セル９が各々１つ有する単セル構造である。実使用では生産性等を考慮し、リチウム溶液セル８およびリチウムイオン分離回収セル９がそれぞれ複数形成されるように、リチウムイオン選択的透過膜５が複数枚使用され、単セルが並列的に並べられたスタック構造とすることもできる。 1 has a single cell structure in which one lithium ion selective permeable membrane 5 is used and one lithium solution cell 8 and one lithium ion separation / recovery cell 9 are provided. In actual use, in consideration of productivity and the like, a plurality of lithium ion selective permeable membranes 5 are used so that a plurality of lithium solution cells 8 and a plurality of lithium ion separation / recovery cells 9 are formed, and single cells are arranged in parallel. It is also possible to have a stacked structure.
図３は、このようなスタック構造のリチウムの回収装置の一実施形態を示す模式図である。図１、２に示したリチウムの回収装置と同じ部分には同一の符号を付し、その説明を省略する。 FIG. 3 is a schematic view showing an embodiment of a lithium recovery apparatus having such a stack structure. The same parts as those in the lithium recovery apparatus shown in FIGS.
図３のリチウムの回収装置１は、電気透析槽２と、複数枚のリチウムイオン選択的透過膜５と、複数枚の陰イオン透過膜１５と、リチウム供給手段６と、リチウム回収手段７と、を備えている。 3 includes an electrodialysis tank 2, a plurality of lithium ion selective permeable membranes 5, a plurality of anion permeable membranes 15, a lithium supply means 6, a lithium recovery means 7, It has.
本実施形態では、アノード電極３とカソード電極４との間にリチウムイオン選択的透過膜５が３枚配置されている。そして、隣り合うリチウムイオン選択的透過膜５同士の間に陰イオン透過膜１５が配置され、電気透析槽２が分画されている。このリチウムイオン選択的透過膜５と陰イオン透過膜１５とにより、リチウムイオン選択的透過膜５を挟んでアノード電極３側にはリチウム溶液セル８ａ，８ｂ，８ｃが形成され、カソード電極４側にはリチウムイオン分離回収セル９ａ，９ｂ，９ｃが形成されている。図３に示すように、アノード電極３に最も近いリチウムイオン選択的透過膜５とアノード電極３との間に陰イオン透過膜１５を配置し、カソード電極４に最も近いリチウムイオン選択的透過膜５とカソード電極４との間に陽イオン透過膜１６を配置することもできる。また、図１の実施形態と同様、海水が供給路６ａからリチウム溶液セル８ａ，８ｂ，８ｃに供給され、希塩酸が供給路７ａからリチウムイオン分離回収セル９ａ，９ｂ，９ｃに供給されている。 In this embodiment, three lithium ion selective permeable membranes 5 are arranged between the anode electrode 3 and the cathode electrode 4. And the anion permeable membrane 15 is arrange | positioned between the lithium ion selective permeable membranes 5 adjacent, and the electrodialysis tank 2 is fractionated. The lithium ion selective permeable membrane 5 and the anion permeable membrane 15 form lithium solution cells 8a, 8b, 8c on the anode electrode 3 side with the lithium ion selective permeable membrane 5 interposed therebetween, and on the cathode electrode 4 side. Are formed with lithium ion separation and recovery cells 9a, 9b, 9c. As shown in FIG. 3, an anion permeable membrane 15 is disposed between the lithium ion selective permeable membrane 5 closest to the anode electrode 3 and the anode electrode 3, and the lithium ion selective permeable membrane 5 closest to the cathode electrode 4. A cation permeable membrane 16 may be disposed between the cathode electrode 4 and the cathode electrode 4. As in the embodiment of FIG. 1, seawater is supplied from the supply path 6a to the lithium solution cells 8a, 8b, and 8c, and diluted hydrochloric acid is supplied from the supply path 7a to the lithium ion separation and recovery cells 9a, 9b, and 9c.
本実施形態では、リチウム供給手段６を構成する供給路６ａおよび排出路６ｂが接続され、循環路１４を形成し、各リチウム溶液セル８ａ，８ｂ，８ｃには海水が循環して流れるようになっている。また、リチウム回収手段７を構成する供給路７ａおよび排出路７ｂが接続され、循環路１５を形成し、各リチウムイオン分離回収セル９ａ，９ｂ，９ｃには希塩酸（Ｌｉ回収液を含む）が循環して流れるようになっている。 In this embodiment, the supply path 6a and the discharge path 6b which comprise the lithium supply means 6 are connected, the circulation path 14 is formed, and seawater circulates and flows through each lithium solution cell 8a, 8b, 8c. ing. A supply path 7a and a discharge path 7b constituting the lithium recovery means 7 are connected to form a circulation path 15, and dilute hydrochloric acid (including a Li recovery liquid) is circulated in each lithium ion separation / recovery cell 9a, 9b, 9c. And is flowing.
陰イオン透過膜１５は、陰イオンの透過性能を有する膜であれば特に制限されるものではなく、例えば、陰イオン交換膜等が挙げられる。 The anion permeable membrane 15 is not particularly limited as long as it has an anion permeation performance, and examples thereof include an anion exchange membrane.
陽イオン透過膜１６は、陽イオンの透過性能を有する膜であれば特に制限されるものではなく、例えば、陽イオン交換膜等が挙げられる。 The cation permeable membrane 16 is not particularly limited as long as it has a cation permeability, and examples thereof include a cation exchange membrane.
本実施形態のリチウムの回収装置１においても、電気透析槽２内の両側に設けられたアノード電極３およびカソード電極４に直流電流を印加すると、リチウム溶液セル８ａ，８ｂ，８ｃ内の海水中の陽イオンおよび陰イオンが逆極性の電極側に移動する。 Also in the lithium recovery apparatus 1 of the present embodiment, when a direct current is applied to the anode electrode 3 and the cathode electrode 4 provided on both sides of the electrodialysis tank 2, the lithium solution cells 8a, 8b, 8c Cations and anions move to the opposite polarity electrode side.
リチウム溶液セル８ａ，８ｂ，８ｃ内の海水中の陽イオンはカソード電極４側に移動するが、リチウムイオンだけがリチウムイオン選択的透過膜５を通過して隣接するリチウムイオン分離回収セル９ａ，９ｂ，９ｃへ移動し、海水中のナトリウムイオン、マグネシウムイオン、カルシウムイオン、カリウムイオンなど、リチウムイオンを除く他の陽イオンはリチウムイオン選択的透過膜５を通過できずにリチウムイオン減損液として排出路６ｂから排出される。排出された、リチウムイオンが減損した海水（リチウムイオン減損液）は、循環路１４を通じて各リチウム溶液セル８ａ，８ｂ，８ｃに供給される。 The cations in the seawater in the lithium solution cells 8a, 8b and 8c move to the cathode electrode 4, but only lithium ions pass through the lithium ion selective permeable membrane 5 and are adjacent to the lithium ion separation and recovery cells 9a and 9b. , 9c, and other cations other than lithium ions such as sodium ion, magnesium ion, calcium ion and potassium ion in seawater cannot pass through the lithium ion selective permeable membrane 5 and are discharged as a lithium ion depletion solution. It is discharged from 6b. The discharged seawater (lithium ion-depleted solution) in which lithium ions are impaired is supplied to the lithium solution cells 8a, 8b, and 8c through the circulation path 14.
複数のリチウム溶液セル８ａ，８ｂ，８ｃのうち、最もアノード電極３に近いリチウム溶液セル８ａ内の海水中の陰イオン、例えば塩化物イオンはアノード電極３に引き寄せられ、陰イオン透過膜１５を通過して塩素ガス（Ｃｌ２）が生成する。それ以外のリチウム溶液セル８ｂ，８ｃ内の海水中の陰イオンは、隣接する陰イオン透過膜１５を通過してリチウムイオン分離回収セル９ａ，９ｂへ移動する。 Among the plurality of lithium solution cells 8a, 8b, 8c, anions in seawater in the lithium solution cell 8a closest to the anode electrode 3, for example, chloride ions, are attracted to the anode electrode 3 and pass through the anion permeable membrane 15. As a result, chlorine gas (Cl 2 ) is generated. The other anions in the seawater in the lithium solution cells 8b and 8c pass through the adjacent anion permeable membrane 15 and move to the lithium ion separation and recovery cells 9a and 9b.
リチウムイオン分離回収セル９ａ，９ｂ，９ｃでは、希塩酸が水素イオンと塩化物イオンに電離される。希塩酸から電離した塩化物イオンおよび隣接するリチウム溶液セル８ｂ，８ｃから移動してきた塩化物イオンは、リチウムイオン選択的透過膜５を通過して移動してきたリチウムイオンと塩を形成しＬｉ回収液として排出路７ｂから排出される。排出されたＬｉ回収液は希塩酸とともに循環路１５を通じて各リチウムイオン分離回収セル９ａ，９ｂ，９ｃに供給される。 In the lithium ion separation / recovery cells 9a, 9b, 9c, dilute hydrochloric acid is ionized into hydrogen ions and chloride ions. Chloride ions ionized from dilute hydrochloric acid and chloride ions that have migrated from the adjacent lithium solution cells 8b and 8c form salts with lithium ions that have migrated through the lithium ion selective permeable membrane 5 to form a Li recovery solution. It is discharged from the discharge path 7b. The discharged Li recovery liquid is supplied to each lithium ion separation / recovery cell 9a, 9b, 9c through the circulation path 15 together with dilute hydrochloric acid.
複数のリチウムイオン分離回収セル９ａ，９ｂ，９ｃのうち、最もカソード電極４に近いリチウムイオン分離回収セル９ｃ内の水素イオンはカソード電極に引き寄せられ、陽イオン透過膜１６を通過して水素ガス（Ｈ２）が生成する。 Among the plurality of lithium ion separation / recovery cells 9a, 9b, 9c, hydrogen ions in the lithium ion separation / recovery cell 9c closest to the cathode electrode 4 are attracted to the cathode electrode and pass through the cation permeable membrane 16 to hydrogen gas ( H 2 ) is produced.
図４のリチウムの回収装置１は、図３のリチウムの回収装置１の変形例である。この実施形態では、リチウムイオン選択的透過膜５として、例えば、図２（ａ）に示した保護膜付リチウムイオン選択的透過膜１１や図２（ｃ）に示した保護膜付リチウムイオン選択的透過膜１３を使用することができる。 A lithium recovery device 1 in FIG. 4 is a modification of the lithium recovery device 1 in FIG. 3. In this embodiment, as the lithium ion selective permeable membrane 5, for example, the lithium ion selective permeable membrane 11 with a protective film shown in FIG. 2A or the lithium ion selective permeable membrane with a protective film shown in FIG. A permeable membrane 13 can be used.
上記した図１（ａ）（ｂ），３，４のリチウムの回収装置１は、リチウムイオン以外の金属イオンが共存していても低濃度のリチウムイオンを含む溶液からリチウムイオンを選択的に効率よく回収できる。更に、低電圧にて電気透析を行った場合は、６リチウム（６Ｌｉ）同位体を多く含むＬｉ回収液を得ることができ、６リチウム同位体を濃縮することも可能である。また、工業化がし易くスケールアップも容易である。さらに図３や図４のように、リチウム溶液セル８およびリチウムイオン分離回収セル９を複数形成できるので生産性を低コストで効果的に高めることができるという利点を有する。 1 (a), 1 (b), 3 and 4 described above, the lithium recovery device 1 selectively converts lithium ions from a solution containing low-concentration lithium ions even when metal ions other than lithium ions coexist. Can be recovered well. Furthermore, when electrodialysis is performed at a low voltage, a Li recovery solution containing a large amount of 6 lithium ( 6 Li) isotopes can be obtained, and the 6 lithium isotopes can be concentrated. It is also easy to industrialize and scale up. Further, as shown in FIGS. 3 and 4, since a plurality of lithium solution cells 8 and lithium ion separation / recovery cells 9 can be formed, there is an advantage that productivity can be effectively increased at low cost.
上記のリチウムの回収装置１において、排出路６ｂを通じて回収したＬｉ回収液は、一般的にはリチウムイオン濃度が低い。このため、逆浸透膜を用いた逆浸透法、または電気透析法によりリチウムイオン濃度の調整をして回収することができる。 In the lithium recovery apparatus 1 described above, the Li recovery liquid recovered through the discharge path 6b generally has a low lithium ion concentration. For this reason, the lithium ion concentration can be adjusted and recovered by a reverse osmosis method using a reverse osmosis membrane or an electrodialysis method.
図５は、逆浸透膜１８を利用したＬｉ回収液の濃度調整装置１７の模式図である。 FIG. 5 is a schematic diagram of the concentration adjustment device 17 for the Li recovery liquid using the reverse osmosis membrane 18.
本装置において濃度調整されるＬｉ回収液は、例えばリチウムイオンと塩化物イオンとが塩として溶解している水溶液である。このＬｉ回収液に浸透圧以上の圧力を加えると水のみが逆浸透膜１８を透過し、Ｌｉ回収液のリチウムイオン濃度が高まる。このように逆浸透膜１８を利用することでＬｉ回収液のリチウムイオンの濃度調整を行うことができる。逆浸透膜１８の材質は、特に制限されるものではなく、酢酸セルロース、芳香族ポリアミド等が挙げられ、逆浸透膜１８としては市販品を使用することができる。 The Li recovery liquid whose concentration is adjusted in this apparatus is, for example, an aqueous solution in which lithium ions and chloride ions are dissolved as salts. When a pressure equal to or higher than the osmotic pressure is applied to this Li recovery liquid, only water permeates the reverse osmosis membrane 18 and the lithium ion concentration of the Li recovery liquid increases. Thus, by using the reverse osmosis membrane 18, the concentration of lithium ions in the Li recovery liquid can be adjusted. The material of the reverse osmosis membrane 18 is not particularly limited, and examples thereof include cellulose acetate and aromatic polyamide. A commercially available product can be used as the reverse osmosis membrane 18.
逆浸透膜１８を利用した方法以外の方法としては、例えば、陽イオン透過膜等を用いてリチウムイオンを透過させるなど、電気透析法によってもＬｉ回収液のリチウムイオンの濃度調整を行うことができる。 As a method other than the method using the reverse osmosis membrane 18, for example, the lithium ion concentration of the Li recovered liquid can be adjusted by electrodialysis, such as allowing lithium ions to permeate using a cation permeable membrane or the like. .
さらにＬｉ回収液からリチウム原料として水酸化リチウム(ＬｉＯＨ)や炭酸リチウム(Ｌｉ２ＣＯ３)を得る方法として、電解透析法を利用することができる。 Furthermore, as a method for obtaining lithium hydroxide (LiOH) or lithium carbonate (Li 2 CO 3 ) as a lithium raw material from the Li recovery liquid, an electrodialysis method can be used.
図６は、電解透析法を利用したＬｉ回収液の電解透析Ｌｉ原料精製装置１９の模式図である。 FIG. 6 is a schematic diagram of an electrodialysis Li raw material purifying apparatus 19 for Li recovery liquid using electrodialysis.
電解透析Ｌｉ原料精製装置１９では、電解透析槽２０のカソード電極２２側に陽イオン透過膜１６が配置され、アノード電極２１側に陰イオン透過膜１５が配置される。電解透析Ｌｉ原料精製装置１９に供給されるＬｉ回収液は、上記のリチウムの回収装置１において排出路７ｂを通じて回収されたＬｉ回収液である。また、この排出路７ｂを通じて回収されたＬｉ回収液を、一旦、逆浸透膜や電気透析等で濃度調整し、再度、この濃度調整した回収液を電解透析Ｌｉ原料精製装置１９に供給することもできる。 In the electrodialysis Li raw material purification device 19, the cation permeable membrane 16 is disposed on the cathode electrode 22 side of the electrodialysis tank 20, and the anion permeable membrane 15 is disposed on the anode electrode 21 side. The Li recovery liquid supplied to the electrodialysis Li raw material purification apparatus 19 is the Li recovery liquid recovered through the discharge path 7b in the lithium recovery apparatus 1 described above. Further, the concentration of the Li recovered solution recovered through the discharge passage 7b is once adjusted by a reverse osmosis membrane or electrodialysis, and the concentration adjusted recovered solution is supplied again to the electrodialysis Li raw material purifier 19. it can.
電解透析Ｌｉ原料精製装置１９のカソード反応及びアノード反応は、Ｌｉ回収液がリチウムイオンと塩化物イオンとが塩として溶解している水溶液の場合には、次のようになる。
［カソード反応］ ２Ｌｉ＋＋２Ｈ２Ｏ＋２ｅ− → ２ＬｉＯＨ＋Ｈ２↑
［アノード反応］ ２Ｃｌ−＋Ｈ２Ｏ＋２ｅ− → ２ＨＣｌ＋１／２Ｏ２↑
カソード反応で生成したＬｉＯＨ溶液を乾燥することでＬｉＯＨ・Ｈ２Ｏ粉末を得、リチウム原料を回収することができる。
The cathode reaction and anode reaction of the electrodialysis Li raw material purifier 19 are as follows when the Li recovery solution is an aqueous solution in which lithium ions and chloride ions are dissolved as salts.
[Cathode reaction] 2Li + + 2H 2 O + 2e − → 2LiOH + H 2 ↑
[Anode Reaction] 2Cl − + H 2 O + 2e − → 2HCl + 1 / 2O 2 ↑
LiOH.H 2 O powder can be obtained by drying the LiOH solution generated by the cathode reaction, and the lithium raw material can be recovered.
以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
＜実施例１＞
図１（ａ）のリチウムの回収装置１を用い、リチウム溶液セル８には海水（大洗海岸の海水をろ過して固形分を除去したもの）、リチウムイオン分離回収セル９には純水Ｈ２Ｏを通液し、１００ｍＡ、１時間の電気透析を行った。
<Example 1>
The lithium recovery device 1 of FIG. 1A is used. The lithium solution cell 8 has seawater (filtered off seawater from Oarai Beach to remove solids), and the lithium ion separation and recovery cell 9 has pure water H 2. O was passed through and electrodialysis was performed at 100 mA for 1 hour.
リチウムイオン選択的透過膜５は、イオン液体PP13-TFSIを密構造緻密有機隔膜（ジャパンゴアテックス（株）製、ゴアテックスハイパーシートＳＧ１０Ｘ）に含浸させた膜を使用した。 As the lithium ion selective permeable membrane 5, a membrane obtained by impregnating an ionic liquid PP13-TFSI into a dense structure dense organic diaphragm (Japan Gore-Tex Co., Ltd., Gore-Tex Hyper Sheet SG10X) was used.
また、上記のリチウムの回収装置１において、リチウムイオン選択的透過膜５を使用する代わりに、このリチウムイオン選択的透過膜５の両側に図２（ａ）のように陽イオン透過膜１０（旭硝子（株）製、セレミオン（登録商標）ＣＭＶ）を保護膜として配設した保護膜付リチウムイオン選択的透過膜１１を使用し、同条件にて電気透析を行った。 Further, in the lithium recovery apparatus 1, instead of using the lithium ion selective permeable membrane 5, a cation permeable membrane 10 (Asahi Glass as shown in FIG. 2A) is formed on both sides of the lithium ion selective permeable membrane 5. Electrodialysis was performed under the same conditions using a lithium ion selective permeation membrane 11 with a protective film in which Selemion (registered trademark) CMV (manufactured by Co., Ltd.) was disposed as a protective film.
その結果を表１に示す。 The results are shown in Table 1.
電気透析の結果、海水の主成分であるナトリウム（Ｎａ）イオン、マグネシウム（Ｍｇ）イオン、およびカルシウム（Ｃａ）イオンは、リチウムイオン選択的透過膜５および保護膜付リチウムイオン選択的透過膜１１を透過せず（分離率はほぼ１００％）、リチウム（Ｌｉ）イオンのみが透過し、海水からリチウムを選択的に回収できることが確認できた。また、保護膜付リチウムイオン選択的透過膜１１を用いた方がリチウムイオン選択的透過膜５を用いたよりもリチウムの回収率が高いことが確認できた。
＜実施例２＞
更に、他の陽イオン交換膜１０においてもリチウムが透過可能であることを確認するため、上記実施例１のリチウムの回収装置１において、リチウムイオン選択的透過膜５の両側に膜・電極接合体(MEA)１０（ケニス（株）製、MEA(型式：JP-STD)）を保護膜として配置した保護膜付リチウムイオン選択的透過膜１１を使用し、リチウム溶液セル８には海水（泊海岸の海水をろ過して固形分を除去したもの）、リチウムイオン分離回収セル９には０．１ｍｏｌ％塩酸ＨＣｌを通液し、2V、24時間の電気透析を行った。
As a result of electrodialysis, sodium (Na) ions, magnesium (Mg) ions, and calcium (Ca) ions, which are main components of seawater, pass through the lithium ion selective permeable membrane 5 and the lithium ion selective permeable membrane 11 with a protective membrane. It was confirmed that lithium did not permeate (separation rate was almost 100%), only lithium (Li) ions permeated, and lithium could be selectively recovered from seawater. Further, it was confirmed that the lithium recovery rate was higher when the lithium ion selective permeable membrane 11 with the protective film was used than when the lithium ion selective permeable membrane 5 was used.
<Example 2>
Further, in order to confirm that lithium can also permeate through other cation exchange membranes 10, in the lithium recovery device 1 of Example 1 above, membrane / electrode assemblies on both sides of the lithium ion selective permeable membrane 5. (MEA) 10 (manufactured by Kennis Co., Ltd., MEA (model: JP-STD)) is used as a protective membrane and a lithium ion selective permeable membrane 11 with a protective membrane is used. The solids were removed by filtration of the seawater), and 0.1 mol% hydrochloric acid HCl was passed through the lithium ion separation and recovery cell 9 and electrodialysis was performed at 2 V for 24 hours.
その結果を表２に示す。 The results are shown in Table 2.
電気透析の結果、前記実施例１でのセレミオンＣＭＶと同様に、膜・電極接合体(MEA)のような陽イオンを透過する性質を有する材料を保護膜として用いることで、海水からリチウムを回収できることが確認できた。
＜実施例３＞
一方、図２（ｃ）のように、イオン液体１２を例えば実施例１での密構造緻密有機隔膜（ジャパンゴアテックス（株）製、ゴアテックスハイパーシートＳＧ１０Ｘ）に含浸せず、イオン液体１２の両端に陽イオン透過膜１０膜を配置したリチウムイオン選択的透過膜１３としても使用可能である。
As a result of electrodialysis, lithium is recovered from seawater by using a material having a property of transmitting a cation such as a membrane-electrode assembly (MEA) as a protective membrane, similar to the selemion CMV in Example 1. I was able to confirm that it was possible.
<Example 3>
On the other hand, as shown in FIG. 2C, the ionic liquid 12 is not impregnated into the dense structure dense organic diaphragm (for example, Gore-Tex Hypersheet SG10X, manufactured by Japan Gore-Tex Co., Ltd.) in Example 1, and both ends of the ionic liquid 12 are used. It can also be used as a lithium ion selective permeable membrane 13 in which a cation permeable membrane 10 is disposed.
図１（ｂ）のリチウムの回収装置１を用い、イオン液体PP13-TFSIの両側にナフィオン等の陽イオン透過膜の両端に微量の白金触媒を添加したカーボンを接着した膜である膜・電極接合体(MEA)１０（ケニス（株）製、MEA(型式：JP-STD)）を配置したリチウムイオン選択的透過膜１３を使用し、リチウム溶液セル８には０．１ｍｏｌ％塩化リチウムＬｉＣｌ、リチウムイオン分離回収セル９には０．００１ｍｏｌ％塩酸ＨＣｌを通液し、５Ｖ、１時間の電気透析を行った。 Using the lithium recovery device 1 in FIG. 1 (b), a membrane / electrode junction that is a membrane in which carbon is added to both ends of a cation permeable membrane such as Nafion on both sides of the ionic liquid PP13-TFSI with a small amount of platinum catalyst added. The lithium ion selective permeable membrane 13 in which the body (MEA) 10 (manufactured by Kennis Co., Ltd., MEA (model: JP-STD)) is disposed is used, and the lithium solution cell 8 has 0.1 mol% lithium chloride LiCl, lithium 0.001 mol% HCl HCl was passed through the ion separation and recovery cell 9 and electrodialysis was performed at 5 V for 1 hour.
その結果を表３に示す。 The results are shown in Table 3.
電気透析の結果、リチウムの回収装置１同様に、リチウムの回収装置２の場合でもリチウムを回収できることが確認できた。
＜実施例４＞
図３のリチウムの回収装置１を用い、リチウム溶液セル８には海水（大洗海岸の海水をろ過して固形分を除去したもの）、リチウムイオン分離回収セル９には０．１ｍｏｌ％塩酸ＨＣｌを通液し、２Ｖの電位にて２時間の電気透析を行った。
As a result of electrodialysis, it was confirmed that lithium could be recovered even in the case of the lithium recovery device 2 as in the case of the lithium recovery device 1.
<Example 4>
Using the lithium recovery device 1 of FIG. 3, the lithium solution cell 8 contains seawater (the seawater of Oarai Coast is filtered to remove solids), and the lithium ion separation and recovery cell 9 contains 0.1 mol% HCl HCl. The solution was passed through and electrodialyzed at a potential of 2 V for 2 hours.
リチウムイオン選択的透過膜５は、イオン液体PP13-TFSIを密構造緻密有機隔膜（ジャパンゴアテックス（株）製、ゴアテックスハイパーシートＳＧ１０Ｘ）に含浸させた膜を使用した。陰イオン透過膜１５は、旭硝子（株）製セレミオンＡＭＶを使用し、陽イオン透過膜１６は、旭硝子（株）製セレミオンＣＭＶを使用した。 As the lithium ion selective permeable membrane 5, a membrane obtained by impregnating an ionic liquid PP13-TFSI into a dense structure dense organic diaphragm (Japan Gore-Tex Co., Ltd., Gore-Tex Hyper Sheet SG10X) was used. As the anion permeable membrane 15, Selemion AMV manufactured by Asahi Glass Co., Ltd. was used, and as the cation permeable membrane 16, Selemion CMV manufactured by Asahi Glass Co., Ltd. was used.
その結果を表４に示す。 The results are shown in Table 4.
電気透析の結果、海水中に高濃度に含まれるナトリウム（Ｎａ）イオン、マグネシウム（Ｍｇ）イオン、カルシウム（Ｃａ）イオンおよびカリウム（Ｋ）イオンは、リチウムイオン選択的透過膜５を透過せず（分離率はほぼ１００％）、リチウム（Ｌｉ）イオンのみが透過した。低電位にもかかわらず、海水からリチウムを選択的に高い回収率で回収できることが確認できた。
＜実施例５＞
ナトリウムイオン、マグネシウムイオン、カルシウムイオン、カリウムイオン、およびリチウムイオンの膜の透過性を評価した。図７はその結果を電気透析時間とイオン濃度との関係として示したものである。
As a result of electrodialysis, sodium (Na) ion, magnesium (Mg) ion, calcium (Ca) ion and potassium (K) ion contained in seawater at a high concentration do not permeate the lithium ion selective permeable membrane 5 ( The separation rate was almost 100%), and only lithium (Li) ions permeated. Despite the low potential, it was confirmed that lithium can be selectively recovered from seawater at a high recovery rate.
<Example 5>
The permeability of sodium ion, magnesium ion, calcium ion, potassium ion, and lithium ion membrane was evaluated. FIG. 7 shows the result as a relationship between electrodialysis time and ion concentration.
評価対象とした膜と図７中での表記の対応は以下のとおりである。 The correspondence between the film to be evaluated and the notation in FIG. 7 is as follows.
すなわち、前記上記リチウムイオン選択的透過膜５（図７ではイオン液体含浸膜と表記している）、実施例１で使用した保護膜付リチウムイオン選択的透過膜１１（図７では保護膜付イオン液体含浸膜と表記している）、および陽イオン透過膜１０（旭硝子（株）製、セレミオンＣＭＶ）である。 That is, the lithium ion selective permeable membrane 5 (shown as an ionic liquid impregnated membrane in FIG. 7), the lithium ion selective permeable membrane 11 with a protective film used in Example 1 (in FIG. 7, ions with a protective film). A liquid impregnated membrane) and a cation permeable membrane 10 (manufactured by Asahi Glass Co., Ltd., Selemion CMV).
これらの膜を用いて、図３及び図４のリチウムの回収装置１を用いて電気透析を行った。なお、リチウムイオン選択的透過膜５（イオン液体含浸膜）に対する各種イオンの透過性は図３のリチウムの回収装置１を用いて評価し、保護膜付リチウムイオン選択的透過膜１１（保護膜付イオン液体含浸膜）に対する各種イオンの透過性は図４のリチウムの回収装置１（図３のリチウムの回収装置１においてリチウムイオン選択的透過膜５の代わりに保護膜付リチウムイオン選択的透過膜１１を用いた装置）を用いて評価した。陽イオン透過膜１０（セレミオンＣＭＶ）に対する各種イオンの透過性は、図３のリチウムの回収装置１においてリチウムイオン選択的透過膜５の代わりに陽イオン透過膜１０を用いた装置で評価した。 Using these membranes, electrodialysis was performed using the lithium recovery apparatus 1 shown in FIGS. Incidentally, the permeability of various ions to the lithium ion selective permeable membrane 5 (ionic liquid impregnated membrane) was evaluated using the lithium recovery device 1 of FIG. 3, and the lithium ion selective permeable membrane 11 with protective film (with protective film) was used. The permeability of various ions with respect to the ionic liquid impregnated membrane) is the lithium ion selective permeable membrane 11 with a protective film instead of the lithium ion selective permeable membrane 5 in the lithium collecting device 1 in FIG. The apparatus was used to evaluate. The permeability of various ions to the cation permeable membrane 10 (Selemion CMV) was evaluated by an apparatus using the cation permeable membrane 10 in place of the lithium ion selective permeable membrane 5 in the lithium recovery device 1 of FIG.
図７に示した結果より、イオン液体を含浸させた膜（リチウムイオン選択的透過膜、および保護膜付リチウムイオン選択的透過膜）を用いたときの、ナトリウムイオン、マグネシウムイオン、カルシウムイオン、およびカリウムイオンの透過性は、陽イオンすべてを透過させる陽イオン透過膜と比べて明らかに低下しており、分離率が高いことが確認できた。また、保護膜付リチウムイオン選択的透過膜を用いた方がリチウムイオン選択的透過膜を用いたよりもリチウムイオンの透過性が良く、リチウム回収率の向上が観察された。
＜実施例６＞
リチウムには、７リチウム（７Ｌｉ）および６リチウム（６Ｌｉ）の二つの同位体が存在し、６リチウムは７．６％しか存在しない。核融合炉の燃料製造に必要なリチウムはこの６リチウム（６Ｌｉ）である。
From the results shown in FIG. 7, sodium ions, magnesium ions, calcium ions, and the like when using a membrane impregnated with an ionic liquid (a lithium ion selective permeable membrane and a lithium ion selective permeable membrane with a protective membrane) The permeability of potassium ions was clearly lower than that of a cation permeable membrane that allows all cations to pass through, and it was confirmed that the separation rate was high. Further, it was observed that the lithium ion selective permeation membrane with the protective film had better lithium ion permeability than the lithium ion selective permeation membrane, and an improvement in the lithium recovery rate was observed.
<Example 6>
Lithium has two isotopes, 7 lithium ( 7 Li) and 6 lithium ( 6 Li), and 6 lithium is only 7.6%. This lithium ( 6 Li) is necessary for the fuel production of the fusion reactor.
そこで６リチウム（６Ｌｉ）の分離試験を行った。分離試験は、実施例２で使用した図３のリチウムの回収装置１を用いた。その結果、図８に示すように、２Ｖ以下の低電圧で電気透析を行うことで、核融合炉の燃料製造に必要なリチウムの同位体である６リチウム（６Ｌｉ）を、同位体分離係数１．０１で得ることができることが分かった。 Therefore, a separation test of 6 lithium ( 6 Li) was performed. In the separation test, the lithium recovery apparatus 1 of FIG. 3 used in Example 2 was used. As a result, as shown in FIG. 8, by performing electrodialysis at a low voltage of 2 V or less, 6 lithium ( 6 Li), which is an isotope of lithium necessary for fuel production in a nuclear fusion reactor, is obtained. It was found that it can be obtained with 1.01.
１ リチウムの回収装置
２ 電気透析槽
３ アノード電極
４ カソード電極
５ リチウムイオン選択的透過膜
６ リチウム供給手段
７ リチウム回収手段
８ リチウム溶液セル
９ リチウムイオン分離回収セル
１０ 陽イオン透過膜
１８ 逆浸透膜
DESCRIPTION OF SYMBOLS 1 Lithium collection | recovery apparatus 2 Electrodialysis tank 3 Anode electrode 4 Cathode electrode 5 Lithium ion selective permeable membrane 6 Lithium supply means 7 Lithium collection means 8 Lithium solution cell 9 Lithium ion separation collection cell 10 Cation permeable membrane 18 Reverse osmosis membrane
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| JP5765850B2 (en) | 2015-08-19 |
| KR101779805B1 (en) | 2017-09-19 |
| KR20120024423A (en) | 2012-03-14 |
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