JPWO2011058841A1 - Lithium adsorbent production method, lithium concentration method, and lithium concentration apparatus - Google Patents
Lithium adsorbent production method, lithium concentration method, and lithium concentration apparatus Download PDFInfo
- Publication number
- JPWO2011058841A1 JPWO2011058841A1 JP2011540450A JP2011540450A JPWO2011058841A1 JP WO2011058841 A1 JPWO2011058841 A1 JP WO2011058841A1 JP 2011540450 A JP2011540450 A JP 2011540450A JP 2011540450 A JP2011540450 A JP 2011540450A JP WO2011058841 A1 JPWO2011058841 A1 JP WO2011058841A1
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- adsorbent
- acid
- spinel
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 348
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 348
- 239000003463 adsorbent Substances 0.000 title claims abstract description 200
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 60
- 239000011572 manganese Substances 0.000 claims abstract description 133
- 238000001179 sorption measurement Methods 0.000 claims abstract description 86
- 239000002253 acid Substances 0.000 claims abstract description 77
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 70
- 238000010828 elution Methods 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 238000010304 firing Methods 0.000 claims abstract description 44
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000010298 pulverizing process Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 77
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 72
- 229910052596 spinel Inorganic materials 0.000 claims description 49
- 239000011029 spinel Substances 0.000 claims description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 16
- 229920002101 Chitin Polymers 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 57
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 47
- 239000000203 mixture Substances 0.000 description 46
- 239000013535 sea water Substances 0.000 description 33
- 230000000694 effects Effects 0.000 description 30
- 238000005342 ion exchange Methods 0.000 description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- -1 sodium (10 Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 238000006479 redox reaction Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052770 Uranium Inorganic materials 0.000 description 4
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002351 wastewater 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910001234 light alloy Inorganic materials 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910008163 Li1+x Mn2-x O4 Inorganic materials 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004448 titration Methods 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
- 238000005406 washing Methods 0.000 description 1
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/28—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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- C—CHEMISTRY; METALLURGY
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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
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Abstract
リチウム含有水から微量に含まれるリチウムを工業的に濃縮・採取するための、リチウムに対する選択吸着性に優れるとともに吸着速度が高くかつ重量当たりの吸着量の大きく、吸着・溶離の繰り返しが可能なリチウム吸着剤の製造方法を提供する。４酸化３マンガンと水酸化リチウムを、マンガン（ｘ）とリチウム（ｙ）のモル比がｘ：ｙ＝１：１〜１．５：１となるように混合しメカノケミカル的に粉砕処理をするメカノケミカル工程と、次いで空気あるいは酸素雰囲気下にて３７５℃〜４５０℃の温度域で仮焼成する仮焼成工程と、次いで冷却し混合粉砕した後で、空気あるいは酸素雰囲気下にて４７５℃〜５５０℃の温度域で本焼成を行いスピネル型酸素過剰マンガン酸リチウムを得る本焼成工程と、該スピネル型酸素過剰マンガン酸リチウムをリチウムに対して大過剰の酸で処理してリチウムを溶離する溶離工程と、を備える。Lithium that can be repeatedly adsorbed and eluted, with excellent adsorption capacity for lithium, high adsorption rate, large adsorption amount per weight, for industrial concentration and extraction of trace amounts of lithium from lithium-containing water A method for producing an adsorbent is provided. Tetramanganese trioxide and lithium hydroxide are mixed so that the molar ratio of manganese (x) to lithium (y) is x: y = 1: 1 to 1.5: 1, and mechanochemically pulverized. A mechanochemical step, followed by a preliminary firing step of preliminary firing in a temperature range of 375 ° C. to 450 ° C. in an air or oxygen atmosphere, and then cooling, mixing and pulverizing, followed by 475 ° C. to 550 in an air or oxygen atmosphere. A main calcination step of obtaining a spinel-type oxygen-rich lithium manganate by performing a main calcination in a temperature range of ° C, and an elution step of eluting lithium by treating the spinel-type oxygen-rich lithium manganate with a large excess of acid relative to lithium And comprising.
Description
本発明は、海水や地熱水等のリチウムを含むリチウム含有水から微量に含まれるリチウムを選択的に濃縮・採取するために用いる、また、廃棄物や廃水に含まれるリチウムを選択的に効率よく分離・回収するために用いるλ型マンガン酸化物からなるリチウム吸着剤の製造方法とそのリチウム吸着剤を用いたリチウム濃縮方法及びリチウム濃縮装置に関する。 The present invention is used for selectively concentrating and collecting a small amount of lithium from lithium-containing water containing lithium such as seawater and geothermal water, and selectively using lithium contained in waste and wastewater. The present invention relates to a method for producing a lithium adsorbent composed of λ-type manganese oxide, which is often used for separation and recovery, a lithium concentration method and a lithium concentration apparatus using the lithium adsorbent.
海水中には多くの溶存成分があり、その絶対量の大きさからその溶存成分を採取することが注目されてきた。海水中の元素量を陸上の推定埋蔵量と比較すると、大部分の元素について海水中の溶存量の方が大きいことが知られている。しかしながら、海水中の元素濃度は極めて低く、工業的に利用可能なものは限られている。この中で、現在、工業化されているものとして、塩化ナトリウム、塩化マグネシウム、臭素、塩化カリウムなどを挙げることができる。 There are many dissolved components in sea water, and it has been noticed that the dissolved components are collected from the absolute amount. When comparing the amount of elements in seawater with the estimated reserves on land, it is known that the dissolved amount in seawater is larger for most elements. However, the concentration of elements in seawater is extremely low, and those that can be used industrially are limited. Among these, sodium chloride, magnesium chloride, bromine, potassium chloride and the like can be cited as industrialized products.
リチウム、ウラン、金、銅などは海水における溶存濃度が極めて低いが、その利用価値が高いために工業的に利用可能な採取技術の開発が進められている。リチウムは、大容量電池や航空機用軽合金のための添加元素、または核融合燃料など将来有望な用途がある。また、リチウムは、ウランなどに比べると海水中の濃度が高く、平均０．１７ｐｐｍであるが、ナトリウム（１０，０００ｐｐｍ以上）など高濃度の共存金属を随伴させることなく、リチウムのみを選択的に採取することが必要である。温泉水等地熱熱水や塩湖かん水には様々な金属イオンが溶け込んでおり、特にリチウムイオンは海水中の溶存濃度に比し格段に濃度が高く、例えば地熱熱水中の濃度は海水中のそれの約１００倍であり、温泉水等地熱熱水や塩湖かん水からリチウムを濃縮・採取するシステムも有望な工業的リチウム採取システムである。 Lithium, uranium, gold, copper, etc. have extremely low dissolved concentrations in seawater, but because of their high utility value, the development of industrially applicable collection techniques is underway. Lithium has promising applications such as additive elements for high capacity batteries and aircraft light alloys, or fusion fuels. Lithium has a higher concentration in seawater than uranium and the average is 0.17 ppm. However, only lithium is selectively used without accompanying a high concentration of coexisting metals such as sodium (10,000 ppm or more). It is necessary to collect. Various metal ions dissolve in geothermal hot water such as hot spring water and salt lake brine. Especially, lithium ions are much higher than the dissolved concentration in seawater. For example, the concentration in geothermal hot water is The system that concentrates and collects lithium from geothermal hot water such as hot spring water and salt lake brine is also a promising industrial lithium collection system.
溶存しているリチウムなどの微量成分の実験室的な採取法として、共沈法、溶媒抽出法、イオン浮選法、沈殿浮選法、クロマトグラフ法、生物濃縮法など様々な方法があり、分析化学的分離などに応用されている。しかしながら、工業的に可能性のある方法は、吸着法のみである。吸着法によって海水中のリチウムを採取する場合、膨大な量の海水と吸着剤とを接触させる必要があるので、さらなる高効率の採取法として、当初水酸化アルミニウムを用いて吸着する方法が注目されたが、実用化にはほど遠い性能であった。 There are various methods such as coprecipitation method, solvent extraction method, ion flotation method, precipitation flotation method, chromatographic method, bioconcentration method as laboratory collection method for trace components such as dissolved lithium, Applied to analytical chemical separation. However, the only industrially possible method is the adsorption method. When collecting lithium in seawater by the adsorption method, it is necessary to bring an enormous amount of seawater into contact with the adsorbent. Therefore, as an even more efficient collection method, the method of initially adsorbing with aluminum hydroxide has attracted attention. However, it was far from being practical.
（特許文献１）には、オキシ水酸化マンガン及び／または三酸化二マンガンと水酸化リチウム水酸化物とを、耐圧容器中で加熱反応させてＬｉＭｎ２Ｏ４の組成をもつリチウムマンガン複合酸化物を得て、さらに酸素存在下で焼成してリチウム吸着剤の原料を得ることが記載されている。(Patent Document 1) describes a lithium manganese composite oxide having a composition of LiMn 2 O 4 by heat-reacting manganese oxyhydroxide and / or dimanganese trioxide and lithium hydroxide hydroxide in a pressure vessel. And further calcining in the presence of oxygen to obtain a raw material for the lithium adsorbent.
ＬｉＭｎ２Ｏ４の組成をもつリチウムマンガン複合酸化物の合成法としては、（非特許文献１）にγ−ＭｎＯＯＨとＬｉＯＨを原料として合成する方法が、（非特許文献２）にＣＨ３ＣＯＯＬｉ−Ｍｎ（ＣＨ３ＣＯＯ）２・Ｈ２Ｏを原料として合成する方法が、（非特許文献３）にＭｎ２Ｏ３−Ｌｉ２ＣＯ３を原料として合成する方法が、（非特許文献４）にＭｎ２Ｏ３−Ｌｉ２ＣＯ３を原料にして固相反応法を用いた方法が記載されている。As a method for synthesizing a lithium manganese composite oxide having a composition of LiMn 2 O 4, a method of synthesizing γ-MnOOH and LiOH as raw materials is described in (Non-patent Document 1), and a method of synthesizing CH 3 COOLi— A method of synthesizing Mn (CH 3 COO) 2 .H 2 O as a raw material is (Non-Patent Document 3), and a method of synthesizing Mn 2 O 3 -Li 2 CO 3 as a raw material is (Non-Patent Document 4). A method using a solid phase reaction method using Mn 2 O 3 —Li 2 CO 3 as a raw material is described.
（特許文献２）には、リチウム含有マンガン酸化物をリチウム吸着剤原料として用いて海水からリチウムを濃縮し、さらに電気透析でリチウムを濃縮する方法が記載されている。 (Patent Document 2) describes a method of concentrating lithium from seawater using lithium-containing manganese oxide as a lithium adsorbent material, and further concentrating lithium by electrodialysis.
（特許文献３）には、「マンガン化合物とリチウム化合物とを原料とし、乾式でメカノケミカル反応を行うことにより反応前駆体を形成し、次いで焼成して、Ｌｉ１＋ｘＭｎ２−ｘＯ４（０≦ｘ≦０．３３）で表されるスピネル型結晶構造を含む複合化合物を得るスピネルマンガンの合成方法。」が開示されている。(Patent Document 3) states that “a reaction precursor is formed by performing a mechanochemical reaction using a manganese compound and a lithium compound as raw materials, followed by firing, and Li 1 + x Mn 2−x O 4 (0 The method for synthesizing spinel manganese to obtain a composite compound containing a spinel crystal structure represented by ≦ x ≦ 0.33) ”is disclosed.
（特許文献４）は本願発明の発明者等によるもので、Ｍｎ３Ｏ４とＬｉＯＨをマンガンとリチウムのモル比を１．５〜２．５となるように混合・粉砕し、仮焼成と本焼成をしてスピネル型酸素過剰マンガンを得て、該スピネル型酸素過剰マンガンを大過剰の酸で処理してリチウムを溶離し、リチウム吸着剤を製造する方法が記載されている。(Patent Document 4) is based on the inventors of the present invention. Mn 3 O 4 and LiOH are mixed and pulverized so that the molar ratio of manganese to lithium is 1.5 to 2.5. A method is described in which a spinel-type oxygen-excess manganese is obtained by calcination, and the spinel-type oxygen-excess manganese is treated with a large excess of acid to elute lithium to produce a lithium adsorbent.
しかしながら上記従来の技術においては、以下のような課題を有していた。
（１）（特許文献１）に記載のリチウム吸着剤は繰り返し使用すると構造が崩れてしまい長期間の実用に耐えないという課題を有していた。
（２）（特許文献２）に記載のリチウム濃縮方法は、リチウム吸着剤の性能が低いために、電気透析を用いてさらにリチウム濃縮をする必要があり、設備が複雑になるという課題を有していた。
（３）（非特許文献１）乃至（非特許文献４）に記載のリチウムマンガン複合酸化物は、リチウムの吸着能が低い上に、繰り返し使用すると構造が崩れてしまい長期間の実用に耐えないという課題を有していた。
（４）（特許文献３）は、酸化還元反応が優勢で正極活物質として有用なスピネルマンガンを与えるが、Ｍｎの不均化が生じ易く、かつ、イオン交換時にＭｎの溶出が生じ易く、吸着剤として使用し難いという課題を有している。これは一回の高温焼成のため原料のＭｎ３Ｏ４が系内に残存し純粋な結晶相が得られ難いことに起因することが判った。本発明者はこの課題を解決するため鋭意研究した結果、低い温度で一旦仮焼成し、それを再び粉砕混合した後、再び低い温度で本焼成することにより単一相の合成が可能であることを見出した。
（５）（特許文献４）に記載の技術は、マンガンとリチウムのモル比を１．５〜２．５において高いリチウム吸着量を持つリチウム吸着剤を得られるが、さらにリチウムイオンの吸着量を上げるためにマンガンのモル比を下げてＭｎ３Ｏ４に対するＬｉＯＨの配合比を上げるとスピネル構造が生成しないか、あるいは、アモルファス等の他の構造との混合物として得られ、酸処理した場合に、吸着剤が溶解したり、スピネル構造が崩れたりしてしまい、（特許文献４）に記載されたより高いリチウム吸着量をもつ吸着剤を得られないという課題があった。
（６）また、（特許文献４）に記載の技術では、記載された比率以上にＬｉＯＨの配合比を上げた場合、出来上がったリチウムマンガン複合酸化物はマンガンとリチウムの結合が不完全となり、リチウムの選択性が低くなるのでリチウムの濃縮率が上がらず、（特許文献４）に記載された以上の性能をもつリチウム吸着剤を得られないという課題があった。
（７）またリチウムマンガン酸化物をリチウム吸着剤として用いる場合に、原料水の硫酸イオン濃度が高いと吸着効果が減少すること、およびリチウム吸着剤の構造が崩れたり、溶解したりするという課題があった。However, the above conventional techniques have the following problems.
(1) The lithium adsorbent described in (Patent Document 1) has a problem that the structure collapses when it is used repeatedly and cannot withstand long-term practical use.
(2) The lithium concentration method described in (Patent Document 2) has a problem in that, since the performance of the lithium adsorbent is low, it is necessary to further concentrate lithium using electrodialysis, resulting in complicated facilities. It was.
(3) The lithium-manganese composite oxides described in (Non-patent Document 1) to (Non-patent Document 4) have a low lithium adsorbing ability, and the structure collapses when used repeatedly and cannot withstand long-term practical use. It had the problem that.
(4) (Patent Document 3) gives spinel manganese useful as a positive electrode active material because of its superior oxidation-reduction reaction, but tends to cause disproportionation of Mn, and elution of Mn easily during ion exchange. It has a problem that it is difficult to use as an agent. It has been found that this is due to the fact that the raw material Mn 3 O 4 remains in the system due to high-temperature firing once, and it is difficult to obtain a pure crystal phase. As a result of intensive research to solve this problem, the present inventor is able to sinter temporarily at a low temperature, pulverize and mix it again, and then sinter again at a low temperature to synthesize a single phase. I found.
(5) The technology described in (Patent Document 4) can obtain a lithium adsorbent having a high lithium adsorption amount at a molar ratio of manganese to lithium of 1.5 to 2.5. When the molar ratio of manganese is lowered to increase the mixing ratio of LiOH with respect to Mn 3 O 4 , spinel structure is not generated, or it is obtained as a mixture with other structures such as amorphous, and when acid-treated, There existed a subject that an adsorbent with a higher lithium adsorption amount described in (patent document 4) could not be obtained because the adsorbent was dissolved or the spinel structure collapsed.
(6) In the technique described in (Patent Document 4), when the mixing ratio of LiOH is increased beyond the stated ratio, the resulting lithium manganese composite oxide has an incomplete bond between manganese and lithium, and lithium Therefore, there is a problem in that a lithium adsorbent having a performance higher than that described in (Patent Document 4) cannot be obtained.
(7) Further, when lithium manganese oxide is used as a lithium adsorbent, there is a problem that if the sulfate ion concentration of the raw material water is high, the adsorption effect is reduced, and the structure of the lithium adsorbent is broken or dissolved. there were.
本発明は上記従来の課題を解決するもので、
（１）低い温度での本焼成によりリチウムイオンのインターカレートと脱インターカレートに伴うＭｎの不均化を阻止し、Ｍｎの溶出を防止できるので、吸着・溶離を繰り返してもスピネル構造が崩れず、通液が容易で目詰まりしにくい形状に造粒されているので工業的に利用しやすく、繰り返し使用可能なリチウム吸着剤の製造方法を提供することを目的とする。
（２）海水中あるいは地熱熱水中に含まれるリチウムを工業的に吸着・採取するための、リチウムイオンに対する選択吸着性に優れるとともに吸着速度が高くかつ重量当たりの吸着量が大きく、入手しやすい原料で工業的に生産でき、化学的に安定であり、吸着・溶離の繰り返しが可能なリチウム吸着剤の製造方法を提供することを目的とする。
（３）耐塩性や耐高温性に優れ、Ｌｉ＋の吸着容量が大きいリチウム吸着剤を製造できるリチウム吸着剤用原料の提供を目的とする。
（４）海水中や地熱熱水中のＬｉ＋を吸着したリチウム吸着剤から高効率でＬｉ＋を溶離し濃縮するとともに、リチウム吸着剤を再生することができるリチウム濃縮装置の提供を目的とする。
（５）海水中あるいは地熱熱水中に含まれるリチウムを効率よく選択的に高濃縮でき、長期の繰り返し使用ができるリチウム濃縮装置を提供することを目的とする。The present invention solves the above conventional problems,
(1) The main firing at a low temperature prevents the disproportionation of Mn accompanying the intercalation and deintercalation of lithium ions and prevents the elution of Mn. An object of the present invention is to provide a method for producing a lithium adsorbent that is easy to use industrially and can be used repeatedly because it is granulated into a shape that does not collapse and is easy to pass through and does not clog.
(2) Excellent in selective adsorption to lithium ions for industrial adsorption and extraction of lithium contained in seawater or geothermal hot water, and has a high adsorption rate and a large amount of adsorption per weight, making it easy to obtain. An object of the present invention is to provide a method for producing a lithium adsorbent that can be industrially produced from raw materials, is chemically stable, and can be repeatedly adsorbed and eluted.
(3) An object is to provide a raw material for a lithium adsorbent that can produce a lithium adsorbent that is excellent in salt resistance and high temperature resistance and has a large Li + adsorption capacity.
(4) An object of the present invention is to provide a lithium concentrator capable of eluting and concentrating Li + from a lithium adsorbent adsorbing Li + in seawater or geothermal hot water with high efficiency and regenerating the lithium adsorbent. .
(5) An object of the present invention is to provide a lithium concentrator capable of efficiently and selectively concentrating lithium contained in seawater or geothermal hot water and capable of being used repeatedly for a long time.
上記従来の課題を解決するために本発明のリチウム吸着剤の製造方法とそのリチウム吸着剤を用いたリチウム濃縮方法及びリチウム濃縮装置は、以下の構成を有している。 In order to solve the above conventional problems, a method for producing a lithium adsorbent of the present invention, a lithium concentration method using the lithium adsorbent, and a lithium concentration apparatus have the following configurations.
本発明の請求項１に記載のリチウム吸着剤の製造方法は、４酸化３マンガン（Ｍｎ３Ｏ４）及び水酸化リチウム（ＬｉＯＨ）を、マンガンとリチウムのモル比がＭｎ：Ｌｉ＝１〜１．５：１となるように混合し、メカノケミカル的に粉砕処理をするメカノケミカル工程と、次いで空気あるいは酸素雰囲気下にて３７５℃〜４５０℃の温度域で仮焼成する仮焼成工程と、次いで冷却し混合粉砕した後、空気あるいは酸素雰囲気下にて４７５℃〜５５０℃の温度域で本焼成を行いスピネル型酸素過剰マンガン酸リチウムを得る本焼成工程と、該スピネル型酸素過剰マンガン酸リチウムをリチウムに対して大過剰の酸で処理してリチウムイオンを溶離する溶離工程と、を備えた構成を有している。
この構成により、以下のような作用が得られる。
（１）メカノケミカル効果によりＭｎ３Ｏ４とＬｉＯＨの相互作用が高まり、従来よりもＬｉの配合比が高くても酸素過剰マンガン酸リチウムがスピネル構造を保つようになった。そのため、リチウムイオンに対する選択吸着性に優れるとともに吸着速度が速くかつ吸着量が大きく、化学的に安定なリチウム吸着剤を製造できる。非量論的化合物であるＭｎ３Ｏ４を用いたので反応性が高い。また、Ｍｎ３Ｏ４とＬｉＯＨの混合物の相転移点がＭｎ：Ｌｉ＝２：１〜１．５の混合物で４２５〜４３０℃、と５００〜５１０℃にあることを見出したので、２段焼成することで安定したスピネル構造のリチウム吸着剤を得ることができる。
（２）低い温度で仮焼成し、次いで低い温度で本焼成を行うので系内に原料のＭｎ３Ｏ４が残らず純粋な単一の結晶相が得られ、結晶構造が強固となり、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤を製造できる。
（３）低い温度での本焼成により、リチウムイオンのインターカレートと脱インターカレートに伴うＭｎの不均化を阻止し、Ｍｎの溶出を防止するので、大過剰の酸でリチウムを溶離することでマンガンの酸化還元反応を抑えて水素イオンとリチウムイオンの交換反応のみを起こさせることができ、結晶構造を壊さない。これにより化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤を製造できる。
（４）リチウムの吸着量が多く、結晶構造が安定なので高能率で繰り返しリチウムイオンを吸着、溶離できるリチウム吸着剤を製造できる。
（５）製造工程が煩雑でなく、入手しやすい原料から工業的に生産可能なリチウム吸着剤が製造できる。In the method for producing a lithium adsorbent according to the first aspect of the present invention, manganese tetraoxide (Mn 3 O 4 ) and lithium hydroxide (LiOH) are used, and the molar ratio of manganese to lithium is Mn: Li = 1 to 1. A mechanochemical process in which the mixture is mixed to have a ratio of 5: 1 and mechanochemically pulverized, and then pre-baked in a temperature range of 375 ° C. to 450 ° C. in an air or oxygen atmosphere; After cooling and mixing and pulverizing, a main firing step of obtaining a spinel-type oxygen-rich lithium manganate by firing in a temperature range of 475 ° C. to 550 ° C. in air or an oxygen atmosphere, and the spinel-type oxygen-rich lithium manganate And an elution step of eluting lithium ions by treating with a large excess of acid with respect to lithium.
With this configuration, the following effects can be obtained.
(1) Due to the mechanochemical effect, the interaction between Mn 3 O 4 and LiOH is increased, and even when the compounding ratio of Li is higher than before, the oxygen-excess lithium manganate has maintained the spinel structure. For this reason, it is possible to produce a lithium adsorbent that is excellent in selective adsorptivity to lithium ions, has a high adsorption rate and a large adsorption amount, and is chemically stable. Since Mn 3 O 4 which is a non-stoichiometric compound is used, the reactivity is high. Further, the phase transition point of the Mn 3 O 4 and a mixture of LiOH is Mn: Li = 2: Since it was found that in the four hundred twenty-five to four hundred and thirty ° C., and 500 to 510 ° C. with a mixture of 1 to 1.5, 2 stage calcination By doing so, a lithium adsorbent having a stable spinel structure can be obtained.
(2) Since preliminary firing is performed at a low temperature and then main firing is performed at a low temperature, a pure single crystal phase is obtained in which no raw material Mn 3 O 4 remains in the system, the crystal structure is strengthened, In addition, it is possible to produce a lithium adsorbent that is stable and does not dissolve even after repeated use.
(3) The main firing at a low temperature prevents Mn disproportionation associated with lithium ion intercalation and deintercalation and prevents Mn elution, so that lithium is eluted with a large excess of acid. Thus, the oxidation-reduction reaction of manganese can be suppressed and only the exchange reaction between hydrogen ions and lithium ions can be caused, and the crystal structure is not broken. This makes it possible to produce a lithium adsorbent that is chemically stable and does not dissolve even after repeated use.
(4) Since the adsorption amount of lithium is large and the crystal structure is stable, a lithium adsorbent capable of repeatedly adsorbing and eluting lithium ions with high efficiency can be produced.
(5) A lithium adsorbent that can be industrially produced can be manufactured from easily available raw materials without complicated manufacturing steps.
ここで、メカノケミカル的粉砕処理とは機械的に粉砕する過程において、物質粒子に機械による圧縮力、剪断力、衝撃力等をかけることによって粒子表面に新しいへき開面を多数生成するとともに表面積を増大し、粒子表面での化学反応性を変化させる処理である。粉砕処理装置としてはアトライター、サンドミル、ボールミル、メディアミル、コロイドミル、ストーンミル、ケディーミル、フロージェットミキサ、スラッシャーミル、メカノヒュージョンシステム（ホソカワミクロン（株）製）、ミラーロ（（株）奈良機械製作所製）などが用いられる。
処理時間、処理条件は使用する機器によって異なるが、仮焼成後にＸＲＤ測定によってＭｎ３Ｏ４のピークの減少・消失度合いを確認することでメカノケミカル的処理条件を決めることができる。Here, mechanochemical pulverization is a process of mechanical pulverization, in which a large number of new cleaved surfaces are generated and surface area is increased by applying mechanical compressive force, shearing force, impact force, etc. to the material particles. In this case, the chemical reactivity on the particle surface is changed. Grinding equipment includes attritors, sand mills, ball mills, media mills, colloid mills, stone mills, keddy mills, flow jet mixers, slasher mills, mechano-fusion systems (manufactured by Hosokawa Micron Corporation), and mirrors (manufactured by Nara Machinery Co., Ltd.) ) Etc. are used.
Although the treatment time and treatment conditions vary depending on the equipment used, the mechanochemical treatment conditions can be determined by confirming the degree of decrease / disappearance of the peak of Mn 3 O 4 by XRD measurement after preliminary firing.
仮焼成の温度が３７５℃より低いと均一な組成の結晶が得られないので好ましくない。また発明者らの知見によると４５０℃を超えると、本焼成を行っても不純物が多く残り結晶構造が脆弱になるので好ましくない。 If the pre-baking temperature is lower than 375 ° C., crystals with a uniform composition cannot be obtained. Further, according to the knowledge of the inventors, if it exceeds 450 ° C., it is not preferable because many impurities remain and the crystal structure becomes brittle even if the main baking is performed.
本焼成の温度が４７５℃より低いと仮焼成物の不純物が本焼成後も残り結晶構造が脆弱になるので好ましくない。５５０℃を超えると、スピネル型の結晶構造が崩れるため好ましくない。 If the temperature of the main baking is lower than 475 ° C., impurities in the temporarily fired product remain after the main baking, and the crystal structure becomes brittle. A temperature exceeding 550 ° C. is not preferable because the spinel crystal structure is broken.
リチウムを溶離するには、大過剰の酸、例えば塩酸、過塩素酸、硝酸等をリチウム（ａ）と酸（ｂ）のモル比が、ａ：ｂ＝１：２０以上、好ましくはａ：ｂ＝１：４０以上となる過剰の酸でリチウムを溶離する必要がある。このときの酸の濃度は、０．１〜２Ｍである。２Ｍを超える濃度の酸を適用すると、Ｍｎを溶解させて好ましくない。また、リチウム：酸＝１：２０以下でリチウムを溶離するとスピネル型結晶構造が崩れて好ましくない。 In order to elute lithium, a large excess of acid, for example, hydrochloric acid, perchloric acid, nitric acid or the like, the molar ratio of lithium (a) to acid (b) is a: b = 1: 20 or more, preferably a: b = 1: It is necessary to elute lithium with an excess of acid that is 40 or more. The concentration of the acid at this time is 0.1 to 2M. If an acid having a concentration exceeding 2M is applied, Mn is dissolved, which is not preferable. Further, it is not preferable to elute lithium with lithium: acid = 1: 20 or less because the spinel crystal structure is broken.
本発明の請求項２に記載のリチウム吸着剤の製造方法は、マンガンとリチウムのモル比が１≦Ｍｎ／Ｌｉ＜１．２５となるように混合してなる構成を有している。
この構成により、請求項１で得られる作用に加えて以下の作用が得られる。
（１）スピネル結晶構造を保ちながらＬｉ含有量を多くすることができる。
（２）結晶構造が安定なので、吸着・脱着作業の繰り返し耐性を高めることができる。The method for producing a lithium adsorbent according to claim 2 of the present invention has a configuration in which the molar ratio of manganese to lithium is mixed so that 1 ≦ Mn / Li <1.25.
With this configuration, the following actions are obtained in addition to the actions obtained in the first aspect.
(1) The Li content can be increased while maintaining the spinel crystal structure.
(2) Since the crystal structure is stable, it is possible to increase the resistance to repeated adsorption and desorption operations.
本発明の請求項３に記載のリチウム吸着剤の製造方法は、請求項１又は２に記載のリチウム吸着剤の製造方法であって、前記本焼成工程で得られた前記スピネル型酸素過剰マンガン酸リチウム１００重量部に対して、酸化アルミニウムやシリカ等の無機系バインダ２重量部〜４０重量部と水を混練したあと、径０．５ｍｍ〜６ｍｍ好ましくは１ｍｍ〜３ｍｍの紐状又は粒状の成形体に加工する成形工程と、次いで前記成形体を４５０℃〜５５０℃の温度域で０．５〜３時間焼結し、成形体とする焼結工程と、を備えた構成を有している。
この構成により、請求項１又は２の作用に加えて、以下のような作用が得られる。
（１）粒状に成形されているので、カラムに詰めて使用する場合に通液が容易である。
（２）焼結により硬度が上がり粉化し難く長寿命化できる。
尚、紐状に成形した場合は、焼結後に、１〜３ｍｍにカッターで粒状に切断される。The method for producing a lithium adsorbent according to claim 3 of the present invention is the method for producing a lithium adsorbent according to claim 1 or 2, wherein the spinel-type oxygen-excess manganic acid obtained in the main firing step. After kneading 2 to 40 parts by weight of an inorganic binder such as aluminum oxide or silica with 100 parts by weight of lithium, a string-like or granular shaped body having a diameter of 0.5 mm to 6 mm, preferably 1 mm to 3 mm. And a sintering step of sintering the molded body at a temperature range of 450 ° C. to 550 ° C. for 0.5 to 3 hours to form a molded body.
With this configuration, in addition to the operation of the first or second aspect, the following operation can be obtained.
(1) Since it is formed into a granular shape, liquid passage is easy when packed in a column and used.
(2) Sintering increases the hardness, making it difficult to powder and extending the life.
In addition, when shape | molding in the shape of a string, after sintering, it is cut | disconnected by a cutter to a granular form at 1-3 mm.
本発明の請求項４に記載のリチウム吸着剤の製造方法は、請求項１又は２に記載のリチウム吸着剤の製造方法であって、前記本焼成工程で得られた前記スピネル型酸素過剰マンガン酸リチウム１００重量部に対して、キチンやＰＶＣ等の有機系バインダ０．５重量部〜２０重量部と水を混練したあと、径０．５ｍｍ〜６ｍｍ好ましくは１ｍｍ〜３ｍｍの粒状の成形体に加工する成形工程と、次いで前記成形体を５０℃〜１００℃の温度域で０．５〜４時間乾燥し、成形体とする乾燥工程と、を備えた構成を有している。
この構成により、請求項３と同様の作用が得られる。The method for producing a lithium adsorbent according to claim 4 of the present invention is the method for producing a lithium adsorbent according to claim 1 or 2, wherein the spinel-type oxygen-excess manganic acid obtained in the main firing step. After kneading 0.5 parts by weight to 20 parts by weight of an organic binder such as chitin or PVC with 100 parts by weight of lithium, it is processed into a granular compact having a diameter of 0.5 mm to 6 mm, preferably 1 mm to 3 mm. And a drying step of drying the molded body in a temperature range of 50 to 100 ° C. for 0.5 to 4 hours to form a molded body.
With this configuration, the same effect as in the third aspect can be obtained.
ここで成形には押し出し造粒機（エクストルーダー）、圧縮造粒機、射出造粒機（ニーダールーダー）など各種造粒機を用いることができる。
ストランド状に成形した場合は成形後、長さ１ｍｍ〜６ｍｍ好ましくは１〜３ｍｍに切断する。
造粒を終えたスピネル型酸素過剰マンガン酸リチウムは篩にかけ微粉を除いた後で、溶離工程に掛けることが好ましい。Here, various granulators such as an extrusion granulator (extruder), a compression granulator, and an injection granulator (kneader ruder) can be used for molding.
When it is formed into a strand shape, it is cut into a length of 1 mm to 6 mm, preferably 1 to 3 mm after the forming.
The spinel-type oxygen-rich lithium manganate after granulation is preferably sieved to remove fine powder and then subjected to an elution step.
本発明の請求項５に記載のリチウム吸着剤は、一般式ＨａＭｎ２Ｏｂ（式中、１．６＜ａ≦２、は４＜ｂ≦４．２である。）の構成を有している。
この構成により、以下の作用が得られる。
（１）酸素を過剰に有しているため、Ｍｎ４＋の含有量を増加させ、Ｌｉ＋とのイオン交換反応量を増やすことができる。また、スピネル結晶構造を電子的により安定化させることができる。
（２）プロトンサイト（イオン交換型サイト）にリチウム溶液中からＬｉ＋を取り込むことができる。
（３）マンガン酸化物にはトンネル構造、層状構造、網目状構造などさまざまな構造を持つ化合物があるが、スピネル型と呼ばれる構造を持つマンガン酸化物は（１×３）網目状構造になっている。スピネル型マンガン酸化物の結晶構造を模式的に表したものを図１に示す。金属イオンに対する吸着選択性はマンガン酸化物の結晶構造に依存するが、非量論型のスピネル型マンガン酸化物としたので、Ｌｉ＋に対して高い選択性を示すと共に多量のＬｉ＋とイオン交換をすることができる。また、鹹水はＬｉ＋よりイオン半径の大きいＮａ＋やＫ＋、Ｃａ２＋等の陽イオンを含むがこれらの陽イオンは網目状構造に入ることができない。その理由は、鋳型であるＬｉ＋を取り込むことで調製された吸着剤の前躯体からＬｉ＋を取り除くことにより、Ｌｉ＋の大きさの鋳型を有する多孔結晶型の吸着剤を得ることができるためである。The lithium adsorbent according to claim 5 of the present invention has a configuration of the general formula H a Mn 2 O b (where 1.6 <a ≦ 2 and 4 <b ≦ 4.2). doing.
With this configuration, the following effects can be obtained.
(1) Since it has oxygen excessively, the content of Mn 4+ can be increased and the amount of ion exchange reaction with Li + can be increased. Also, the spinel crystal structure can be more electronically stabilized.
(2) Li + can be taken into the proton site (ion exchange type site) from the lithium solution.
(3) Manganese oxides include compounds with various structures such as tunnel structures, layered structures, and network structures, but manganese oxides with a structure called spinel type have a (1 × 3) network structure. Yes. A schematic representation of the crystal structure of spinel manganese oxide is shown in FIG. Adsorption selectivity for metal ions depends on the crystal structure of manganese oxide but, since the spinel-type manganese oxide of the non-stoichiometric form, a large amount of Li + ion exchange exhibit both high selectivity for Li + Can do. Further, the brine contains cations such as Na + , K + , and Ca 2+ having an ionic radius larger than that of Li +, but these cations cannot enter the network structure. The reason is that by removing the Li + from the precursor of the adsorbent prepared by incorporating the Li + as a template, it is possible to obtain a porous crystalline adsorbent having a Li + in the size of the mold It is.
本発明の請求項６に記載のリチウム吸着剤用原料は、一般式ＬｉｘＭｎ２Ｏｙ（式中、１．６＜ｘ≦２、４＜ｙ≦４．２である。）からなる構成を有している。
この構成により、以下の作用が得られる。
（１）酸洗時（溶離時）に定量的にＬｉ＋を溶離させ、かつ、吸着時の繰り返し耐性に優れる。The raw material for a lithium adsorbent according to claim 6 of the present invention is composed of the general formula Li x Mn 2 O y (where 1.6 <x ≦ 2, 4 <y ≦ 4.2). have.
With this configuration, the following effects can be obtained.
(1) Li + is eluted quantitatively during pickling (during elution) and is excellent in repeated resistance during adsorption.
本発明の請求項７に記載のリチウム濃縮方法は、原水から請求項１乃至４の内いずれか１に記載のリチウム吸着剤を用いて選択的にリチウムイオンを吸着する吸着工程と、リチウムイオンを吸着したリチウム吸着剤を大過剰の酸で処理してリチウムイオンを溶離する溶離工程とを有し、前記溶離工程でリチウムイオンを溶離する酸が、０．１Ｍ〜２．０Ｍの塩酸又は過塩素酸、硝酸の内いずれか１である構成を有している。
この構成により、以下のような作用が得られる。
（１）リチウムイオンの選択性に優れ、リチウムイオンの吸着速度が速く、リチウムイオンの吸着量が多いリチウム吸着体を、安定して繰り返し使用できるので、工業的にリチウムを高濃縮できる。
（２）溶離工程で用いる酸がリチウム吸着剤を溶かさず、またリチウム吸着剤の結晶構造を崩さないので、リチウム吸着剤が劣化しないので、効率のよいリチウム濃縮を工業的に継続できる。The lithium concentration method according to claim 7 of the present invention comprises an adsorption step of selectively adsorbing lithium ions from raw water using the lithium adsorbent according to any one of claims 1 to 4, and lithium ions. An elution step of eluting lithium ions by treating the adsorbed lithium adsorbent with a large excess of acid, and the acid eluting lithium ions in the elution step is 0.1 M to 2.0 M hydrochloric acid or perchlorine It has a configuration that is one of acid and nitric acid.
With this configuration, the following effects can be obtained.
(1) Since a lithium adsorbent having excellent lithium ion selectivity, a high lithium ion adsorption rate, and a large amount of lithium ion adsorption can be stably and repeatedly used, lithium can be industrially highly concentrated.
(2) Since the acid used in the elution step does not dissolve the lithium adsorbent and does not destroy the crystal structure of the lithium adsorbent, the lithium adsorbent does not deteriorate, so that efficient lithium concentration can be continued industrially.
ここで、リチウム吸着剤からリチウムイオンを溶離させる酸の濃度が０．１Ｍ未満の場合、溶離の初期において酸の濃度が薄い状態がリチウム吸着剤において部分的に発生し、マンガンの酸化還元反応が起こり、結晶構造が崩れてＭｎが溶出する恐れがあり好ましくない。またリチウム吸着剤からリチウムイオンを溶離させる酸の濃度が２．０Ｍ超であると、長期の反復使用で少しずつ吸着剤が溶解して劣化する恐れがあり好ましくない。
より好ましくは０．５Ｍ〜１．５Ｍの酸が採用される。カラム内の残液による希釈や、溶離液の混合ムラによる吸着剤の損傷を防ぐためである。Here, when the concentration of the acid that elutes lithium ions from the lithium adsorbent is less than 0.1 M, a state where the acid concentration is low occurs partially in the lithium adsorbent at the beginning of the elution, and the oxidation-reduction reaction of manganese occurs. This is not preferable because the crystal structure is broken and Mn is eluted. Further, if the concentration of the acid eluting lithium ions from the lithium adsorbent is more than 2.0M, the adsorbent may be gradually dissolved and deteriorated by repeated use over a long period, which is not preferable.
More preferably, an acid of 0.5M to 1.5M is employed. This is to prevent damage to the adsorbent due to dilution with residual liquid in the column and uneven mixing of the eluent.
本発明の請求項８に記載のリチウム濃縮装置は請求項１乃至４の内いずれか１に記載された又は請求項５に記載されたリチウム吸着剤が充填されたリチウム吸着カラムを持つ構成を有している。
この構成により、以下のような作用が得られる。
（１）繰り返し使用でき、選択性の高く吸着速度が高く吸着量の多いリチウム吸着剤を充填したカラムを利用するので高能率でリチウムを濃縮できる装置となる。The lithium concentrator according to claim 8 of the present invention has a configuration having a lithium adsorption column filled with the lithium adsorbent described in any one of claims 1 to 4 or claim 5. doing.
With this configuration, the following effects can be obtained.
(1) Since a column packed with a lithium adsorbent that can be used repeatedly, has a high selectivity, a high adsorption rate, and a large amount of adsorption is used, the apparatus can concentrate lithium with high efficiency.
ここで、リチウム吸着剤を充填したカラムをパッケージとして脱着を容易にすることで、リチウムイオンを吸着する工程と溶離工程を分離することができ、装置の設計・配置の自由度を増すことができる。 Here, by using a column packed with a lithium adsorbent as a package for easy desorption, the process of adsorbing lithium ions and the elution process can be separated, and the degree of freedom in designing and arranging the apparatus can be increased. .
以上のように本発明のリチウム吸着剤の製造方法及びリチウム吸着剤、リチウム吸着剤用原料、リチウム濃縮方法、リチウム濃縮装置によれば、以下のような有利な効果が得られる。
請求項１に記載の発明によれば、
（１）メカノケミカル効果によりＭｎ３Ｏ４とＬｉＯＨの相互作用が高まり、従来よりもＬｉの配合比が高くても酸素過剰マンガン酸リチウムがスピネル構造を保つようになったため、リチウムに対する選択吸着性に優れるとともに吸着速度が速くかつ吸着量が大きく、化学的に安定なリチウム吸着剤の製造方法を提供できる。
（２）非量論的化合物であるＭｎ３Ｏ４を用いたので反応性が高い。また、Ｍｎ３Ｏ４とＬｉＯＨの混合物の相転移点がＭｎ：Ｌｉ＝２：１〜１．５の混合物で４２５〜４３０℃、と５００〜５１０℃にあることを見出したので、２段焼成することで安定したスピネル構造のリチウム吸着剤を得ることができる。仮焼成工程と本焼成工程を有するので、結晶構造が強固となり、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤の製造方法を提供できる。
（３）大過剰の酸でリチウムイオンを溶離することでマンガンの酸化還元反応を抑えて水素イオンとリチウムイオンの交換反応のみを起こさせることができ、結晶構造を壊さないので、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤の製造方法を提供できる。
（４）リチウムイオンの吸着量が多く、結晶構造が安定なので高能率で繰り返しリチウムイオンを吸着、溶離できるリチウム吸着剤の製造方法を提供できる。
（５）製造工程が煩雑でなく、入手しやすい原料から工業的に生産可能なので、低原価で量産性に優れたリチウム吸着剤の製造方法を提供できる。As described above, according to the method for producing a lithium adsorbent, the lithium adsorbent, the lithium adsorbent raw material, the lithium concentration method, and the lithium concentrator of the present invention, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) The interaction between Mn 3 O 4 and LiOH is enhanced due to the mechanochemical effect, and the oxygen-rich lithium manganate maintains the spinel structure even when the Li content is higher than before. In addition, it is possible to provide a method for producing a chemically stable lithium adsorbent that has a high adsorption rate and a large adsorption amount.
(2) Since Mn 3 O 4 which is a non-stoichiometric compound is used, the reactivity is high. Further, the phase transition point of the Mn 3 O 4 and a mixture of LiOH is Mn: Li = 2: Since it was found that in the four hundred twenty-five to four hundred and thirty ° C., and 500 to 510 ° C. with a mixture of 1 to 1.5, 2 stage calcination By doing so, a lithium adsorbent having a stable spinel structure can be obtained. Since the pre-baking step and the main baking step are provided, the method for producing a lithium adsorbent that has a strong crystal structure, is chemically stable, and does not dissolve even after repeated use can be provided.
(3) By eluting lithium ions with a large excess of acid, it is possible to suppress the oxidation-reduction reaction of manganese and to cause only the exchange reaction between hydrogen ions and lithium ions, and since the crystal structure is not destroyed, it is chemically stable. In addition, a method for producing a lithium adsorbent that does not dissolve even after repeated use can be provided.
(4) Since the adsorption amount of lithium ions is large and the crystal structure is stable, a method for producing a lithium adsorbent capable of repeatedly adsorbing and eluting lithium ions with high efficiency can be provided.
(5) Since the production process is not complicated and can be industrially produced from readily available raw materials, it is possible to provide a method for producing a lithium adsorbent with low cost and excellent mass productivity.
請求項２に記載の発明によれば、請求項１の効果に加え、
（１）安定なスピネル結晶構造を保ち、Ｌｉ含有量が多く、吸着・脱着作業の繰り返し耐久性の高いリチウム吸着剤を低原価で量産できるリチウム吸着剤の製造方法を提供できる。According to invention of Claim 2, in addition to the effect of Claim 1,
(1) A method for producing a lithium adsorbent capable of mass-producing a lithium adsorbent having a stable spinel crystal structure, a high Li content, and a high durability for repeated adsorption / desorption operations at a low cost can be provided.
請求項３に記載の発明によれば、請求項１又は２の効果に加え、
（１）径０．５ｍｍ〜６ｍｍ好ましくは１〜３ｍｍの粒状に成形されているので、カラム等に充填しても通液性がよく使用しやすいリチウム吸着剤の製造方法を提供することができる。
（２）焼結により硬度が上がり粉化し難く耐久性に優れたリチウム吸着剤の製造方法を提供することができる。According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) Since it is formed into a particle having a diameter of 0.5 mm to 6 mm, preferably 1 to 3 mm, a method for producing a lithium adsorbent that is easy to use even when packed in a column or the like can be provided. .
(2) It is possible to provide a method for producing a lithium adsorbent that is hard to be pulverized by sintering and excellent in durability.
請求項４に記載の発明によれば、請求項３の効果に加え、
（１）強固に成形されるので機械的強度に優れ、吸着溶離を繰り返しても、形状が崩れないリチウム吸着剤の製造方法を提供することができる。According to invention of Claim 4, in addition to the effect of Claim 3,
(1) A method for producing a lithium adsorbent that is excellent in mechanical strength because it is firmly molded and does not collapse even when adsorption and elution is repeated can be provided.
請求項５の発明によれば、次の有利な効果を実現できるリチウム吸着剤を提供できる。
（１）酸素を過剰に有しているため、Ｍｎ４＋の含有量を増加させ、Ｌｉ＋とのイオン交換反応量を増やすことができる。
（２）プロトンサイト（イオン交換型サイト）にリチウム溶液中からＬｉ＋を取り込むことができる。
（３）マンガン酸化物にはトンネル構造、層状構造、網目状構造などさまざまな構造を持つ化合物があるが、スピネル型と呼ばれる構造を持つマンガン酸化物は（１×３）網目状構造になっている。スピネル型マンガン酸化物の結晶構造を模式的に表したものを図１に示す。金属イオンに対する吸着選択性はマンガン酸化物の結晶構造に依存するが、非量論型のスピネル型マンガン酸化物としたので、Ｌｉ＋に対して高い選択性を示すと共に多量のＬｉ＋とイオン交換をすることができる。また、鹹水はＬｉ＋よりイオン半径の大きいＮａ＋やＫ＋、Ｃａ２＋等の陽イオンを含むがこれらの陽イオンは網目状構造に入ることができない。その理由は、鋳型であるＬｉ＋を取り込むことで調製された吸着剤の前躯体からＬｉ＋を取り除くことにより、Ｌｉ＋の大きさの鋳型を有する多孔結晶型の吸着剤を得ることができるためである。According to invention of Claim 5, the lithium adsorbent which can implement | achieve the following advantageous effects can be provided.
(1) Since it has oxygen excessively, the content of Mn 4+ can be increased and the amount of ion exchange reaction with Li + can be increased.
(2) Li + can be taken into the proton site (ion exchange type site) from the lithium solution.
(3) Manganese oxides include compounds with various structures such as tunnel structures, layered structures, and network structures, but manganese oxides with a structure called spinel type have a (1 × 3) network structure. Yes. A schematic representation of the crystal structure of spinel manganese oxide is shown in FIG. Adsorption selectivity for metal ions depends on the crystal structure of manganese oxide but, since the spinel-type manganese oxide of the non-stoichiometric form, a large amount of Li + ion exchange exhibit both high selectivity for Li + Can do. Further, the brine contains cations such as Na + , K + , and Ca 2+ having an ionic radius larger than that of Li +, but these cations cannot enter the network structure. The reason is that by removing the Li + from the precursor of the adsorbent prepared by incorporating the Li + as a template, it is possible to obtain a porous crystalline adsorbent having a Li + in the size of the mold It is.
請求項６の発明によれば、
（１）酸洗時（溶離時）に定量的にＬｉ＋を溶離させ、かつ、吸着時の繰り返し耐久性に優れるリチウム吸着剤を与えるリチウム吸着剤用原料を提供できる。According to the invention of claim 6,
(1) It is possible to provide a raw material for a lithium adsorbent that elutes Li + quantitatively during pickling (at the time of elution) and gives a lithium adsorbent that is excellent in repeated durability during adsorption.
請求項７に記載の発明によれば、
（１）リチウムイオンの選択性に優れ、リチウムイオンの吸着速度が高く、リチウムイオンの吸着量が高いリチウム吸着体を、安定して繰り返し使用できるので、工業的にリチウムを高濃縮できるリチウム濃縮方法を提供できる。
（２）溶離工程で用いる酸がリチウム吸着剤を溶かさず、またリチウム吸着剤の結晶構造を崩さないので、リチウム吸着剤が劣化しないので、効率のよいリチウム濃縮を工業的に継続できるリチウム濃縮方法を提供できる。According to the invention of claim 7,
(1) A lithium concentrating method that can highly concentrate lithium industrially because a lithium adsorbent having excellent lithium ion selectivity, a high lithium ion adsorption rate, and a high lithium ion adsorption amount can be stably and repeatedly used. Can provide.
(2) Since the acid used in the elution step does not dissolve the lithium adsorbent and does not destroy the crystal structure of the lithium adsorbent, the lithium adsorbent does not deteriorate, so that efficient lithium concentration can be continued industrially. Can provide.
請求項８に記載の発明によれば、
（１）高性能で化学的に安定なリチウム吸着体を有しているので安定で効率的運転が可能なリチウム濃縮装置を提供できる。According to the invention described in claim 8,
(1) A lithium concentrator capable of stable and efficient operation can be provided because it has a high-performance and chemically stable lithium adsorbent.
以下、本発明を実施するための形態について説明する。
本発明の、リチウム吸着剤として機能する層状λ型二酸化マンガン組成物は、スピネル型構造を持ち粒径が１μｍ〜１００μｍの微粒子状あるいは膜状を呈している。Hereinafter, modes for carrying out the present invention will be described.
The layered λ-type manganese dioxide composition that functions as a lithium adsorbent of the present invention has a spinel structure and has a fine particle shape or a film shape with a particle diameter of 1 μm to 100 μm.
本発明のリチウム吸着剤である、層状λ型二酸化マンガン組成物を製造するときに用いるスピネル型マンガン酸リチウム（一般組成：ＬｉＭｎ２Ｏ４）は電池材料として知られており、一般的に、酸化マンガンとリチウム塩の化合物を加熱することによって得られる。その際、酸化マンガンとリチウム塩の混合割合、焼成温度、時間などを変化させることによって、様々な組成を得ることができる。The spinel type lithium manganate (general composition: LiMn 2 O 4 ) used when producing the layered λ-type manganese dioxide composition, which is the lithium adsorbent of the present invention, is known as a battery material and is generally oxidized. It is obtained by heating a compound of manganese and lithium salt. At that time, various compositions can be obtained by changing the mixing ratio of the manganese oxide and the lithium salt, the firing temperature, the time, and the like.
この実施形態においては、リチウム吸着剤を次のようにして得る。即ち、４酸化３マンガン（Ｍｎ３Ｏ４）と水酸化リチウム（ＬｉＯＨ）を、マンガンとリチウムのモル比がＭｎ：Ｌｉ＝１〜１．５：１、好ましくは１≦Ｍｎ／Ｌｉ＜１．２５となるように混合する。これを遊星型高速ボールミルなどメカノケミカル的な粉砕ができる装置で１時間〜２時間処理し、粉砕するとともに物理的な圧縮力、剪弾力、衝撃力を与えるメカノケミカル的な処理を行う。次いでこの粉砕物を、空気雰囲気下３７５℃〜４５０℃の温度域で１時間〜１０時間仮焼成する。仮焼成後、仮焼成物を混合、粉砕し、これを空気雰囲気下に４７５℃〜５２５℃で１時間〜１０時間本焼成する。これにより、（化１）、（化２）で示す反応式により非量論型のリチウム吸着剤を得ることができる。
得られたスピネル型酸素過剰マンガン酸リチウムを造粒した後で、酸処理してλ型二酸化マンガン組成物を得る。即ち、スピネル型酸素過剰マンガン酸リチウムに酸を適用して、イオン交換反応によってリチウムイオンを溶離する。（造粒については後述する。） The obtained spinel-type oxygen-rich lithium manganate is granulated and then acid-treated to obtain a λ-type manganese dioxide composition. That is, an acid is applied to spinel oxygen-rich lithium manganate and lithium ions are eluted by an ion exchange reaction. (The granulation will be described later.)
焼成によって得られたスピネル型酸素過剰マンガン酸リチウムから酸によって初めてリチウムイオンを溶離するに際しては、大過剰の酸たとえば塩酸、過塩素酸、硝酸をリチウムと酸のモル比が、１：２０超、好ましくはリチウム：酸＝１：４０以上となる過剰の酸でリチウムイオンを溶離する必要がある。このときの酸の濃度は０．１Ｍ〜２Ｍである。２Ｍを超える濃度の酸を適用すると、Ｍｎを溶解させて好ましくない。 When eluting lithium ions for the first time with an acid from spinel-type oxygen-excess lithium manganate obtained by firing, a molar ratio of lithium to acid of a large excess of acid such as hydrochloric acid, perchloric acid, or nitric acid is more than 1:20, It is necessary to elute lithium ions with an excess of acid, preferably lithium: acid = 1: 40 or more. The acid concentration at this time is 0.1M to 2M. If an acid having a concentration exceeding 2M is applied, Mn is dissolved, which is not preferable.
大過剰の酸でリチウムイオンを溶離することによって、マンガンの酸化還元反応を抑えて水素イオンとリチウムイオンのイオン交換反応を優先して起こさせることができ、マンガンの溶出を防ぎスピネル構造を維持できる。発明者らの知見によれば、リチウムと酸のモル比を、１：１０乃至１：２０としてスピネル型酸素過剰マンガン酸リチウムからリチウムを溶離すると、λ型二酸化マンガンの結晶構造が崩れることがわかった。スピネル型酸素過剰マンガン酸リチウムから酸によってリチウムを溶離する場合、マンガンの酸化還元反応と水素イオンとリチウムイオンのイオン交換反応が起こることが理由と考えられる。 By eluting lithium ions with a large excess of acid, the redox reaction of manganese can be suppressed and the ion exchange reaction between hydrogen ions and lithium ions can be prioritized, preventing the elution of manganese and maintaining the spinel structure. . According to the knowledge of the inventors, it is found that when lithium is eluted from spinel-type oxygen-rich lithium manganate at a molar ratio of lithium to acid of 1:10 to 1:20, the crystal structure of λ-type manganese dioxide is destroyed. It was. When lithium is eluted with acid from spinel-type oxygen-rich lithium manganate, it is considered that manganese redox reaction and ion exchange reaction between hydrogen ion and lithium ion occur.
スピネル型酸素過剰マンガン酸リチウムから酸によってリチウムを溶離するに際して用いる酸は鉱酸が好ましく、塩酸、過塩素酸、硝酸を用いることができる。発明者らの知見によれば、硫酸水溶液を用いると、得られるλ型二酸化マンガンの結晶構造が破壊されるため好ましくない。 The acid used for eluting lithium from the spinel oxygen-rich lithium manganate with an acid is preferably a mineral acid, and hydrochloric acid, perchloric acid, or nitric acid can be used. According to the knowledge of the inventors, it is not preferable to use a sulfuric acid aqueous solution because the crystal structure of the obtained λ-type manganese dioxide is destroyed.
本発明のリチウム吸着剤製造方法におけるリチウム吸着剤を造粒する方法について説明する。
本焼成によって得られたスピネル型酸素過剰マンガン酸リチウムに対してアルミナやシリカ等の無機バインダ又はキチンやポリ塩化ビニルからなる有機系バインダを１５重量％〜５０重量％加え、少量の水でよく攪拌混合し、押し出し成形機を用いて径０．５ｍｍ〜６ｍｍ好ましくは１〜３ｍｍのペレット状や、ロッド状、紐状に成形する。次いで、無機バインダを用いた場合は、５００℃〜５５０℃で約３時間焼成する。ロッド状や紐状に成形した場合は室温に冷却後に長さ１〜３ｍｍにカッターで切断する。篩に掛けて微粉を除いた後、カラムに充填し前述の方法でリチウムを溶離するとリチウム吸着カラムとなる。
尚、キチンとＰＶＣを比べた場合、海水や鹹水からリチウムを採取する場合は、キチンが好ましい。アルカリ域の水では不溶であり、ＰＶＣバインダより高粘性であり、造粒効率も高く、また、キチンはバイオマスポリマーであり、環境に対して無害なので好適である。A method for granulating a lithium adsorbent in the method for producing a lithium adsorbent of the present invention will be described.
Add 15 wt% to 50 wt% of an inorganic binder such as alumina or silica or an organic binder made of chitin or polyvinyl chloride to the spinel type oxygen-rich lithium manganate obtained by this firing, and stir well with a small amount of water. They are mixed and formed into pellets, rods or strings with a diameter of 0.5 mm to 6 mm, preferably 1 to 3 mm, using an extrusion molding machine. Next, when an inorganic binder is used, baking is performed at 500 ° C. to 550 ° C. for about 3 hours. When it is formed into a rod shape or string shape, it is cut to a length of 1 to 3 mm with a cutter after cooling to room temperature. After removing the fine powder by sieving, if the column is packed and lithium is eluted by the above-mentioned method, it becomes a lithium adsorption column.
In addition, when chitin and PVC are compared, chitin is preferable when extracting lithium from seawater or brine. It is insoluble in alkaline water, is more viscous than PVC binder, has high granulation efficiency, and chitin is a biomass polymer and is suitable because it is harmless to the environment.
４酸化３マンガン（Ｍｎ３Ｏ４）（９９．９％ 添川化学製）と水酸化リチウム・１水和物（ＬｉＯＨ・Ｈ２Ｏ）（関東化学製）を、マンガンとリチウムのモル比が１．２：１となるように、瑪瑙乳鉢にて１５分間混合・粉砕した混合・粉砕物を高速遊星型ボールミル（ドイツ フリッチュ社製、モデルＰ−５）によって、ディスク回転数５０ｒｐｍ、ポット回転数４００ｒｐｍで１５分〜２時間メカノケミカル的な粉砕処理をした。次いで処理物を、空気雰囲気中で３７５℃に保たれた電気炉にて５時間、仮焼成を行った。
仮焼成物を一旦冷却した後１５分〜２時間瑪瑙乳鉢で混合・粉砕し、再び空気雰囲気下、５００℃に保たれた電気炉にて５時間、本焼成を行った。Tetramanganese tetraoxide (Mn 3 O 4 ) (99.9% manufactured by Soekawa Chemical) and lithium hydroxide monohydrate (LiOH.H 2 O) (manufactured by Kanto Chemical Co., Ltd.) with a molar ratio of manganese to lithium of 1 The mixed and pulverized material mixed and pulverized for 15 minutes in an agate mortar so as to have a ratio of 2: 1 was rotated at a disc rotation speed of 50 rpm and a pot rotation speed of 400 rpm by a high-speed planetary ball mill (Model F-5, manufactured by Friitch Germany). For 15 minutes to 2 hours. Next, the treated product was temporarily fired in an electric furnace maintained at 375 ° C. in an air atmosphere for 5 hours.
The temporarily fired product was once cooled, mixed and pulverized in an agate mortar for 15 minutes to 2 hours, and again fired for 5 hours in an electric furnace maintained at 500 ° C. in an air atmosphere.
図１に実施例１の仮焼成後の仮焼成物のＸ線回折の結果を示す。メカノケミカル的な処理の時間を長くしていくにつれて４酸化３マンガンのピーク（図中の矢印で示したピーク）が消失してスピネル構造になっていくことが示された。またメカノケミカル的処理が短いと仮焼成後に４酸化３マンガンが未反応で残ることが示された。
図２に実施例１の本焼成後の焼成物のＸ線回折の結果を示す。本焼成後の焼成物のＸ線回折のパターンでは、メカノケミカル的な処理の時間を変えても、図１に見られたような変化は見られなかった。FIG. 1 shows the result of X-ray diffraction of the calcined product after calcining in Example 1. It was shown that the peak of 3 manganese tetroxide (the peak indicated by the arrow in the figure) disappears and becomes a spinel structure as the mechanochemical treatment time is increased. Further, it was shown that when the mechanochemical treatment was short, trimanganese tetroxide remained unreacted after calcination.
FIG. 2 shows the result of X-ray diffraction of the fired product after the main firing of Example 1. In the X-ray diffraction pattern of the fired product after the main firing, even if the time of mechanochemical treatment was changed, the change as seen in FIG. 1 was not observed.
しかし、発明者らの知見によるとメカノケミカル的処理が短く、４酸化３マンガンが未反応で残っているものは、本焼成をしても、強度が弱く、酸によるリチウムの溶離によって崩れやすいことがわかった。Ｘ線回折のパターンでは現れない結晶構造の違いがあるものと考えられる。 However, according to the knowledge of the inventors, the mechanochemical treatment is short, and those in which 3 manganese tetraoxide is left unreacted are weak in strength even after the main calcination, and are liable to collapse due to elution of lithium by acid. I understood. It is considered that there is a difference in crystal structure that does not appear in the X-ray diffraction pattern.
実施例１の本焼成後の試料を３Ｍ 塩酸／１０％Ｈ２Ｏ２に全溶解し、ＩＣＰ−ＡＥＳによってＬｉとＭｎの比を求めた。
メカノケミカル的な処理の時間が１５分のもの及び３０分のものではどちらもＬｉ１．４Ｍｎ２Ｏ４．２（有意差なし）であった。
メカノケミカル的な処理の時間が４５分〜１２０分のものではいずれもＬｉ１．８Ｍｎ２Ｏ４．２（有意差なし）であった。
メカノケミカル的な処理により結晶構造に取り込まれるＬｉの量が増えていることが示された。The sample after the main firing of Example 1 was completely dissolved in 3M hydrochloric acid / 10% H 2 O 2 and the ratio of Li to Mn was determined by ICP-AES.
Both the mechanochemical treatment time of 15 minutes and 30 minutes was Li 1.4 Mn 2 O 4.2 (no significant difference).
When the time of mechanochemical treatment was 45 minutes to 120 minutes, all were Li 1.8 Mn 2 O 4.2 (no significant difference).
It was shown that the amount of Li incorporated into the crystal structure is increased by mechanochemical treatment.
実施例１でメカノケミカル的な処理の時間を９０分として得られたスピネル型酸素過剰マンガン酸リチウム６．５ｇとアルミナバインダ（日揮触媒化成工業製ＡＰ−１）３．５ｇとを少量のイオン交換水とよく混合し、団子状とし、ビニル袋に入れて一晩室温放置する。一晩放置した団子状の混合物を押し出し成形機（自作エクストルーダー）を用いて直径１ｍｍのロッド状にした。ロッド状に成形したものを再度、一晩室温放置する。一晩放置したロッド状の混合物を電気炉で５５０℃で３時間焼結した。室温まで冷ましたロッド状の焼結物を１〜２ｍｍ長さにカッターで切断した。篩い分けによって微粉を除いた後、このリチウムを含んだ状態の吸着剤を長さ１０ｃｍのカラムに充填し（３．２ｇ、湿容量＝ ３．５ｃｍ３）、１．０ Ｍの塩酸で５回、酸処理を行い、リチウムイオンを溶離して、リチウム吸着剤を得た。
このカラムを用いて海水（ｐＨｉｎｉ = ８．１）を流した場合のリチウムの溶離について調べた。供給溶液としては海水を用い、送液ポンプを用いて流速０．２ｃｍ３／分でカラムに通液した。溶出液は、一定時間ごとにフラクションコレクターを用いて採取した。リチウムイオンの破過を確認した後、イオン交換水を２時間流してカラム洗浄を行い、続いて１．０Ｍの塩酸をカラムに通液することでリチウムの溶離を行った。ベッドボリューム（ＢＶ）は、以下の式を用いて計算した。
ＢＶ = ｖ×ｔ／Ｖ
ここで、ｖは供給溶液の流速［ｃｍ３／分］、ｔはサンプリング時間［分］、Ｖはカラムに充填した粒子状吸着剤のウェットボリューム［ｃｍ３］である。リチウムの最大吸着量は、溶離曲線を積分することによって得られたリチウム溶出量と、用いた造粒リチウム吸着剤の量から計算することによって求めた。粒子状吸着剤中のリチウム吸着剤の量は、粒子状吸着剤の重量からバインダ量を差し引くことによって計算した。A small amount of ion exchange was performed using 6.5 g of spinel-type oxygen-rich lithium manganate obtained in Example 1 with a mechanochemical treatment time of 90 minutes and 3.5 g of alumina binder (AP-1 manufactured by JGC Catalysts & Chemicals). Mix well with water to form dumplings, place in a plastic bag, and let stand at room temperature overnight. The dumpling mixture left overnight was formed into a rod having a diameter of 1 mm using an extrusion molding machine (self-made extruder). The rod-shaped material is again left overnight at room temperature. The rod-like mixture left overnight was sintered in an electric furnace at 550 ° C. for 3 hours. The rod-shaped sintered product cooled to room temperature was cut into a length of 1 to 2 mm with a cutter. After removing fine powder by sieving, the adsorbent containing lithium was packed in a column of 10 cm in length (3.2 g, wet capacity = 3.5 cm 3 ), and 5 times with 1.0 M hydrochloric acid. Then, acid treatment was performed and lithium ions were eluted to obtain a lithium adsorbent.
Using this column, the elution of lithium when seawater (pH ini = 8.1) was passed was examined. Seawater was used as the feed solution, and the solution was passed through the column at a flow rate of 0.2 cm 3 / min using a liquid feed pump. The eluate was collected using a fraction collector at regular intervals. After confirming the breakthrough of lithium ions, ion exchange water was flowed for 2 hours to perform column washing, and then 1.0M hydrochloric acid was passed through the column to elute lithium. The bed volume (BV) was calculated using the following formula.
BV = v x t / V
Here, v is the flow rate of the feed solution [cm 3 / min], t is the sampling time [min], and V is the wet volume [cm 3 ] of the particulate adsorbent packed in the column. The maximum lithium adsorption amount was determined by calculating from the lithium elution amount obtained by integrating the elution curve and the amount of granulated lithium adsorbent used. The amount of lithium adsorbent in the particulate adsorbent was calculated by subtracting the binder amount from the weight of the particulate adsorbent.
実施例１でメカノケミカル的な処理の時間を９０分として得られたスピネル型酸素過剰マンガン酸リチウム１０ｇとシリカバインダスラリー（ＡＧＣエスアイテック製サンラブリーＬＦＳ）３．０ｇとをビニル袋内に入れてよく混合し、団子状にする。硬さはイオン交換水で調整する。団子状の混合物をビニル袋内で一晩室温放置する。一晩放置した混合物を押し出し成形機（自作エクストルーダー）を用いて直径１ｍｍのロッド状にした。ロッド状に成形したものを再度、一晩室温放置する。一晩放置したロッド状の混合物を電気炉で５５０℃で３時間焼結した。室温まで冷ましたロッド状の焼結物を１〜２ｍｍ長さにカッターで切断した。篩い分けによって微粉を除いた後、実施例２と同様にカラムに充填し、リチウムイオンを溶離してリチウム吸着剤を得た。このカラムを用いて海水（ｐＨｉｎｉ = ８．１）を流した場合のリチウムの溶離について実施例２と同様にして調べた。10 g of spinel type oxygen-rich lithium manganate and 3.0 g of silica binder slurry (Sun Lovely LFS manufactured by AGC S-Tech) were obtained in Example 1 with a mechanochemical treatment time of 90 minutes. Mix well and dump. The hardness is adjusted with ion exchange water. The dumpling mixture is left in a vinyl bag overnight at room temperature. The mixture left overnight was formed into a rod shape having a diameter of 1 mm using an extruder (self-made extruder). The rod-shaped material is again left overnight at room temperature. The rod-like mixture left overnight was sintered in an electric furnace at 550 ° C. for 3 hours. The rod-shaped sintered product cooled to room temperature was cut into a length of 1 to 2 mm with a cutter. After removing fine powder by sieving, the column was packed in the same manner as in Example 2, and lithium ions were eluted to obtain a lithium adsorbent. The elution of lithium when seawater (pH ini = 8.1) was passed using this column was examined in the same manner as in Example 2.
キチン（東京化成製）０．５ｇと塩化リチウム・１水和物（ＬｉＣｌ・Ｈ２Ｏ）（関東化学製）２．５ｇとＮ−メチルピロリジン（関東化学製）５０ｍＬを混ぜ、２日間攪拌し、高粘性の液状キチンバインダ（キチン含量１重量％）を得た。実施例１でメカノケミカル的な処理の時間を９０分として得られたスピネル型酸素過剰マンガン酸リチウム１０ｇと前記液状キチンバインダスラリー１０ｇとを２−プロパノール中に滴下し、キチンを不溶化することによって粒状化した。粒状化した沈殿物をろ過によって回収し、６０℃で１０時間乾燥させた。これを実施例２と同様にカラムに充填し、リチウムイオンを溶離してリチウム吸着剤を得た。このカラムを用いて海水（ｐＨｉｎｉ＝８．１）を流した場合のリチウムイオンの溶離について実施例２と同様にして調べた。Mix 0.5 g of chitin (manufactured by Tokyo Chemical Industry), 2.5 g of lithium chloride monohydrate (LiCl.H 2 O) (manufactured by Kanto Chemical) and 50 mL of N-methylpyrrolidine (manufactured by Kanto Chemical) and stir for 2 days. A highly viscous liquid chitin binder (chitin content 1% by weight) was obtained. 10 g of spinel-type oxygen-rich lithium manganate and 10 g of the above liquid chitin binder slurry obtained in Example 1 with a mechanochemical treatment time of 90 minutes were dropped into 2-propanol to insolubilize the chitin. Turned into. The granulated precipitate was collected by filtration and dried at 60 ° C. for 10 hours. This was packed into a column in the same manner as in Example 2, and lithium ions were eluted to obtain a lithium adsorbent. The elution of lithium ions when seawater (pH ini = 8.1) was passed using this column was examined in the same manner as in Example 2.
図３に実施例２の海水（ｐＨｉｎｉ＝８．１）を流した場合のリチウムイオンの破過曲線（ａ）を示した。これにより、ナトリウムイオンが大量に（１０，７８０ｐｐｍ）存在する海水の場合においても、微量成分であるリチウムイオンを選択的に吸着・回収できることが明らかとなった。
図４に実施例３の１．０Ｍの塩酸溶液を用いて溶離した場合の、リチウム、ナトリウム、マンガンの各イオンの溶離曲線を示した。この結果から、リチウムイオンは早い段階で容易に溶離できること、および、溶離溶液中にはナトリウムイオンはほとんど含有されていないことが明らかとなった。また、溶離液中のリチウム濃度は最大３７７７ｐｐｍとなり、供給溶液の約４００倍に濃縮することに成功した。また、溶離曲線を積分して得られるリチウム吸着量は、２．３１ｍｍｏｌ／ｇとなり、リチウム吸着剤の性能試験で得られた最大吸着量とほぼ一致した。また、造粒リチウム吸着剤からのマンガンの溶出量は、吸着剤中のマンガン０．１５重量％が溶出するにとどまった。これに対して実施例４の有機系バインダによる造粒法は、マンガンの溶出が０．４２重量％であった。また（特許文献３）に記載の有機系ポリマーによる造粒ではマンガンの溶出が０．４６重量%であるので、無機系バインダの使用によって６０重量％のマンガンの溶出を抑制できることが示された。実施例２と実施例３の無機系バインダの種類の違いによる差は認められなかった。FIG. 3 shows a lithium ion breakthrough curve (a) when the seawater (pH ini = 8.1) of Example 2 was passed. Thereby, even in the case of seawater in which sodium ions are present in large quantities (10,780 ppm), it has become clear that lithium ions, which are trace components, can be selectively adsorbed and recovered.
FIG. 4 shows the elution curves of lithium, sodium, and manganese ions when eluted with the 1.0 M hydrochloric acid solution of Example 3. From this result, it became clear that lithium ions can be easily eluted at an early stage, and that sodium ions are hardly contained in the elution solution. In addition, the maximum concentration of lithium in the eluent was 3777 ppm, which was successfully concentrated to about 400 times that of the supplied solution. Further, the lithium adsorption amount obtained by integrating the elution curve was 2.31 mmol / g, which almost coincided with the maximum adsorption amount obtained in the performance test of the lithium adsorbent. Further, the elution amount of manganese from the granulated lithium adsorbent was only 0.15% by weight of manganese in the adsorbent. On the other hand, in the granulation method using the organic binder of Example 4, manganese elution was 0.42% by weight. In addition, since elution of manganese is 0.46% by weight in the granulation with an organic polymer described in (Patent Document 3), it was shown that elution of 60% by weight of manganese can be suppressed by using an inorganic binder. No difference due to the difference in the type of inorganic binder between Example 2 and Example 3 was observed.
実施例２と同じ方法で作成したＨＭｎ２Ｏ４型のリチウム吸着剤１０ｍｇをサンプル１としてＬｉＣｌ溶液１０ｍL（０．５〜２０ｐｐｍ）をそれぞれ三角フラスコに入れ、２５℃の振とう機で約１２時間振とうさせ、振とう後のリチウムの濃度を原子吸光で測定しリチウム吸着剤の性能を調べた。サンプル２として、特許文献４のリチウム吸着剤１０ｍｇを準備し、サンプル１と同様に行った。10 mL of HMn 2 O 4 type lithium adsorbent prepared in the same manner as in Example 2 was used as sample 1 and 10 mL of LiCl solution (0.5 to 20 ppm) was placed in each Erlenmeyer flask, and the mixture was shaken at 25 ° C. for about 12 hours. The lithium concentration after shaking was measured by atomic absorption to examine the performance of the lithium adsorbent. As Sample 2, 10 mg of the lithium adsorbent disclosed in Patent Document 4 was prepared and performed in the same manner as Sample 1.
図５に実施例５の結果を示す。横軸が吸着平衡に達したときの水溶液中に残っているリチウム濃度を示し、縦軸がリチウム吸着量を示す。サンプル１を×印でサンプル２を△印で示している。
この吸着等温実験からサンプル１とサンプル２のリチウム最大吸着量はそれぞれ２．３６ｍｍｏｌ／ｇ、２．０８ｍｍｏｌ／ｇとなった。この値は、（特許文献４）の吸着剤のそれぞれ１．６倍、１．４倍高い値であり、メカノケミカル効果によりリチウム吸着量が増えたことが示された。 FIG. 5 shows the results of Example 5. The horizontal axis indicates the concentration of lithium remaining in the aqueous solution when the adsorption equilibrium is reached, and the vertical axis indicates the lithium adsorption amount. Sample 1 is indicated by x and sample 2 is indicated by Δ.
From this adsorption isothermal experiment, the maximum lithium adsorption amounts of Sample 1 and Sample 2 were 2.36 mmol / g and 2.08 mmol / g, respectively. These values were 1.6 times and 1.4 times higher than the adsorbent of (Patent Document 4), respectively, indicating that the lithium adsorption amount increased due to the mechanochemical effect.
実施例１で得られたリチウム吸着剤（Ｌｉ１．４Ｍｎ２Ｏ４．２，Ｌｉ１．８Ｍｎ２Ｏ４．２）を用い、リチウム吸着に対する、吸着剤のｐH依存性を調べた。ＬｉＣｌ溶液のｐHを６．０、７．０、８．０、８．３、８．５、９．８、９．０にした以外は実施例４と同様にして、それぞれ三角フラスコに入れ、２５℃の振とう機で約１２時間振とう（回転数：１５０ｒｐｍ）させ、振とう後の溶液のｐＨ（平衡ｐＨ）とリチウムの濃度を測定した。
尚、比較例として、特許文献４の実施例に基づいて、リチウム吸着剤を作製した。Ｘ線回折で確認したところ、Ｌｉ１．０Ｍｎ２Ｏ４．２であった。この試料を用い同様にしてｐＨ依存性を測定した。Using the lithium adsorbent (Li 1.4 Mn 2 O 4.2 , Li 1.8 Mn 2 O 4.2 ) obtained in Example 1, the pH dependence of the adsorbent on lithium adsorption was examined. In the same manner as in Example 4 except that the pH of the LiCl solution was 6.0, 7.0, 8.0, 8.3, 8.5, 9.8, 9.0, The mixture was shaken with a shaker at 25 ° C. for about 12 hours (rotation number: 150 rpm), and the pH (equilibrium pH) and lithium concentration of the solution after shaking were measured.
As a comparative example, a lithium adsorbent was prepared based on the example of Patent Document 4. When confirmed by X-ray diffraction, it was Li 1.0 Mn 2 O 4.2 . Using this sample, the pH dependency was measured in the same manner.
その結果を図６に示した。Ｌｉ１．４Ｍｎ２Ｏ４．２は◆印、Ｌｉ１．８Ｍｎ２Ｏ４．２は■印、Ｌｉ１．０Ｍｎ２Ｏ４．２は△印で示した。図６において、横軸が平衡ｐＨで、縦軸がリチウム吸着量を表す。比較例として（特許文献４）に記載のＬｉＭｎ２Ｏ４．２の結果を三角印で示している。弱酸性〜アルカリ域で実施例１で得られたリチウム吸着剤が特許文献４に記載のリチウム吸着剤ＬｉＭｎ２Ｏ４．２より高い吸着性能を示した。また、図６から明らかなように、Ｌｉ１．８Ｍｎ２Ｏ４．２（Ｍｎ／Ｌｉ＝１．１１）がＬｉ１．４Ｍｎ２Ｏ４．２（Ｍｎ／Ｌｉ＝１．４３）よりもｐＨ６〜８の間でリチウム吸着量が１３５〜１４５％優れていることがわかった。The results are shown in FIG. Li 1.4 Mn 2 O 4.2 is indicated by ◆, Li 1.8 Mn 2 O 4.2 is indicated by ■, and Li 1.0 Mn 2 O 4.2 is indicated by Δ. In FIG. 6, the horizontal axis represents the equilibrium pH, and the vertical axis represents the lithium adsorption amount. As a comparative example, the results of LiMn 2 O 4.2 described in (Patent Document 4) are indicated by triangles. The lithium adsorbent obtained in Example 1 in weakly acidic to alkaline range showed higher adsorption performance than the lithium adsorbent LiMn 2 O 4.2 described in Patent Document 4. Further, as is apparent from FIG. 6, Li 1.8 Mn 2 O 4.2 (Mn / Li = 1.11) is more than Li 1.4 Mn 2 O 4.2 (Mn / Li = 1.43). It was also found that the lithium adsorption amount was 135 to 145% superior between pH 6 and 8.
（１）リチウム吸着剤の作製
スピネル型マンガン酸リチウムのイオン交換によるリチウムの吸着量に対する酸素モル数の依存性について確認した。
４酸化３マンガン（Ｍｎ３Ｏ４）（９９．９％ 添川化学製）と水酸化リチウム・１水和物（ＬｉＯＨ・Ｈ２Ｏ）（関東化学製）、ＴｉＯ２（関東化学製）、ＮｉＯ（関東化学製）を準備し、（表１）に示すモル比となるように調整し、瑪瑙乳鉢にて１５分間混合・粉砕した混合・粉砕物を高速遊星型ボールミル（ドイツ フリッチュ社製、モデルＰ−５）によって、ディスク回転数５０ｒｐｍ、ポット回転数４００ｒｐｍで９０分間メカノケミカル的な粉砕処理をした。次いで処理物を、空気雰囲気中で３７５℃に保たれた電気炉にて５時間、仮焼成を行った。
各仮焼成物を一旦冷却した後１５分〜２時間瑪瑙乳鉢で混合・粉砕し、再び空気雰囲気下、５００℃に保たれた電気炉にて５時間、本焼成を行った。(1) Production of Lithium Adsorbent The dependence of the number of moles of oxygen on the amount of lithium adsorbed by ion exchange of spinel type lithium manganate was confirmed.
Tetramanganese tetramanganese (Mn 3 O 4 ) (99.9% manufactured by Soekawa Chemical) and lithium hydroxide monohydrate (LiOH · H 2 O) (manufactured by Kanto Chemical), TiO 2 (manufactured by Kanto Chemical), NiO (Manufactured by Kanto Chemical Co., Inc.), adjusted to the molar ratio shown in (Table 1), mixed and pulverized for 15 minutes in an agate mortar, and mixed and pulverized product is a high-speed planetary ball mill (made by Frichtu, Germany, model According to P-5), a mechanochemical grinding process was performed for 90 minutes at a disc rotation speed of 50 rpm and a pot rotation speed of 400 rpm. Next, the treated product was temporarily fired in an electric furnace maintained at 375 ° C. in an air atmosphere for 5 hours.
Each temporarily fired product was once cooled, mixed and pulverized in an agate mortar for 15 minutes to 2 hours, and again fired for 5 hours in an electric furnace maintained at 500 ° C. in an air atmosphere.
本焼成後の各試料を３Ｍ 塩酸／１０％Ｈ２Ｏ２に全溶解し、ＩＣＰ−ＡＥＳによってＬｉ、Ｍｎ、Ｏのモル比を求めた。その結果を表１の組成式に示した。Each sample after the main firing was completely dissolved in 3M hydrochloric acid / 10% H 2 O 2, and the molar ratios of Li, Mn and O were determined by ICP-AES. The results are shown in the composition formula of Table 1.
（２）吸着剤の再生
（イ）サンプルを１ｇずつ秤量し、１ｍｏｌ／塩酸２０ｍｌと三角フラスコに入れ密封して、空気浴振盪機で一晩振盪した（温度：３０℃ 回転数：１５０ｒｐｍ）。
（ロ）ロートを用いて減圧濾過し、蒸留水で丁寧に洗浄した。その後そのまま６０℃に設定した乾燥機にいれ１時間乾燥させた。これを１回酸処理物とし５回同じ操作で酸処理を行った。そしてリチウム吸着剤（Ｈ型）とした。(2) Regeneration of adsorbent (i) 1 g of each sample was weighed, sealed in an Erlenmeyer flask with 1 mol / hydrochloric acid 20 ml, and shaken overnight in an air bath shaker (temperature: 30 ° C., rotational speed: 150 rpm).
(B) The solution was filtered under reduced pressure using a funnel and washed carefully with distilled water. Thereafter, it was placed in a dryer set at 60 ° C. and dried for 1 hour. This was treated once as an acid-treated product, and acid-treated by the same operation 5 times. And it was set as the lithium adsorbent (H type).
（３）吸着剤のリチウム吸着実験
（イ）５ｍｍｏｌ／ＬのＮａＣｌ、ＬｉＣｌを含むｐＨ＝８．１の０．１ｍｏｌ／Ｌ‐ＮＨ４Ｃｌ・ＮＨ４ＯＨ緩衝溶液を調整し、この緩衝溶液１０ｍｌと酸処理済みの吸着剤０．０２ｇを三角フラスコにいれ密封し、空気浴振盪機で一晩振盪した（温度：３０℃ 回転数：１５０ｒｐｍ）。
（ロ）その後自然濾過し、濾液はＡＡＳを用いてＬｉ、Ｎａの定量を行った。その結果を図７に示す。(3) Lithium adsorption experiment of adsorbent (a) 0.1 mol / L-NH 4 Cl · NH 4 OH buffer solution with pH = 8.1 containing 5 mmol / L NaCl and LiCl was prepared, and 10 ml of this buffer solution And 0.02 g of the acid-treated adsorbent were put in an Erlenmeyer flask, sealed, and shaken overnight with an air bath shaker (temperature: 30 ° C., rotation speed: 150 rpm).
(B) Thereafter, the solution was naturally filtered, and the filtrate was subjected to quantitative determination of Li and Na using AAS. The result is shown in FIG.
（４）結果と考察
酸素過剰型の実験Ｎｏ．１，７，８が一般組成型より極めて高いＬｉ吸着能を示した。しかもＮａの吸着は全試料において認められなかった。
この結果、海水や地熱水等からＬｉを選択的に高収率で採取できることがわかった。(4) Results and Discussion Oxygen-rich experiment No. 1, 7 and 8 showed Li adsorption capacity much higher than that of the general composition type. Moreover, no Na adsorption was observed in all samples.
As a result, it was found that Li can be selectively collected in high yield from seawater, geothermal water, and the like.
本願発明によれば、太陽電池やバッテリー材料として重要な元素でありながら、従来の鉱物資源からの供給では、資源の枯渇が心配されていたリチウムを海水や地熱水などの環境水から、リチウム資源として活用できるリチウム吸着剤の製造方法を提供できる。さらに、廃棄物や廃水などから効果的にリチウムを回収できるリチウム吸着剤の製造方法を提供できる。また本願発明によれば、海水や地熱水などの微量のリチウムを含む水や、リチウムを含む廃棄物や廃水などから、工業的に、安定に、継続してリチウムを濃縮できるリチウムの濃縮方法とその装置を提供できる。
According to the present invention, lithium, which is an element that is important as a solar cell or battery material, but has been worried about resource depletion in the supply from conventional mineral resources, is obtained from environmental water such as seawater and geothermal water. A method for producing a lithium adsorbent that can be used as a resource can be provided. Furthermore, it is possible to provide a method for producing a lithium adsorbent capable of effectively recovering lithium from waste or waste water. Further, according to the present invention, a lithium concentration method capable of continuously and stably concentrating lithium from water containing a small amount of lithium, such as seawater or geothermal water, and waste and waste water containing lithium. And its apparatus.
【０００１】
技術分野
［０００１］
本発明は、海水や地熱水等のリチウムを含むリチウム含有水から微量に含まれるリチウムを選択的に濃縮・採取するために用いる、また、廃棄物や廃水に合まれるリチウムを選択的に効率よく分離・回収するために用いるλ型マンガン酸化物からなるリチウム吸着剤の製造方法とそのリチウム吸着剤を用いたリチウム濃縮方法及びリチウム濃縮装置に関する。
背景技術
［０００２］
海水中には多くの溶存成分があり、その絶対量の大きさからその溶存成分を採取することが注目されてきた。海水中の元素量を陸上の推定埋蔵量と比較すると、大部分の元素について海水中の溶存量の方が大きいことが知られている。しかしながら、海水中の元素濃度は極めて低く、工業的に利用可能なものは限られている。この中で、現在、工業化されているものとして、塩化ナトリウム、塩化マグネシウム、臭素、塩化カリウムなどを挙げることができる。
［０００３］
リチウム、ウラン、金、銅などは海水における溶存濃度が極めて低いが、その利用価値が高いために工業的に利用可能な採取技術の開発が進められている。リチウムは、大容量電池や航空機用軽合金のための添加元素、または核融合燃料など将来有望な用途がある。また、リチウムは、ウランなどに比べると海水中の濃度が高く、平均０．１７ｐｐｍであるが、ナトリウム（１０，０００ｐｐｍ以上）など高濃度の共存金属を随伴させることなく、リチウムのみを選択的に採取することが必要である。温泉水等地熱熱水や塩湖かん水には様々な金属イオンが溶け込んでおり、特にリチウムイオンは海水中の溶存濃度に比し格段に濃度が高く、例えば地熱熱水中の濃度は海水中のそ[0001]
Technical field [0001]
The present invention is used for selectively concentrating and collecting a small amount of lithium from lithium-containing water containing lithium such as seawater and geothermal water, and selectively using lithium combined with waste and wastewater. The present invention relates to a method for producing a lithium adsorbent composed of λ-type manganese oxide used for efficient separation and recovery, a lithium concentration method using the lithium adsorbent, and a lithium concentrator.
Background art [0002]
There are many dissolved components in sea water, and it has been noticed that the dissolved components are collected from the absolute amount. When comparing the amount of elements in seawater with the estimated reserves on land, it is known that the dissolved amount in seawater is larger for most elements. However, the concentration of elements in seawater is extremely low, and those that can be used industrially are limited. Among these, sodium chloride, magnesium chloride, bromine, potassium chloride and the like can be cited as industrialized products.
[0003]
Lithium, uranium, gold, copper, etc. have extremely low dissolved concentrations in seawater, but because of their high utility value, the development of industrially applicable collection techniques is underway. Lithium has promising applications such as additive elements for high capacity batteries and aircraft light alloys, or fusion fuels. Lithium has a higher concentration in seawater than uranium and the average is 0.17 ppm. However, only lithium is selectively used without accompanying a high concentration of coexisting metals such as sodium (10,000 ppm or more). It is necessary to collect. Various metal ions dissolve in geothermal hot water such as hot spring water and salt lake brine. Especially, lithium ions are much higher than the dissolved concentration in seawater. For example, the concentration in geothermal hot water is So
【０００３】
をマンガンとリチウムのモル比を１．５〜２．５となるように混合・粉砕し、仮焼成と本焼成をしてスピネル型酸素過剰マンガンを得て、該スピネル型酸素過剰マンガンを大過剰の酸で処理してリチウムを溶離し、リチウム吸着剤を製造する方法が記載されている。
先行技術文献
特許文献
［００１０］
特許文献１：特許第３８７６３０８号公報
特許文献２：特許第３８８３４９１号公報
特許文献３：特開２００４−１１５３１４号公報
特許文献４：特許第３９３７８６５号公報
非特許文献
［００１１］
非特許文献１：Ｒ．Ｃｈｉｔｒａｋａｒ，Ｈ．Ｋｎｏｈ，Ｙ．Ｍｉｙａｉ，Ｋ．Ｏｏｉ，“Ｒｅｃｏｖｅｒｙ ｏｆ ｌｉｔｈｉｕｍ ｆｒｏｍ ｓｅａｗａｔｅｒ ｕｓｉｎｇ ｍａｎｇａｎｅｓｅ ｏｘｉｄｅ ａｄｓｏｒｂｅｎｔ（Ｈ１．６Ｍｎ１．６Ｏ４）ｄｅｒｉｖｅｄ ｆｒｏｍ Ｌｉ１．６Ｍｎ１．６Ｏ４”，Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．Ｒｅｓ．，４０，２０５４−２０５８（２００１）
非特許文献２：Ｋ．−Ｓ．Ｃｈｕｎｇ，Ｊ．−Ｃ．Ｌｅｅ，Ｅ．−Ｊ．Ｋｉｍ，Ｋ．−Ｃ．Ｌｅｅ，Ｙ．−Ｓ．Ｋｉｍ，Ｋ．Ｏｏｉ，“Ｒｅｃｏｖｅｒｙ ｏｆ ｌｉｔｈｉｕｍ ｆｒｏｍ ｓｅａｗａｔｅｒ ｕｓｉｎｇ ｎａｎｏ−ｍａｎｇａｎｅｓｅ ｏｘｉｄｅ ａｄｓｏｒｂｅｎｔｓ ｐｒｅｐａｒｅｄ ｂｙ ｇｅｌ ｐｒｏｃｅｓｓ”，Ｍａｔｅｒｉａｌｓ Ｓｃｉｅｎｃｅ Ｆｏｒｕｍ，４４９−４５２，２７７−２８０（２００４）
非特許文献３：Ｋ．Ｏｏｉ，Ｙ．Ｍｉｙａｉ，Ｓ．Ｋａｔｏｈ，Ｈ．Ｍａｅｄａ，Ｍ．Ａｂｅ，“Ａｎａｌｙｓｉｓ ｏｆ ｐＨ ｔｉｔｒａｔｉｏｎｄａｔａ ｉｎ ａ λ・ＭｎＯ２＋ＬｉＯＨ ｓｙｓｔｅｍ ｏｎ ｔｈｅ ｂａｓｉｓ ｏｆ ｒｅｄｏｘ ｍｅｃｈａｎｉｓｍ”，Ｌａｎｇｍｕｉｒ，６，２８９−９１（１９９０）[0003]
Is mixed and pulverized so that the molar ratio of manganese to lithium is 1.5 to 2.5, and is subjected to preliminary firing and main firing to obtain spinel-type oxygen-excess manganese, and the spinel-type oxygen-excess manganese is largely excessive. A method for producing a lithium adsorbent by eluting lithium with an acid is described.
Prior Art Literature Patent Literature [0010]
Patent Document 1: Japanese Patent No. 3876308 Patent Document 2: Japanese Patent No. 3883491 Patent Document 3: Japanese Patent Application Laid-Open No. 2004-115314 Patent Document 4: Japanese Patent No. 3937865 Non-Patent Document [0011]
Non-Patent Document 1: R.A. Chitrakar, H.C. Knoh, Y .; Miyai, K .; Ooi, “Recovery of lithium from water aging manganese oxide adsorbent (H 1.6 Mn 1.6 O 4 ) derived from Li Li 1.6 Mn 1.6 O 4 ”, Ind. Eng. Chem. Res. , 40, 2054-2058 (2001)
Non-Patent Document 2: K.K. -S. Chung, J. et al. -C. Lee, E .; -J. Kim, K .; -C. Lee, Y .; -S. Kim, K .; Ooi, “Recovery of lithium from water waving nano-manganese oxidative ads prepared by gel process”, Materials Science Forum, 449-452, 44-2-4.
Non-Patent Document 3: K.K. Ooi, Y .; Miyai, S .; Katoh, H .; Maeda, M .; Abe, “Analysis of pH titration data in a λ · MnO 2 + LiOH system on the basis of redox mechanism”, Langmuir, 6, 289-91 (1990).
【０００６】
ウム濃縮装置の提供を目的とする。
（５）海水中あるいは地熱熱水中に含まれるリチウムを効率よく選択的に高濃縮でき、長期の繰り返し使用ができるリチウム濃縮装置を提供することを目的とする。
課題を解決するための手段
［００１４］
上記従来の課題を解決するために本発明のリチウム吸着剤の製造方法とそのリチウム吸着剤を用いたリチウム濃縮方法及びリチウム濃縮装置は、以下の構成を有している。
［００１５］
本発明の請求項１に記載のリチウム吸着剤の製造方法は、４酸化３マンガン（Ｍｎ３Ｏ４）及び水酸化リチウム（ＬｉＯＨ）を、マンガンとリチウムのモル比がＭｎ：Ｌｉ＝１〜１．５：１となるように混合し、仮焼成後の仮焼成物のＸＲＤにおけるＭｎ３Ｏ４の２θ＝３２．６度のピークの強度が１０％以上低下するまでメカノケミカル的に粉砕処理をするメカノケミカル工程と、次いで空気あるいは酸素雰囲気下にて３７５℃〜４５０℃の温度域で仮焼成する仮焼成工程と、次いで冷却し混合粉砕した後、空気あるいは酸素雰囲気下にて４７５℃〜５５０℃の温度域で本焼成を行いスピネル型酸素過剰マンガン酸リチウムを得る本焼成工程と、該スピネル型酸素過剰マンガン酸リチウムをリチウムに対して大過剰の酸で処理してリチウムイオンを溶離する溶離工程と、を備えた構成を有している。
この構成により、以下のような作用が得られる。
（１）メカノケミカル効果によりＭｎ３Ｏ４とＬｉＯＨの相互作用が高まり、従来よりもＬｉの配合比が高くても酸素過剰マンガン酸リチウムがスピネル構造を保つようになった。そのため、リチウムイオンに対する選択吸着性に優れるとともに吸着速度が速くかつ吸着量が大きく、化学的に安定なリチウム吸着剤を製造できる。非量論的化合物であるＭｎ３Ｏ４を用いたので反応性が高い。また、Ｍｎ３Ｏ４とＬｉＯＨの混合物の相転移点がＭｎ：Ｌｉ＝１〜１．５：１の混合物で４２５〜４３０℃、と５００〜５１０℃にあることを見出したので、２段焼成することで安定したスピネル構造のリチウム吸着剤を得ることができる。[0006]
The purpose is to provide an apparatus for concentrating um.
(5) An object of the present invention is to provide a lithium concentrator capable of efficiently and selectively concentrating lithium contained in seawater or geothermal hot water and capable of being used repeatedly for a long time.
Means for Solving the Problems [0014]
In order to solve the above conventional problems, a method for producing a lithium adsorbent of the present invention, a lithium concentration method using the lithium adsorbent, and a lithium concentration apparatus have the following configurations.
[0015]
In the method for producing a lithium adsorbent according to the first aspect of the present invention, manganese tetraoxide (Mn 3 O 4 ) and lithium hydroxide (LiOH) are used, and the molar ratio of manganese to lithium is Mn: Li = 1 to 1. The mixture is mixed to 5: 1 and subjected to mechanochemical grinding until the intensity of the 2θ = 32.6 degree peak of Mn 3 O 4 in XRD of the calcined product after calcining is reduced by 10% or more. A mechanochemical process, followed by a prefiring process in a temperature range of 375 ° C. to 450 ° C. in an air or oxygen atmosphere; A main firing step of obtaining a spinel-type oxygen-rich lithium manganate by performing a main firing in a temperature range of ℃, and treating the spinel-type oxygen-rich lithium manganate with a large excess of acid with respect to lithium. Has a structure in which and a elution step of eluting-ion.
With this configuration, the following effects can be obtained.
(1) Due to the mechanochemical effect, the interaction between Mn 3 O 4 and LiOH is increased, and even when the compounding ratio of Li is higher than before, the oxygen-excess lithium manganate has maintained the spinel structure. For this reason, it is possible to produce a lithium adsorbent that is excellent in selective adsorptivity to lithium ions, has a high adsorption rate and a large adsorption amount, and is chemically stable. Since Mn 3 O 4 which is a non-stoichiometric compound is used, the reactivity is high. Further, the phase transition point of the Mn 3 O 4 and a mixture of LiOH is Mn: Li = 1~1.5: Since it was found that in the 425 to 430 ° C., and 500 to 510 ° C. with a mixture of 1, 2-stage calcination By doing so, a lithium adsorbent having a stable spinel structure can be obtained.
【０００７】
（２）低い温度で仮焼成し、次いで低い温度で本焼成を行うので系内に原料のＭｎ３Ｏ４が残らず純粋な単一の結晶相が得られ、結晶構造が強固となり、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤を製造できる。
（３）低い温度での本焼成により、リチウムイオンのインターカレートと脱インターカレートに伴うＭｎの不均化を阻止し、Ｍｎの溶出を防止するので、大過剰の酸でリチウムを溶離することでマンガンの酸化還元反応を抑えて水素イオンとリチウムイオンの交換反応のみを起こさせることができ、結晶構造を壊さない。これにより化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤を製造できる。
（４）リチウムの吸着量が多く、結晶構造が安定なので高能率で繰り返しリチウムイオンを吸着、溶離できるリチウム吸着剤を製造できる。
（５）製造工程が煩雑でなく、入手しやすい原料から工業的に生産可能なリチウム吸着剤が製造できる。
（６）スピネル結晶構造を保ちながらＬｉ含有量を多くすることができる。
（７）結晶構造が安定なので、吸着・脱着作業の繰り返し耐性を高めることができる。
［００１６］
ここで、メカノケミカル的粉砕処理とは機械的に粉砕する過程において、物質粒子に機械による圧縮力、剪断力、衝撃力等をかけることによって粒子表面に新しいへき開面を多数生成するとともに表面積を増大し、粒子表面での化学反応性を変化させる処理である。粉砕処理装置としてはアトライター、サンドミル、ボールミル、メディアミル、コロイドミル、ストーンミル、ケディーミル、フロージェットミキサ、スラッシャーミル、メカノヒュージョンシステム（ホソカワミクロン（株）製）、ミラーロ（（株）奈良機械製作所製）などが用いられる。
処理時間、処理条件は使用する機器によって異なるが、仮焼成後にＸＲＤ測定によってＭｎ３Ｏ４のピークの減少・消失度合いを確認することでメカノケミカル的処理条件を決めることができる。
［００１７］
仮焼成の温度が３７５℃より低いと均一な組成の結晶が得られないので好ましくない。また発明者らの知見によると４５０℃を超えると、本焼成を行っても不純物が多く残り結晶構造が脆弱になるので好ましくない。[0007]
(2) Since preliminary firing is performed at a low temperature and then main firing is performed at a low temperature, a pure single crystal phase is obtained in which no raw material Mn 3 O 4 remains in the system, the crystal structure is strengthened, In addition, it is possible to produce a lithium adsorbent that is stable and does not dissolve even after repeated use.
(3) The main firing at a low temperature prevents Mn disproportionation associated with lithium ion intercalation and deintercalation and prevents Mn elution, so that lithium is eluted with a large excess of acid. Thus, the oxidation-reduction reaction of manganese can be suppressed and only the exchange reaction between hydrogen ions and lithium ions can be caused, and the crystal structure is not broken. This makes it possible to produce a lithium adsorbent that is chemically stable and does not dissolve even after repeated use.
(4) Since the adsorption amount of lithium is large and the crystal structure is stable, a lithium adsorbent capable of repeatedly adsorbing and eluting lithium ions with high efficiency can be produced.
(5) A lithium adsorbent that can be industrially produced can be manufactured from easily available raw materials without complicated manufacturing steps.
(6) The Li content can be increased while maintaining the spinel crystal structure.
(7) Since the crystal structure is stable, it is possible to increase the resistance to repeated adsorption and desorption operations.
[0016]
Here, mechanochemical pulverization is a process of mechanical pulverization, in which a large number of new cleaved surfaces are generated and surface area is increased by applying mechanical compressive force, shearing force, impact force, etc. to the material particles. In this case, the chemical reactivity on the particle surface is changed. Grinding equipment includes attritors, sand mills, ball mills, media mills, colloid mills, stone mills, keddy mills, flow jet mixers, slasher mills, mechano-fusion systems (manufactured by Hosokawa Micron Corporation), and mirrors (manufactured by Nara Machinery Co., Ltd.) ) Etc. are used.
Although the treatment time and treatment conditions vary depending on the equipment used, the mechanochemical treatment conditions can be determined by confirming the degree of decrease / disappearance of the peak of Mn 3 O 4 by XRD measurement after preliminary firing.
[0017]
If the pre-baking temperature is lower than 375 ° C., crystals with a uniform composition cannot be obtained. Further, according to the knowledge of the inventors, if it exceeds 450 ° C., it is not preferable because many impurities remain and the crystal structure becomes brittle even if the main baking is performed.
【０００８】
［００１８］
本焼成の温度が４７５℃より低いと仮焼成物の不純物が本焼成後も残り結晶構造が脆弱になるので好ましくない。５５０℃を超えると、スピネル型の結晶構造が崩れるため好ましくない。
［００１９］
リチウムを溶離するには、大過剰の酸、例えば塩酸、過塩素酸、硝酸等をリチウム（ａ）と酸（ｂ）のモル比が、ａ：ｂ＝１：２０以上、好ましくはａ：ｂ＝１：４０以上となる過剰の酸でリチウムを溶離する必要がある。このときの酸の濃度は、０．１〜２Ｍである。２Ｍを超える濃度の酸を適用すると、Ｍｎを溶解させて好ましくない。また、リチウム：酸＝１：２０以下でリチウムを溶離するとスピネル型結晶構造が崩れて好ましくない。
［００２０］
［００２１］
本発明の請求項２に記載のリチウム吸着剤の製造方法は、請求項１に記載のリチウム吸着剤の製造方法であって、前記本焼成工程で得られた前記スピネル型酸素過剰マンガン酸リチウム１００重量部に対して、酸化アルミニウムやシリカの無機系バインダ２重量部〜４０重量部と水を混練したあと、径０．５ｍｍ〜６ｍｍ好ましくは１ｍｍ〜３ｍｍの紐状又は粒状の成形体に加工する成形工程と、次いで前記成形体を４５０℃〜５５０℃の温度域で０．５〜３時間焼結し、成形体とする焼結工程と、を備えた構成を有している。
この構成により、請求項１の作用に加えて、以下のような作用が得られる。
（１）粒状に成形されているので、カラムに詰めて使用する場合に通液が容[0008]
[0018]
If the temperature of the main baking is lower than 475 ° C., impurities in the temporarily fired product remain after the main baking, and the crystal structure becomes brittle. A temperature exceeding 550 ° C. is not preferable because the spinel crystal structure is broken.
[0019]
In order to elute lithium, a large excess of acid, for example, hydrochloric acid, perchloric acid, nitric acid or the like, the molar ratio of lithium (a) to acid (b) is a: b = 1: 20 or more, preferably a: b = 1: It is necessary to elute lithium with an excess of acid that is 40 or more. The concentration of the acid at this time is 0.1 to 2M. If an acid having a concentration exceeding 2M is applied, Mn is dissolved, which is not preferable. Further, it is not preferable to elute lithium with lithium: acid = 1: 20 or less because the spinel crystal structure is broken.
[0020]
[0021]
The method for producing a lithium adsorbent according to claim 2 of the present invention is the method for producing a lithium adsorbent according to claim 1, wherein the spinel-type oxygen-rich lithium manganate 100 obtained in the main firing step. After kneading 2 to 40 parts by weight of an inorganic binder of aluminum oxide or silica and water with respect to parts by weight, it is processed into a string-like or granular shaped body having a diameter of 0.5 to 6 mm, preferably 1 to 3 mm. It has the structure provided with the shaping | molding process and the sintering process which then sinters the said molded object for 0.5 to 3 hours in the temperature range of 450 to 550 degreeC, and makes it a molded object.
With this configuration, the following operation is obtained in addition to the operation of the first aspect.
(1) Since it is formed into a granular shape, liquid can be passed through when packed in a column.
【０００９】
易である。
（２）焼結により硬度が上がり粉化し難く長寿命化できる。
尚、紐状に成形した場合は、焼結後に、１〜３ｍｍにカッターで粒状に切断される。
［００２２］
本発明の請求項３に記載のリチウム吸着剤の製造方法は、請求項１に記載のリチウム吸着剤の製造方法であって、前記本焼成工程で得られた前記スピネル型酸素過剰マンガン酸リチウム１００重量部に対して、キチンやＰＶＣの有機系バインダ０．５重量部〜２０重量部と水を混練したあと、径０．５ｍｍ〜６ｍｍ好ましくは１ｍｍ〜３ｍｍの粒状の成形体に加工する成形工程と、次いで前記成形体を５０℃〜１００℃の温度域で０．５〜４時間乾燥し、成形体とする乾燥工程と、を備えた構成を有している。
この構成により、請求項２と同様の作用が得られる。
［００２３］
ここで成形には押し出し造粒機（エクストルーダー）、圧縮造粒機、射出造粒機（ニーダールーダー）など各種造粒機を用いることができる。
ストランド状に成形した場合は成形後、長さ１ｍｍ〜６ｍｍ好ましくは１〜３ｍｍに切断する。
造粒を終えたスピネル型酸素過剰マンガン酸リチウムは篩にかけ微粉を除いた後で、溶離工程に掛けることが好ましい。
［００２４］
リチウム吸着剤は、一般式ＨａＭｎ２Ｏｂ（式中、１．８≦ａ≦２、４＜ｂ≦４．２である。）の構成を有している。
この構成により、以下の作用が得られる。
（１）酸素を過剰に有しているため、Ｍｎ４＋の含有量を増加させ、Ｌｉ＋とのイオン交換反応量を増やすことができる。また、スピネル結晶構造を電子的により安定化させることができる。
（２）プロトンサイト（イオン交換型サイト）にリチウム溶液中からＬｉ＋を取り込むことができる。
（３）マンガン酸化物にはトンネル構造、層状構造、網目状構造などさまざまな構造を持つ化合物があるが、スピネル型と呼ばれる構造を持つマンガン[0009]
Easy.
(2) Sintering increases the hardness, making it difficult to powder and extending the life.
In addition, when shape | molding in the shape of a string, after sintering, it is cut | disconnected by a cutter to a granular form at 1-3 mm.
[0022]
The method for producing a lithium adsorbent according to claim 3 of the present invention is the method for producing a lithium adsorbent according to claim 1, wherein the spinel-type oxygen-rich lithium manganate 100 obtained in the main firing step is provided. A molding step in which 0.5 to 20 parts by weight of an organic binder of chitin or PVC and water are kneaded with parts by weight and then processed into a granular molded body having a diameter of 0.5 mm to 6 mm, preferably 1 mm to 3 mm. And then drying the molded body in a temperature range of 50 ° C. to 100 ° C. for 0.5 to 4 hours to form a molded body.
With this configuration, the same effect as in the second aspect can be obtained.
[0023]
Here, various granulators such as an extrusion granulator (extruder), a compression granulator, and an injection granulator (kneader ruder) can be used for molding.
When it is formed into a strand shape, it is cut into a length of 1 mm to 6 mm, preferably 1 to 3 mm after the forming.
The spinel-type oxygen-rich lithium manganate after granulation is preferably sieved to remove fine powder and then subjected to an elution step.
[0024]
The lithium adsorbent has a configuration of a general formula H a Mn 2 O b (where 1.8 ≦ a ≦ 2, 4 <b ≦ 4.2).
With this configuration, the following effects can be obtained.
(1) Since it has oxygen excessively, the content of Mn 4+ can be increased and the amount of ion exchange reaction with Li + can be increased. Also, the spinel crystal structure can be more electronically stabilized.
(2) Li + can be taken into the proton site (ion exchange type site) from the lithium solution.
(3) Manganese oxides include compounds with various structures such as tunnel structures, layered structures, and network structures, but manganese has a structure called spinel type.
【００１０】
酸化物は（１×３）網目状構造になっている。金属イオンに対する吸着選択性はマンガン酸化物の結晶構造に依存するが、非量論型のスピネル型マンガン酸化物としたので、Ｌｉ＋に対して高い選択性を示すと共に多量のＬｉ＋とイオン交換をすることができる。また、鹹水はＬｉ＋よりイオン半径の大きいＮａ＋やＫ＋、Ｃａ２＋等の陽イオンを含むがこれらの陽イオンは網目状構造に入ることができない。その理由は、鋳型であるＬｉ＋を取り込むことで調製された吸着剤の前躯体からＬｉ＋を取り除くことにより、Ｌｉ＋の大きさの鋳型を有する多孔結晶型の吸着剤を得ることができるためである。
［００２５］
リチウム吸着剤用原料は、一般式ＬｉｘＭｎ２Ｏｙ（式中、１．８≦ｘ≦２、４＜ｙ≦４．２である。）からなる構成を有している。
この構成により、以下の作用が得られる。
（１）酸洗時（溶離時）に定量的にＬｉ＋を溶離させ、かつ、吸着時の繰り返し耐性に優れる。
［００２６］
本発明の請求項４に記載のリチウム濃縮方法は、原水から請求項１乃至３の内いずれか１に記載の製法で作製されたリチウム吸着剤を用いて選択的にリチウムイオンを吸着する吸着工程と、リチウムイオンを吸着したリチウム吸着剤を大過剰の酸で処理してリチウムイオンを溶離する溶離工程とを有し、前記溶離工程でリチウムイオンを溶離する酸が、０．１Ｍ〜２．０Ｍの塩酸又は過塩素酸、硝酸の内いずれか１である構成を有している。
この構成により、以下のような作用が得られる。
（１）リチウムイオンの選択性に優れ、リチウムイオンの吸着速度が速く、リチウムイオンの吸着量が多いリチウム吸着体を、安定して繰り返し使用できるので、工業的にリチウムを高濃縮できる。
（２）溶離工程で用いる酸がリチウム吸着剤を溶かさず、またリチウム吸着剤の結晶構造を崩さないので、リチウム吸着剤が劣化しないので、効率のよいリチウム濃縮を工業的に継続できる。[0010]
The oxide has a (1 × 3) network structure. Adsorption selectivity for metal ions depends on the crystal structure of manganese oxide but, since the spinel-type manganese oxide of the non-stoichiometric form, a large amount of Li + ion exchange exhibit both high selectivity for Li + Can do. Further, the brine contains cations such as Na + , K + , and Ca 2+ having an ionic radius larger than that of Li +, but these cations cannot enter the network structure. The reason is that by removing the Li + from the precursor of the adsorbent prepared by incorporating the Li + as a template, it is possible to obtain a porous crystalline adsorbent having a Li + in the size of the mold It is.
[0025]
The raw material for the lithium adsorbent has a configuration of the general formula Li x Mn 2 O y (where 1.8 ≦ x ≦ 2, 4 <y ≦ 4.2).
With this configuration, the following effects can be obtained.
(1) Li + is eluted quantitatively during pickling (during elution) and is excellent in repeated resistance during adsorption.
[0026]
The lithium concentration method according to claim 4 of the present invention is an adsorption step of selectively adsorbing lithium ions from raw water using the lithium adsorbent produced by the production method according to any one of claims 1 to 3. And an elution step of eluting lithium ions by treating the lithium adsorbent adsorbing lithium ions with a large excess of acid, and the acid eluting lithium ions in the elution step is 0.1M to 2.0M. The composition is any one of hydrochloric acid, perchloric acid, and nitric acid.
With this configuration, the following effects can be obtained.
(1) Since a lithium adsorbent having excellent lithium ion selectivity, a high lithium ion adsorption rate, and a large amount of lithium ion adsorption can be stably and repeatedly used, lithium can be industrially highly concentrated.
(2) Since the acid used in the elution step does not dissolve the lithium adsorbent and does not destroy the crystal structure of the lithium adsorbent, the lithium adsorbent does not deteriorate, so that efficient lithium concentration can be continued industrially.
【００１１】
［００２７］
ここで、リチウム吸着剤からリチウムイオンを溶離させる酸の濃度が０．１Ｍ未満の場合、溶離の初期において酸の濃度が薄い状態がリチウム吸着剤において部分的に発生し、マンガンの酸化還元反応が起こり、結晶構造が崩れてＭｎが溶出する恐れがあり好ましくない。またリチウム吸着剤からリチウムイオンを溶離させる酸の濃度が２．０Ｍ超であると、長期の反復使用で少しずつ吸着剤が溶解して劣化する恐れがあり好ましくない。
より好ましくは０．５Ｍ〜１．５Ｍの酸が採用される。カラム内の残液による希釈や、溶離液の混合ムラによる吸着剤の損傷を防ぐためである。
［００２８］
本発明の請求項５に記載のリチウム濃縮装置は請求項１乃至３の内いずれか１に記載の製法で作製されたリチウム吸着剤が充填されたリチウム吸着カラムを持つ構成を有している。
この構成により、以下のような作用が得られる。
（１）繰り返し使用でき、選択性の高く吸着速度が高く吸着量の多いリチウム吸着剤を充填したカラムを利用するので高能率でリチウムを濃縮できる装置となる。
［００２９］
ここで、リチウム吸着剤を充填したカラムをパッケージとして脱着を容易にすることで、リチウムイオンを吸着する工程と溶離工程を分離することができ、装置の設計・配置の自由度を増すことができる。
発明の効果
［００３０］
以上のように本発明のリチウム吸着剤の製造方法及びリチウム吸着剤、リチウム吸着剤用原料、リチウム濃縮方法、リチウム濃縮装置によれば、以下のような有利な効果が得られる。
請求項１に記載の発明によれば、
（１）メカノケミカル効果によりＭｎ３Ｏ４とＬｉＯＨの相互作用が高まり、従来よりもＬｉの配合比が高くても酸素過剰マンガン酸リチウムがスピネル構造を保つようになったため、リチウムに対する選択吸着性に優れるとともに吸着速度が速くかつ吸着量が大きく、化学的に安定なリチウム吸着剤の製造方法を提供できる。[0011]
[0027]
Here, when the concentration of the acid that elutes lithium ions from the lithium adsorbent is less than 0.1 M, a state where the acid concentration is low occurs partially in the lithium adsorbent at the beginning of the elution, and the oxidation-reduction reaction of manganese occurs. This is not preferable because the crystal structure is broken and Mn is eluted. Further, if the concentration of the acid eluting lithium ions from the lithium adsorbent is more than 2.0M, the adsorbent may be gradually dissolved and deteriorated by repeated use over a long period, which is not preferable.
More preferably, an acid of 0.5M to 1.5M is employed. This is to prevent damage to the adsorbent due to dilution with residual liquid in the column and uneven mixing of the eluent.
[0028]
A lithium concentrator according to a fifth aspect of the present invention has a structure having a lithium adsorption column filled with a lithium adsorbent produced by the production method according to any one of the first to third aspects.
With this configuration, the following effects can be obtained.
(1) Since a column packed with a lithium adsorbent that can be used repeatedly, has a high selectivity, a high adsorption rate, and a large amount of adsorption is used, the apparatus can concentrate lithium with high efficiency.
[0029]
Here, by using a column packed with a lithium adsorbent as a package for easy desorption, the process of adsorbing lithium ions and the elution process can be separated, and the degree of freedom in designing and arranging the apparatus can be increased. .
Effect of the Invention [0030]
As described above, according to the method for producing a lithium adsorbent, the lithium adsorbent, the lithium adsorbent raw material, the lithium concentration method, and the lithium concentrator of the present invention, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) The interaction between Mn 3 O 4 and LiOH is enhanced due to the mechanochemical effect, and the oxygen-rich lithium manganate maintains the spinel structure even when the Li content is higher than before. In addition, it is possible to provide a method for producing a chemically stable lithium adsorbent that has a high adsorption rate and a large adsorption amount.
【００１２】
（２）非量論的化合物であるＭｎ３Ｏ４を用いたので反応性が高い。また、Ｍｎ３Ｏ４とＬｉＯＨの混合物の相転移点がＭｎ：Ｌｉ＝１〜１．５：１の混合物で４２５〜４３０℃、と５００〜５１０℃にあることを見出したので、２段焼成することで安定したスピネル構造のリチウム吸着剤を得ることができる。仮焼成工程と本焼成工程を有するので、結晶構造が強固となり、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤の製造方法を提供できる。
（３）大過剰の酸でリチウムイオンを溶離することでマンガンの酸化還元反応を抑えて水素イオンとリチウムイオンの交換反応のみを起こさせることができ、結晶構造を壊さないので、化学的に安定な上、繰り返しの使用にも溶解しないリチウム吸着剤の製造方法を提供できる。
（４）リチウムイオンの吸着量が多く、結晶構造が安定なので高能率で繰り返しリチウムイオンを吸着、溶離できるリチウム吸着剤の製造方法を提供できる。
（５）製造工程が煩雑でなく、入手しやすい原料から工業的に生産可能なので、低原価で量産性に優れたリチウム吸着剤の製造方法を提供できる。
（６）安定なスピネル結晶構造を保ち、Ｌｉ含有量が多く、吸着・脱着作業の繰り返し耐久性の高いリチウム吸着剤を低原価で量産できるリチウム吸着剤の製造方法を提供できる。
（７）メカノケミカル的な粉砕処理により結晶構造に取り込まれるリチウムの量が増える。
［００３１］
［００３２］
請求項２に記載の発明によれば、請求項１の効果に加え、
（１）径０．５ｍｍ〜６ｍｍ好ましくは１〜３ｍｍの粒状に成形されているので、カラム等に充填しても通液性がよく使用しやすいリチウム吸着剤の製造方法を提供することができる。
（２）焼結により硬度が上がり粉化し難く耐久性に優れたリチウム吸着剤の製造方法を提供することができる。
［００３３］
請求項３に記載の発明によれば、請求項２の効果に加え、
（１）強固に成形されるので機械的強度に優れ、吸着溶離を繰り返しても、[0012]
(2) Since Mn 3 O 4 which is a non-stoichiometric compound is used, the reactivity is high. Further, the phase transition point of the Mn 3 O 4 and a mixture of LiOH is Mn: Li = 1~1.5: Since it was found that in the 425 to 430 ° C., and 500 to 510 ° C. with a mixture of 1, 2-stage calcination By doing so, a lithium adsorbent having a stable spinel structure can be obtained. Since the pre-baking step and the main baking step are provided, the method for producing a lithium adsorbent that has a strong crystal structure, is chemically stable, and does not dissolve even after repeated use can be provided.
(3) By eluting lithium ions with a large excess of acid, it is possible to suppress the oxidation-reduction reaction of manganese and to cause only the exchange reaction between hydrogen ions and lithium ions, and since the crystal structure is not destroyed, it is chemically stable. In addition, a method for producing a lithium adsorbent that does not dissolve even after repeated use can be provided.
(4) Since the adsorption amount of lithium ions is large and the crystal structure is stable, a method for producing a lithium adsorbent capable of repeatedly adsorbing and eluting lithium ions with high efficiency can be provided.
(5) Since the production process is not complicated and can be industrially produced from readily available raw materials, it is possible to provide a method for producing a lithium adsorbent with low cost and excellent mass productivity.
(6) It is possible to provide a method for producing a lithium adsorbent capable of mass-producing a lithium adsorbent having a stable spinel crystal structure, a large Li content, and a high durability for repeated adsorption / desorption operations at a low cost.
(7) The amount of lithium taken into the crystal structure is increased by mechanochemical grinding.
[0031]
[0032]
According to invention of Claim 2, in addition to the effect of Claim 1,
(1) Since it is formed into a particle having a diameter of 0.5 mm to 6 mm, preferably 1 to 3 mm, a method for producing a lithium adsorbent that is easy to use even when packed in a column or the like can be provided. .
(2) It is possible to provide a method for producing a lithium adsorbent that is hard to be pulverized by sintering and excellent in durability.
[0033]
According to invention of Claim 3, in addition to the effect of Claim 2,
(1) Excellent mechanical strength due to strong molding, repeated adsorption and elution,
【００１３】
形状が崩れないリチウム吸着剤の製造方法を提供することができる。
［００３４］
請求項１乃至３の内いずれか１の製造方法により、次の有利な効果を実現できるリチウム吸着剤を提供できる。
（１）酸素を過剰に有しているため、Ｍｎ４＋の含有量を増加させ、Ｌｉ＋とのイオン交換反応量を増やすことができる。
（２）プロトンサイト（イオン交換型サイト）にリチウム溶液中からＬｉ＋を取り込むことができる。
（３）マンガン酸化物にはトンネル構造、層状構造、網目状構造などさまざまな構造を持つ化合物があるが、スピネル型と呼ばれる構造を持つマンガン酸化物は（１×３）網目状構造になっている。金属イオンに対する吸着選択性はマンガン酸化物の結晶構造に依存するが、非量論型のスピネル型マンガン酸化物としたので、Ｌｉ＋に対して高い選択性を示すと共に多量のＬｉ＋とイオン交換をすることができる。また、鹹水はＬｉ＋よりイオン半径の大きいＮａ＋やＫ＋、Ｃａ２＋等の陽イオンを含むがこれらの陽イオンは網目状構造に入ることができない。その理由は、鋳型であるＬｉ＋を取り込むことで調製された吸着剤の前躯体からＬｉ＋を取り除くことにより、Ｌｉ＋の大きさの鋳型を有する多孔結晶型の吸着剤を得ることができるためである。
［００３５］
請求項１乃至３の内いずれか１の製造方法により、次の有利な効果を実現できるリチウム吸着剤用原料を提供できる。
（１）酸洗時（溶離時）に定量的にＬｉ＋を溶離させ、かつ、吸着時の繰り返し耐久性に優れるリチウム吸着剤を与えるリチウム吸着剤用原料を提供できる。
［００３６］
請求項４に記載の発明によれば、
（１）リチウムイオンの選択性に優れ、リチウムイオンの吸着速度が高く、リチウムイオンの吸着量が高いリチウム吸着体を、安定して繰り返し使用できるので、工業的にリチウムを高濃縮できるリチウム濃縮方法を提供できる。
（２）溶離工程で用いる酸がリチウム吸着剤を溶かさず、またリチウム吸着[0013]
A method for producing a lithium adsorbent that does not lose its shape can be provided.
[0034]
By the manufacturing method of any one of Claims 1 thru | or 3, the lithium adsorbent which can implement | achieve the following advantageous effects can be provided.
(1) Since it has oxygen excessively, the content of Mn 4+ can be increased and the amount of ion exchange reaction with Li + can be increased.
(2) Li + can be taken into the proton site (ion exchange type site) from the lithium solution.
(3) Manganese oxides include compounds with various structures such as tunnel structures, layered structures, and network structures, but manganese oxides with a structure called spinel type have a (1 × 3) network structure. Yes. Adsorption selectivity for metal ions depends on the crystal structure of manganese oxide but, since the spinel-type manganese oxide of the non-stoichiometric form, a large amount of Li + ion exchange exhibit both high selectivity for Li + Can do. Further, the brine contains cations such as Na + , K + , and Ca 2+ having an ionic radius larger than that of Li +, but these cations cannot enter the network structure. The reason is that by removing the Li + from the precursor of the adsorbent prepared by incorporating the Li + as a template, it is possible to obtain a porous crystalline adsorbent having a Li + in the size of the mold It is.
[0035]
By the manufacturing method of any one of Claims 1 thru | or 3, the raw material for lithium adsorbents which can implement | achieve the following advantageous effects can be provided.
(1) It is possible to provide a raw material for a lithium adsorbent that elutes Li + quantitatively during pickling (at the time of elution) and gives a lithium adsorbent that is excellent in repeated durability during adsorption.
[0036]
According to invention of Claim 4,
(1) A lithium concentrating method that can highly concentrate lithium industrially because a lithium adsorbent having excellent lithium ion selectivity, a high lithium ion adsorption rate, and a high lithium ion adsorption amount can be stably and repeatedly used. Can provide.
(2) The acid used in the elution process does not dissolve the lithium adsorbent, and lithium adsorption
【００１４】
剤の結晶構造を崩さないので、リチウム吸着剤が劣化しないので、効率のよいリチウム濃縮を工業的に継続できるリチウム濃縮方法を提供できる。
［００３７］
請求項５に記載の発明によれば、
（１）高性能で化学的に安定なリチウム吸着体を有しているので安定で効率的運転が可能なリチウム濃縮装置を提供できる。
図面の簡単な説明
［００３８］
［図１］実施例１のメカノケミカル的処理時間による仮焼成物のＸ線回折の変化を示す図
［図２］実施例１のメカノケミカル的処理時間による本焼成後のＸ線回折の変化を示す図
［図３］実施例２の破過曲線を示す図
［図４］実施例３の溶離曲線を示す図
［図５］実施例５のリチウム吸着等温線を示す図
［図６］実施例６のリチウム吸着等温線を示す図
［図７］リチウム吸着量と吸着剤組成との関係図
発明を実施するための形態
［００３９］
以下、本発明を実施するための形態について説明する。
本発明の、リチウム吸着剤として機能する層状λ型二酸化マンガン組成物は、スピネル型構造を持ち粒径が１μｍ〜１００μｍの微粒子状あるいは膜状を呈している。
［００４０］
本発明のリチウム吸着剤である、層状λ型二酸化マンガン組成物を製造するときに用いるスピネル型マンガン酸リチウム（一般組成：ＬｉＭｎ２Ｏ４）は電池材料として知られており、一般的に、酸化マンガンとリチウム塩の化合物を加熱することによって得られる。その際、酸化マンガンとリチウム塩の混合割合、焼成温度、時間などを変化させることによって、様々な組成を得ることができる。
［００４１］
この実施形態においては、リチウム吸着剤を次のようにして得る。即ち、４酸化３マンガン（Ｍｎ３Ｏ４）と水酸化リチウム（ＬｉＯＨ）を、マンガン[0014]
Since the crystal structure of the agent is not destroyed, the lithium adsorbent is not deteriorated, and therefore a lithium concentration method capable of continuing efficient lithium concentration industrially can be provided.
[0037]
According to the invention of claim 5,
(1) A lithium concentrator capable of stable and efficient operation can be provided because it has a high-performance and chemically stable lithium adsorbent.
BRIEF DESCRIPTION OF THE DRAWINGS [0038]
[FIG. 1] A diagram showing a change in X-ray diffraction of a pre-baked product according to a mechanochemical treatment time in Example 1. [FIG. 2] A change in X-ray diffraction after main firing according to a mechanochemical treatment time in Example 1. FIG. 3 shows a breakthrough curve of Example 2. FIG. 4 shows an elution curve of Example 3. FIG. 5 shows a lithium adsorption isotherm of Example 5. FIG. FIG. 7 is a diagram showing the lithium adsorption isotherm of FIG. 6 [FIG. 7] Relationship diagram between lithium adsorption amount and adsorbent composition [0039]
Hereinafter, modes for carrying out the present invention will be described.
The layered λ-type manganese dioxide composition that functions as a lithium adsorbent of the present invention has a spinel structure and has a fine particle shape or a film shape with a particle diameter of 1 μm to 100 μm.
[0040]
The spinel type lithium manganate (general composition: LiMn 2 O 4 ) used when producing the layered λ-type manganese dioxide composition, which is the lithium adsorbent of the present invention, is known as a battery material and is generally oxidized. It is obtained by heating a compound of manganese and lithium salt. At that time, various compositions can be obtained by changing the mixing ratio of the manganese oxide and the lithium salt, the firing temperature, the time, and the like.
[0041]
In this embodiment, the lithium adsorbent is obtained as follows. That is, trimanganese tetroxide (Mn 3 O 4 ) and lithium hydroxide (LiOH)
【００１５】
とリチウムのモル比がＭｎ：Ｌｉ＝１〜１．５：１となるように混合する。これを遊星型高速ボールミルなどメカノケミカル的な粉砕ができる装置で１時間〜２時間処理し、粉砕するとともに物理的な圧縮力、剪弾力、衝撃力を与えるメカノケミカル的な処理を行う。尚、メカノケミカル工程は、仮焼成後の仮焼成物のＸＲＤにおけるＭｎ３Ｏ４の２θ＝３２．６度のピークの強度が１０％以上低下するまで行う。次いでこの粉砕物を、空気雰囲気下３７５℃〜４５０℃の温度域で１時間〜１０時間仮焼成する。仮焼成後、仮焼成物を混合、粉砕し、これを空気雰囲気下に４７５℃〜５２５℃で１時間〜１０時間本焼成する。これにより、（化１）、（化２）で示す反応式により非量論型のリチウム吸着剤を得ることができる。
［化１］
［化２］
発明者らの知見によれば、本焼成のみ（１回焼成）で得られるスピネル型のマンガン酸リチウムは不純物が多く、これを酸処理してリチウムを溶離すると結晶構造が崩れ、層状のλ型二酸化マンガン組成物を得ることが困難になることがわかった。これに対し、本実施の形態においては、低温の仮焼成で非量論的化合物のＭｎ３Ｏ４と低融点のＬｉＯＨを、溶融インターカレーション法を用いて合成することで安定したスピネル構造でイオン交換性に優れたリチウム吸着剤が得られる。次いで、本焼成でＬｉＯＨの融点より少し高めで焼成することにより、反応性が非常に高い非量論型のＭｎ３Ｏ４に溶液状で反応性に富むＬｉＯＨが接触し、Ｌｉ＋がＭｎ３Ｏ４の結晶格子に入り強固な網目構造を形成する酸化還元型でなく、イオン交換型のリチウム吸着剤を形成するものと思われる。
［００４２］
得られたスピネル型酸素過剰マンガン酸リチウムを造粒した後で、酸処理[0015]
And lithium are mixed so that the molar ratio of Mn: Li = 1 to 1.5: 1. This is processed for 1 to 2 hours with an apparatus capable of mechanochemical pulverization such as a planetary high-speed ball mill, and pulverized and mechanochemically processed to give physical compressive force, shredding force and impact force. The mechanochemical process is performed until the intensity of the peak at 2θ = 32.6 degrees of Mn 3 O 4 in XRD of the calcined product after calcining is reduced by 10% or more. Subsequently, this pulverized product is temporarily fired in an air atmosphere at a temperature range of 375 ° C. to 450 ° C. for 1 hour to 10 hours. After calcination, the calcination product is mixed and pulverized, and this is baked at 475 ° C. to 525 ° C. for 1 hour to 10 hours in an air atmosphere. Thereby, a non-stoichiometric lithium adsorbent can be obtained by the reaction formulas shown in (Chemical Formula 1) and (Chemical Formula 2).
[Chemical 1]
[Chemical formula 2]
According to the knowledge of the inventors, the spinel type lithium manganate obtained only by the main firing (single firing) has many impurities, and when this is acid-treated to elute lithium, the crystal structure collapses, and the layered λ-type It has been found that it becomes difficult to obtain a manganese dioxide composition. In contrast, in the present embodiment, a stable spinel structure is obtained by synthesizing a non-stoichiometric compound Mn 3 O 4 and a low melting point LiOH by low temperature pre-baking using a melt intercalation method. A lithium adsorbent having excellent ion exchange properties can be obtained. Next, by firing at a temperature slightly higher than the melting point of LiOH in the main firing, non-stoichiometric Mn 3 O 4 having a very high reactivity is brought into contact with LiOH that is in solution and rich in reactivity, and Li + becomes Mn 3. It is considered that an ion exchange type lithium adsorbent is formed instead of a redox type that enters a crystal lattice of O 4 and forms a strong network structure.
[0042]
After granulating the obtained spinel-type oxygen-rich lithium manganate, acid treatment
【００１６】
してλ型二酸化マンガン組成物を得る。即ち、スピネル型酸素過剰マンガン酸リチウムに酸を適用して、イオン交換反応によってリチウムイオンを溶離する。（造粒については後述する。）
［００４３］
焼成によって得られたスピネル型酸素過剰マンガン酸リチウムから酸によって初めてリチウムイオンを溶離するに際しては、大過剰の酸たとえば塩酸、過塩素酸、硝酸をリチウムと酸のモル比が、１：２０超、好ましくはリチウム：酸＝１：４０以上となる過剰の酸でリチウムイオンを溶離する必要がある。このときの酸の濃度は０．１Ｍ〜２Ｍである。２Ｍを超える濃度の酸を適用すると、Ｍｎを溶解させて好ましくない。
［００４４］
大過剰の酸でリチウムイオンを溶離することによって、マンガンの酸化還元反応を抑えて水素イオンとリチウムイオンのイオン交換反応を優先して起こさせることができ、マンガンの溶出を防ぎスピネル構造を維持できる。発明者らの知見によれば、リチウムと酸のモル比を、１：１０乃至１：２０としてスピネル型酸素過剰マンガン酸リチウムからリチウムを溶離すると、λ型二酸化マンガンの結晶構造が崩れることがわかった。スピネル型酸素過剰マンガン酸リチウムから酸によってリチウムを溶離する場合、マンガンの酸化還元反応と水素イオンとリチウムイオンのイオン交換反応が起こることが理由と考えられる。
［００４５］
スピネル型酸素過剰マンガン酸リチウムから酸によってリチウムを溶離するに際して用いる酸は鉱酸が好ましく、塩酸、過塩素酸、硝酸を用いることができる。発明者らの知見によれば、硫酸水溶液を用いると、得られるλ型二酸化マンガンの結晶構造が破壊されるため好ましくない。
［００４６］
本発明のリチウム吸着剤の製造方法におけるリチウム吸着剤を造粒する方法について説明する。
本焼成によって得られたスピネル型酸素過剰マンガン酸リチウムに対してアルミナやシリカ等の無機バインダ又はキチンやポリ塩化ビニルからなる有機系バインダを１５重量％〜５０重量％加え、少量の水でよく攪拌混合し、押し出し成形機を用いて径０．５ｍｍ〜６ｍｍ好ましくは１〜３ｍｍのペレ[0016]
Thus, a λ-type manganese dioxide composition is obtained. That is, an acid is applied to spinel oxygen-rich lithium manganate and lithium ions are eluted by an ion exchange reaction. (The granulation will be described later.)
[0043]
When eluting lithium ions for the first time with an acid from spinel-type oxygen-excess lithium manganate obtained by firing, a molar ratio of lithium to acid of a large excess of acid such as hydrochloric acid, perchloric acid, or nitric acid is more than 1:20, It is necessary to elute lithium ions with an excess of acid, preferably lithium: acid = 1: 40 or more. The acid concentration at this time is 0.1M to 2M. If an acid having a concentration exceeding 2M is applied, Mn is dissolved, which is not preferable.
[0044]
By eluting lithium ions with a large excess of acid, the redox reaction of manganese can be suppressed and the ion exchange reaction between hydrogen ions and lithium ions can be prioritized, preventing the elution of manganese and maintaining the spinel structure. . According to the knowledge of the inventors, it is found that when lithium is eluted from spinel-type oxygen-rich lithium manganate at a molar ratio of lithium to acid of 1:10 to 1:20, the crystal structure of λ-type manganese dioxide is destroyed. It was. When lithium is eluted with acid from spinel-type oxygen-rich lithium manganate, it is considered that manganese redox reaction and ion exchange reaction between hydrogen ion and lithium ion occur.
[0045]
The acid used for eluting lithium from the spinel oxygen-rich lithium manganate with an acid is preferably a mineral acid, and hydrochloric acid, perchloric acid, or nitric acid can be used. According to the knowledge of the inventors, it is not preferable to use a sulfuric acid aqueous solution because the crystal structure of the obtained λ-type manganese dioxide is destroyed.
[0046]
A method for granulating a lithium adsorbent in the method for producing a lithium adsorbent of the present invention will be described.
Add 15 wt% to 50 wt% of an inorganic binder such as alumina or silica or an organic binder made of chitin or polyvinyl chloride to the spinel type oxygen-rich lithium manganate obtained by this firing, and stir well with a small amount of water. Mix and use pellets with a diameter of 0.5 mm to 6 mm, preferably 1 to 3 mm, using an extruder.
【００２１】
サンプル１としてＬｉＣｌ溶液１０ｍＬ（０．５〜２０ｐｐｍ）をそれぞれ三角フラスコに入れ、２５℃の振とう機で約１２時間振とうさせ、振とう後のリチウムの濃度を原子吸光で測定しリチウム吸着剤の性能を調べた。サンプル２として、特許文献４のリチウム吸着剤１０ｍｇを準備し、サンプル１と同様に行った。
［００５６］
図５に実施例５の結果を示す。横軸が吸着平衡に達したときの水溶液中に残っているリチウム濃度を示し、縦軸がリチウム吸着量を示す。サンプル１を×印でサンプル２を△印で示している。
この吸着等温実験からサンプル１とサンプル２のリチウム最大吸着量はそれぞれ２．３６ｍｍｏｌ／ｇ、２．０８ｍｍｏｌ／ｇとなった。この値は、（特許文献４）の吸着剤のそれぞれ１．６倍、１．４倍高い値であり、メカノケミカル効果によりリチウム吸着量が増えたことが示された。
実施例６
［００５７］
実施例１で得られたリチウム吸着剤（Ｌｉ１．４Ｍｎ２Ｏ４．２，Ｌｉ１．８Ｍｎ２Ｏ４．２）を用い、リチウム吸着に対する、吸着剤のｐＨ依存性を調べた。ＬｉＣｌ溶液のｐＨを６．０、７．０、８．０、８．３、８．５、８．８、９．０にした以外は実施例４と同様にして、それぞれ三角フラスコに入れ、２５℃の振とう機で約１２時間振とう（回転数：１５０ｒｐｍ）させ、振とう後の溶液のｐＨ（平衡ｐＨ）とリチウムの濃度を測定した。
尚、比較例として、特許文献４の実施例に基づいて、リチウム吸着剤を作製した。Ｘ線回折で確認したところ、Ｌｉ１．０Ｍｎ２Ｏ４．２であった。この試料を用い同様にしてｐＨ依存性を測定した。
［００５８］
その結果を図６に示した。Ｌｉ１．４Ｍｎ２Ｏ４．２は◆印、Ｌｉ１．８Ｍｎ２Ｏ４．２は■印、Ｌｉ１．０Ｍｎ２Ｏ４．２は△印で示した。図６において、横軸が平衡ｐＨで、縦軸がリチウム吸着量を表す。比較例として（特許文献４）に記載のＬｉＭｎ２Ｏ４．２の結果を三角印で示している。弱酸性〜アルカリ域で実施例１で得られたリチウム吸着剤が特許文献４に記載のリチウム吸着剤ＬｉＭｎ２Ｏ４．２より高い吸着性能を示した。また、図６から明らかなように、Ｌｉ１．８ [0021]
As sample 1, 10 mL of LiCl solution (0.5 to 20 ppm) was put in an Erlenmeyer flask, shaken for about 12 hours with a shaker at 25 ° C., and the concentration of lithium after shaking was measured by atomic absorption to obtain a lithium adsorbent. The performance of was investigated. As Sample 2, 10 mg of the lithium adsorbent disclosed in Patent Document 4 was prepared and performed in the same manner as Sample 1.
[0056]
FIG. 5 shows the results of Example 5. The horizontal axis indicates the concentration of lithium remaining in the aqueous solution when the adsorption equilibrium is reached, and the vertical axis indicates the lithium adsorption amount. Sample 1 is indicated by x and sample 2 is indicated by Δ.
From this adsorption isothermal experiment, the maximum lithium adsorption amounts of Sample 1 and Sample 2 were 2.36 mmol / g and 2.08 mmol / g, respectively. These values were 1.6 times and 1.4 times higher than the adsorbent of (Patent Document 4), respectively, indicating that the lithium adsorption amount increased due to the mechanochemical effect.
Example 6
[0057]
Using the lithium adsorbent obtained in Example 1 (Li 1.4 Mn 2 O 4.2 , Li 1.8 Mn 2 O 4.2 ), the pH dependence of the adsorbent on lithium adsorption was examined. In the same manner as in Example 4 except that the pH of the LiCl solution was 6.0, 7.0, 8.0, 8.3, 8.5, 8.8, 9.0, The mixture was shaken with a shaker at 25 ° C. for about 12 hours (rotation number: 150 rpm), and the pH (equilibrium pH) and lithium concentration of the solution after shaking were measured.
As a comparative example, a lithium adsorbent was prepared based on the example of Patent Document 4. When confirmed by X-ray diffraction, it was Li 1.0 Mn 2 O 4.2 . Using this sample, the pH dependency was measured in the same manner.
[0058]
The results are shown in FIG. Li 1.4 Mn 2 O 4.2 is indicated by ◆, Li 1.8 Mn 2 O 4.2 is indicated by ■, and Li 1.0 Mn 2 O 4.2 is indicated by Δ. In FIG. 6, the horizontal axis represents the equilibrium pH, and the vertical axis represents the lithium adsorption amount. As a comparative example, the results of LiMn 2 O 4.2 described in (Patent Document 4) are indicated by triangles. The lithium adsorbent obtained in Example 1 in weakly acidic to alkaline range showed higher adsorption performance than the lithium adsorbent LiMn 2 O 4.2 described in Patent Document 4. As is clear from FIG. 6, Li 1.8
Claims (8)
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