JP2022515389A - アルカリの添加を伴うブラインからリチウムを回収するためのプロセス - Google Patents
アルカリの添加を伴うブラインからリチウムを回収するためのプロセス Download PDFInfo
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- JP2022515389A JP2022515389A JP2021535116A JP2021535116A JP2022515389A JP 2022515389 A JP2022515389 A JP 2022515389A JP 2021535116 A JP2021535116 A JP 2021535116A JP 2021535116 A JP2021535116 A JP 2021535116A JP 2022515389 A JP2022515389 A JP 2022515389A
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- Prior art keywords
- lithium ion
- lithium
- ion sieve
- reactor
- sieve
- 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.)
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Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 123
- 239000012267 brine Substances 0.000 title claims abstract description 109
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 72
- 230000008569 process Effects 0.000 title claims abstract description 62
- 239000003513 alkali Substances 0.000 title claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 296
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 292
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000002253 acid Substances 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000012528 membrane Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 238000010828 elution Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000010586 diagram Methods 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000484 niobium oxide Inorganic materials 0.000 abstract 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 239000011734 sodium Substances 0.000 description 15
- 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 14
- 229910052708 sodium Inorganic materials 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 11
- 238000011069 regeneration method Methods 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000003480 eluent Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000007654 immersion Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000009285 membrane fouling Methods 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
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000012500 ion exchange media Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3804—Affinity chromatography
- B01D15/3828—Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
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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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
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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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/10—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J47/02—Column or bed processes
- B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2311/18—Details relating to membrane separation process operations and control pH control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2321/18—Use of gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
本出願は、2018年12月18日に出願された同時係属出願第16/224,463号の一部継続出願であり、2017年12月27日に出願された米国仮出願第62/610,575号の利益を主張し、そのすべてが参照により本出願に明示的に組み込まれる。
LIS.H+Li+→LIS.Li+H+ (1)
式中、LIS.Hは、新たに再生された水素型のリチウムイオンふるいを表し、LIS.Liは、リチウム担持型のリチウムイオンふるいを表す。
Lis.Li+H+→Lis.H+Li+ (2)
Chitrakarの図4aに示す吸着剤からのリチウムおよびチタンの初期抽出に対するHCl濃度の効果を評価するために、Chitrakarで重要な試験が行われた。Chitrakarの図4aは、HCl濃度の関数として、抽出されたリチウムおよびチタンの量を示す。Chitrakarのデータは、HCl濃度が0.2M以上であるべきであることを示している。実際、本発明を実施するのに好ましい酸濃度である0.1Mの酸濃度未満では吸着剤からのリチウム抽出についてのデータは、Chitrakarの図4aには示されていない。本発明では、LTO吸着剤のリチウム成分およびチタン成分は、Chitrakarによって予測されるよりもはるかに低い酸濃度で抽出される。
Claims (29)
- リチウム含有ブラインからリチウムイオンを回収するためのプロセスであって、
第1のリアクタ内で、前記リチウム含有ブラインをリチウムイオンふるいと接触させて、前記リチウムイオンふるいを含むリチウムイオン錯体を形成することと、
第2のリアクタ内で、リチウムイオンを前記リチウムイオンふるいから脱錯化して、前記リチウムイオンふるいから分離された酸性リチウム塩溶出液を形成することと、
を含み、
前記リチウムイオンふるいは、チタンまたはニオブの酸化物を含み、
前記第1のリアクタのpHが、無水アンモニアまたは水酸化アンモニウムを含むアルカリの添加によって、一定の値に維持される、
プロセス。 - 前記脱錯化が、酸を使用した溶離によって行われる、請求項1に記載のプロセス。
- 前記酸の濃度が、前記酸の添加によって、一定の値に維持される、請求項2に記載のプロセス。
- 前記酸の前記濃度が、0.1M未満である、請求項2または請求項3に記載のプロセス。
- 前記酸のpHが、1を超え3未満である、請求項2から4のいずれか一項に記載のプロセス。
- 前記酸のpHが、約2である、請求項2から4のいずれか一項に記載のプロセス。
- 前記pHが、4を超え9未満の一定の値に維持される、請求項1から3のいずれか一項に記載のプロセス。
- 前記第1のリアクタ内の前記pHが、6を超え8未満である、請求項1から7のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいの90%超が、40μm未満の平均粒子直径を有し、前記リチウムイオンふるいの90%超が、0.4μmを超える平均粒子直径を有する、請求項1から8のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいの粒子の90体積%超が、直径100μm未満および直径0.5μm超である、請求項1から8のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいの粒子の90体積%超が、直径0.5μm超である、請求項1から9のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいが、メタチタン酸を含む、請求項1から11のいずれか一項に記載のプロセス。
- 請求項1から12のいずれか一項に記載のプロセスであって、
固体/液体分離デバイスを用いて、前記リチウムイオンふるいを含む前記リチウムイオン錯体を前記ブラインから分離することと、
前記リチウムイオンふるいを含む前記リチウムイオン錯体を水と接触させた後、前記第2のリアクタ中で、脱錯化することと、
をさらに含む、プロセス。 - 請求項1から13のいずれか一項に記載のプロセスであって、
固体/液体分離デバイスを用いて、前記リチウムイオンふるいを前記酸性リチウム塩溶出液から分離することと、
前記第2のリアクタ中での脱錯化後に、前記リチウムイオンふるいを水と接触させて、再生リチウムイオンふるいおよび希酸水洗浄液を得ることと、
前記再生リチウムイオンふるいを前記第1のリアクタに加えることと、
をさらに含む、プロセス。 - 前記希酸水洗浄液および追加の濃酸を、前記第2のリアクタに添加することをさらに含む、請求項1から14のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいを含む前記リチウムイオン錯体と前記酸との平均接触時間が、1時間未満である、請求項2から15のいずれか一項に記載のプロセス。
- 前記第1のリアクタが、限外濾過または精密濾過膜を含む、請求項1から16のいずれか一項に記載のプロセス。
- 空気が、前記第1のリアクタの内容物を撹拌するために使用される、請求項1から17のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいの濃度が、50g/L超である、請求項1から18のいずれか一項に記載のプロセス。
- 前記限外濾過膜または前記精密濾過膜を通る流速が、30kPa未満の膜貫通圧で30LMHを超える、請求項17から19のいずれか一項に記載のプロセス。
- 前記リチウム含有ブラインを前記リチウムイオンふるいと接触させる前に、1μm未満の平均粒子直径を有するリチウムイオンふるいを除去することをさらに含む、請求項1から20のいずれか一項に記載のプロセス。
- 前記第2のリアクタ中で、前記リチウムイオンを前記リチウムイオンふるいから脱錯化する前に、前記リチウムイオンふるいを含む前記リチウムイオン錯体を、水分含有量が90重量%未満になるまで脱水することをさらに含む、請求項1から21のいずれか一項に記載のプロセス。
- 前記第1のリアクタに添加する前に、前記再生リチウムイオンふるいを脱水することをさらに含む、請求項14から22のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいを水と接触させることが、前記リチウムイオンふるいから脱錯化された前記リチウムイオンの50%超を、前記再生リチウムイオンふるいを前記第1のリアクタに加える前に、前記リチウムイオンふるいから洗浄するように、前記リチウムイオンふるいを十分な水と接触させることを含む、請求項14から23のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいを水と接触させることが、前記リチウムイオンふるいから脱錯化された前記リチウムイオンの50%超を、前記再生リチウムイオンふるいを前記第1の撹拌リアクタに加える前に、前記リチウムイオンふるいから洗浄するように、2つ以上の向流段階で前記リチウムイオンふるいを水と接触させることを含む、請求項24に記載のプロセス。
- 前記アルカリが、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、水酸化マグネシウム、または水酸化カルシウムをさらに含む、請求項1から25のいずれか一項に記載のプロセス。
- 前記酸が、塩酸または硫酸を含む、請求項2から26のいずれか一項に記載のプロセス。
- 前記リチウムイオンふるいの濃度が、100g/L超である、請求項1から27のいずれか一項に記載のプロセス。
- リチウム含有ブラインからリチウムイオンを回収するためのプロセスであって、
第1のリアクタ内で、リチウム含有ブラインをリチウムイオンふるいと接触させて、リチウムイオンふるいを含むリチウムイオン錯体を形成することと、
第2のリアクタ内で、リチウムイオンを前記リチウムイオンふるいから脱錯化して、前記リチウムイオンふるいから分離された酸性リチウム塩溶出液を形成することと、
を含み、
前記リチウムイオンふるいが、チタンまたはニオブの酸化物を含み、
前記第1のリアクタのpHが、8%w/w未満の濃度の水酸化ナトリウムを含むアルカリの添加によって、一定の値に維持される、
プロセス。
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US16/224,463 US11534748B2 (en) | 2017-12-27 | 2018-12-18 | Process for recovery of lithium from brine |
US16/224,463 | 2018-12-18 | ||
CAPCT/CA2018/000240 | 2018-12-20 | ||
PCT/CA2018/000240 WO2019126862A1 (en) | 2017-12-27 | 2018-12-20 | Process for recovery of lithium from brine |
US16/410,523 | 2019-05-13 | ||
US16/410,523 US11518686B2 (en) | 2017-12-27 | 2019-05-13 | Process for recovery of lithium from brine |
PCT/CA2019/000064 WO2020124192A1 (en) | 2018-12-18 | 2019-05-14 | Process for recovery of lithium from brine with addition of alkali |
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