WO2024126601A1 - Lithium extraction - Google Patents
Lithium extraction Download PDFInfo
- Publication number
- WO2024126601A1 WO2024126601A1 PCT/EP2023/085653 EP2023085653W WO2024126601A1 WO 2024126601 A1 WO2024126601 A1 WO 2024126601A1 EP 2023085653 W EP2023085653 W EP 2023085653W WO 2024126601 A1 WO2024126601 A1 WO 2024126601A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- solution
- release
- ion
- acid
- Prior art date
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000605 extraction Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000005342 ion exchange Methods 0.000 claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 35
- 150000007524 organic acids Chemical class 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 16
- 239000000920 calcium hydroxide Substances 0.000 claims description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- -1 hydrogen titanium oxide Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 72
- 239000000243 solution Substances 0.000 description 72
- 235000011116 calcium hydroxide Nutrition 0.000 description 15
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 14
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 14
- 239000012510 hollow fiber Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 150000004692 metal hydroxides Chemical class 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229940071264 lithium citrate Drugs 0.000 description 4
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 150000003891 oxalate salts Chemical class 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000012500 ion exchange media Substances 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001470 polyketone Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000545744 Hirudinea Species 0.000 description 1
- 229910013596 LiOH—H2O Inorganic materials 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000006152 selective media Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
Definitions
- the present invention relates to a method of processing lithium-containing solutions to extract or recover lithium, in the form of lithium hydroxide, for further use. More particularly, the invention provides a method of extracting lithium through direct lithium extraction.
- Lithium hydroxide (specifically, lithium hydroxide monohydrate) is one of two main forms of lithium used for the production of lithium-ion batteries.
- the demand for lithium hydroxide is growing exponentially due to the increased demand for electric vehicles.
- the production of lithium hydroxide requires energy-intensive electrolytic methods or additional precipitation steps compared to the second main form, lithium carbonate.
- Direct Lithium Extraction is a process involving the selective extraction of lithium from aqueous sources such as natural brines, seawater or industrial wastewaters. This can be achieved in various ways including adsorption, ion exchange, electrodialysis, nanofiltration or others.
- ion exchange represents an energy-efficient process that is driven by adjustments in pH rather than applied pressure or electrical current.
- a lithium-containing feedstock solution such as brine over lithium-selective ion exchange media
- lithium ions migrate into the selective media (that is, are extracted or leeched from the feedstock), leaving other components in the feedstock, to replace ions already present.
- the remaining feedstock can be removed.
- release solution dilute acid solution
- the lithium-rich release solution that is created from this process can then undergo further concentration and crystallisation stages to produce salts such as lithium hydroxide or lithium carbonate.
- Such lithium-selective ion exchange media are sometimes referred to as Lithium-Ion Sieves (LISs).
- the acid used to release the lithium ions from the lithium-selective ion exchange medium is hydrochloric acid.
- hydrochloric acid is introduced into the column, lithium ions are removed and the enriched release solution that is formed comprises lithium chloride (typically with small amounts of impurities).
- That lithium chloride still needs to be converted into lithium carbonate or more preferably lithium hydroxide in order to be used in battery production.
- Lithium carbonate can be produced from the lithium chloride-containing release solution by way of addition of sodium carbonate as per equation (1 ): 2LICI (aq) + Na2CO3 (aq) — » I 2CO3 (s) + 2NaCI (aq) (1 )
- lithium hydroxide In order to then produce lithium hydroxide, an additional processing step is required, treating the lithium carbonate with calcium hydroxide as per equation (2). This forms a precipitate of calcium carbonate, leaving a lithium hydroxide solution which can then be crystallised through evaporation or antisolvent addition.
- the present invention has been devised in the light of the above considerations.
- the present inventors sought to provide an improved and more environmentally friendly process for DLE of lithium from lithium-containing solutions such as geothermal brines.
- the inventors have found that by replacing hydrochloric acid with an organic acid (such as oxalic acid or citric acid) in the release step, a solution of the lithium salt of the organic acid is produced and hence included in the lithium-enriched release solution.
- This solution can be reacted with a suitable precipitant, in the form of an alkali (suitably a non-lithium metal hydroxide) to produce lithium hydroxide, without having to first produce lithium carbonate.
- the non-lithium metal hydroxide can be added directly to the solution of the lithium salt of the organic acid (i.e. the lithium enriched release solution).
- a non-lithium metal hydroxide such as calcium hydroxide
- the non-lithium metal hydroxide can be added directly to the solution of the lithium salt of the organic acid (i.e. the lithium enriched release solution).
- calcium hydroxide may be added to a solution of lithium oxalate as per equation (3) for lithium oxalate.
- organic acids and non-lithium metal hydroxides may be used for which the non-lithium metal cation of the hydroxide and the organic conjugate base anion of the organic acid yields a product that is insoluble or has low solubility in water.
- the invention provides a method of direct lithium extraction from a lithium- containing feedstock, the method comprising:
- a release step in which a release solution comprising a protic acid is contacted with the lithium-ion-exchange material, whereby lithium ions are released from the lithium-ion-exchange material into the release solution;
- a precipitation step in which a precipitant is mixed with the lithium-enriched release solution; wherein the protic acid is an organic acid; and the precipitant is a non-lithium containing alkali.
- the lithium ions enter the release solution to form the lithium salt of the organic acid, to be replaced in the lithium-ion-exchange material by protons. Then, in the precipitation step, by a further ion exchange lithium hydroxide is formed along with the non-lithium metal salt of the organic acid. That non-lithium metal salt of the organic acid precipitates out of the solution, leaving a solution of lithium hydroxide.
- non-lithium containing alkali means an alkali which does not contain lithium.
- Alkali as used herein means any base that is soluble in water and forms hydroxide ions, or the solution of a base in water.
- the alkali therefore is necessarily a source of hydroxide ions, as is necessary for the desired ion exchange to form lithium hydroxide, and the consequent precipitation.
- a non-lithium metal hydroxide is used.
- the organic acid is suitably chosen to release lithium ions in the release step; it is therefore a protic acid.
- the non-lithium metal hydroxide is chosen such that the salt of its metal with the organic acid is not soluble in water to an appreciable degree ( ⁇ 1 mg/mL, suitably ⁇ 0.5 mg/mL, more suitably ⁇ 0.1 mg/mL), so that it precipitates in the precipitation step.
- the organic acid may suitably be, for example, citric acid or oxalic acid. Of these oxalic acid may be preferred.
- the precipitant may preferably be, for example, calcium hydroxide, magnesium hydroxide or barium hydroxide. Of these calcium hydroxide may be preferred.
- a lithium-containing feedstock has lithium ions ‘removed’ from it by the lithium-ion- exchange material. Those are replaced by, generally, protons.
- This extraction step is therefore characterised as a first ion exchange.
- a release solution is used to perform the equivalent ion exchange, in reverse. That is, protons from the release solution exchange with lithium ions and release the lithium ions into the release solution.
- the depleted feedstock is suitably removed after the extraction step. It may then be, for example, subject to further processing; or recycled back into the feed to act as a ‘new’ feedstock for lithium ion extraction.
- a single aliquot of feedstock may be subject to the above extraction and release steps multiple times (cycles), gradually reducing the lithium content each time.
- the first washing step in which the lithium-ion-exchange material is washed with water (suitably deionised water).
- the first washing step may be conducted for, for example, about 10-120 minutes.
- the desired ion exchange lithium in the feedstock switching with protons in the lithium-ion-exchange material
- the feedstock used in the extraction step may suitably have a pH of greater than 7, for example greater than 8 or greater than 9. This may be achieved in a step, before the extraction step, of increasing the pH of the feedstock by addition of an alkaline solution or basic compound, for example NaOH, in the amount required to raise the pH to the desired level.
- the extraction step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C.
- a temperature above room temperature for example around 25-70°C, suitably 50-70°C.
- geothermal brines are used as the feedstock, they are often naturally of elevated temperature (for example about 40-70°C) and hence the extraction step necessarily proceeds at above room temperature where such a feedstock is used directly from the ground source.
- the desired ion exchange lithium in the lithium-ion- exchange material switching with protons in the release solution
- a release solution of reduced pH i.e. a proton-rich environment
- the release solution may suitably have a pH of less than 7, for example less than 6 or less than 5.
- a suitable choice of release solution is an acidic solution such as citric acid, for example a 0.2 M citric acid solution.
- a lithium citrate solution is obtained. This can be processed to extract lithium citrate (for example by crystallisation, precipitation etc.). Lithium citrate can then be processed to form, for example, lithium hydroxide as described above.
- the release step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C.
- the lithium-ion-exchange material may suitably comprise a lithium-ion selective material (lithium-ion sieve) and a matrix material.
- the lithium-ion-exchange material may suitably be provided in the form of beads or hollow fibers, with hollow fibers being preferred.
- the hollow fibers themselves comprise (that is, preferably are in the form of) membranes, comprising a matrix material and an ion selective material.
- the matrix material comprises or consists of PES.
- lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material.
- Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
- the ion selective material comprises LTO or HTO derived from LTO. That is particularly the case where the matrix material is PES.
- the selective material Before the extraction step, the selective material may be subjected to a priming step, wherein it (especially, LTO or LMO contained within it) is contacted with a priming solution (which may have the same properties as the release solution discussed herein, especially it may be a protic acid).
- a priming solution which may have the same properties as the release solution discussed herein, especially it may be a protic acid.
- HTO derived from LTO
- HMO derived from LMO
- the HTO (derived from HTO) or HMO (derived from LMO) selectively ion exchanges its protons for lithium ions from the feedstock.
- HTO derived from LTO or HMO derived from LMO can act as a selective sieve or adsorbent for lithium ions.
- the process comprises one fewer steps than the conventional method; (b) the process reduces impurities in the lithium enriched solution produced in the second step; and (c) the overall yield may be increased due to the lower solubility of the precipitated organic acid salts when compared to lithium carbonate.
- the precipitate from the (iii) precipitation step comprises a salt of the organic acid with few impurities. This allows for further processing or re-sale of the precipitate, making the process more environmentally friendly.
- the claimed processes are advantageous when compared to the known methods of the prior art which comprise multiple solid-liquid separations and non-zero solubility of by-products results in expensive and contaminated lithium hydroxide. This can detrimentally affect the economics of the process and produces more waste.
- the invention includes the combination of the aspects and preferred features described except where such a combination is clearly impermissible or expressly avoided. Detailed Description of the Invention
- Direct lithium extraction is a process where lithium is selectively extracted from impure solutions containing large amounts of multiple ionic species, wherein the majority of other components are left in solution.
- DLE techniques including electrodialysis, nanofiltration, adsorption and ion-exchange. The latter two approaches hold the most promise in terms of lithium selectivity, energy consumption and cost.
- DLE represents an alternative to conventional lithium brine extraction processes which utilise successive crystallisation stages (often with the use of evaporation ponds) which remove impurity compounds such as sodium chloride and leave the lithium in solution.
- the selective material may be provided as beads in a column, with the feedstock poured into/through the column; or it may be provided in the form of hollow fibers, with the feedstock fed through or over the fibers. This facilitates the uptake of the lithium and replaces protons in the material.
- This initial contact, removing the lithium from the feedstock and ‘storing’ it in the selective material, can be termed an ‘extraction step’ of the DLE process.
- rate must also be balanced against other factors such as acid/base safety and toxicity, additional cost and so on.
- a lithium selective material (Lithium-Ion Sieve, LIS) is needed for the desired ion exchanges to occur in the extraction and release steps.
- Lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material.
- Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from LMO, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
- the lithium selective material is not used in the pure form, but it is rather contained within or embedded in a matrix.
- the matrix used here is not particularly limited given that it has good chemical and thermal stability.
- Suitable matrix materials include ceramics and polymers. Suitable ceramics include oxides such as alumina, zirconia and titania.
- Suitable polymers include both thermoplastics and thermosetting plastics.
- the matrix material comprises one or more selected from: polysulfone (PSU), polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyimide. In some embodiments it consists of one of those. PES is particularly preferred. Therefore preferably the matrix material comprises or consists of PES.
- the matrix is suitably porous; this increases the flow of the feedstock to the selective material (which may not necessarily be present on the outer surface of the matrix material) and facilitates transfer of lithium ions.
- the pores effectively increase the active surface area of the material. Accordingly larger pores, for example of an average pore size 0.1-2 pm, for example 0.5-1 pm, are preferable.
- a porosity of > 60% may be suitable, in particular > 80%.
- the pores may have a size (Dso) of 2 pm, for example ⁇ 1 pm.
- the selective material may suitably be provided in the form of particles.
- the particle size of the selective material is ⁇ 50 pm, suitably ⁇ 25 pm, or ⁇ 10 pm. Most suitable is a particle size of ⁇ 5 pm, or ⁇ 3 pm.
- the particles may suitably have a size of > 200 nm, for example > 400 nm, > 1 pm, or > 2 pm.
- the present lithium-ion-exchange material includes a selective material and a matrix material. It may be provided in various morphologies; for example, it may be formed into beads (for example, substantially spherical beads of average diameter 0.01-10 mm) or, more suitably, into a membrane form.
- Such a membrane might be a simple flat (e.g. cast) membrane, or have a more complex structure such as that of a hollow fiber.
- Hollow fiber membranes have been found by the inventors to have several advantages in DLE processes; in particular, a high useful surface area especially where the feedstock is flown in contact with the lithium-ion-exchange material.
- Such hollow fibers are known in the art of water treatment; they are elongate, generally extruded members with a bore (hollow part) inside the substantially circular cross-section fiber.
- a hollow fiber morphology of the material may be preferable as a feedstock brought into contact with the fiber has surface contact with a large active area.
- Hollow fibers can also be packed into a housing to form a membrane module; flow of feedstock through the module again allows high surface contact and hence efficient lithium extraction and release.
- Suitable hollow fiber dimensions will be apparent to those skilled in the art. For example, a hollow fiber length of 0.2-2 m, an outer diameter of 0.4-5 mm, and a wall thickness of 10-200 pm may be used.
- the hollow fibers themselves may have, for example, a length of about 1 m, an outer diameter of about 1 mm, and an inner (bore) diameter of about 0.9 mm.
- the lithium-ion-exchange material is contacted to a lithium-containing solution (feedstock).
- a lithium-containing solution feedstock
- this can be done batch-wise or using a continual flow of the lithium-containing solution.
- Lithium-containing brines are a typical feedstock for DLE, typically containing from 50 to 4000 ppm lithium content.
- the brines typically also contain multiple other ionic species including Na + , K + , Ca 2+ , Mg 2+ , F’, Cl", Br, SO ', PO -, NO 3 -, CO 3 2 -, and HCO 3 ‘.
- lithium-containing solutions suitable as a feedstock include the product of leeching lithium from solid materials such as lithium-rich ores, lithium-rich recycled material, lithium-containing anodes and the like. This is often done using sulfuric acid, resulting in acidic lithium-containing solutions.
- the feedstock is preferably adjusted to a pH of >7, optionally the pH may be raised yet higher, for example >8, >9, >10 or >11 .
- Suitable bases used to adjust the pH of the feedstock solution are not particularly limited as the lithium- ion sieve is highly selective for lithium ions.
- Suitable bases include NaOH, KOH, NaCO 3 , KCO 3 , NaHCO 3 , KHCO 3 , NH4OH, ammonium carbonate, ammonium persulfate, ammonia, Ca(OH)2 and Ba(OH)2 (and their associated oxides). In terms of cost, NaOH is preferred.
- the extraction step may also or instead suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
- a temperature of 25-70°C, and particularly 50-70°C, may be preferred.
- the length of time for which there is contact between the feedstock and the selective material depends on several factors, for example how the selective material is provided. If it is provided in fibers, or a column, through which a feedstock is flown, the rate of flow is important. If the selective material is simply placed in contact with a stationary feedstock for some length of time, the time it is left is the relevant feature.
- the extraction step may be conducted for 10-150 minutes.
- the de-lithiated feedstock is suitably removed from contact with the selective material, and the selective material may be rinsed with fresh water. This can remove any impurities loosely bound to the lithium-ion-exchange material before the release step is carried out.
- a protic acidic solution (release solution) is introduced; this replaces the lithium ions with protons.
- the lithium is released from the selective material, forming a lithium-rich solution which can be removed for further processing. This can be termed a ‘release step’ of the DLE process.
- Suitable acids include oxalic acid and citric acid.
- Citric acid is preferable as it is a relatively easily obtainable, low toxicity acid which provides lithium citrate solutions that are readily processed.
- oxalic acid may be preferred due to the relatively lower solubility of metal oxalates (especially calcium oxalate, 6.1 mg/L at 20°C, where the precipitant is calcium hydroxide) than of metal citrates (especially calcium citrate, 850 mg/L at 18°C, where the precipitant is calcium hydroxide).
- the pH of the release solution (which is generally aqueous) depends of course on the acid included in it and how much is included; generally, it has a pH ⁇ 7, for example ⁇ 6, ⁇ 5, ⁇ 4, or ⁇ 3.
- the lithium-ion exchange material is exposed to a solution of an organic acid.
- a solution of an organic acid can be done batch-wise or using a continual flow of organic acid solution.
- the organic acid may be one which comprises a carboxylic acid group.
- the organic acid comprises two or more carboxylic acid groups.
- the organic acid is not particularly limited, provided the solubility of its lithium salt is greater than that of another metal salt of the organic acid.
- Suitable organic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, malic acid, and tartaric acid. Of these, citric and especially oxalic acid are preferable as lithium oxalate is soluble in water whereas other oxalate salts are insoluble in water.
- the release step may suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
- the release step may suitably be conducted at up to 70°C.
- a temperature above room temperature, for example around 25-70°C, suitably 50-70°C, may be preferred.
- a precipitant is added to the lithium-enriched release solution in order to perform a double-displacement reaction to liberate lithium hydroxide and precipitate the organic conjugate base anions as an insoluble salt.
- the precipitant is an alkali (that is, produces an alkali solution upon addition to water; any base that is soluble in water and forms hydroxide ions, or the solution of a base in water).
- the precipitant contains metal cations that form insoluble salts with organic acids such as oxalic acid and citric acid
- Suitable precipitants for use in the precipitation step may include alkaline earth metal hydroxides such as Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2, alkaline earth metal oxides (which hydrate to provide alkaline earth metal hydroxides) such as MgO, CaO, SrO and BaO, or an alkali metal hydroxide such as NaOH or KOH.
- alkaline earth metal hydroxides such as Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2
- alkaline earth metal oxides which hydrate to provide alkaline earth metal hydroxides
- an alkali metal hydroxide such as NaOH or KOH.
- the precipitant cannot be a lithium hydroxide or oxide.
- the precipitant is preferably Mg(OH)2 or Ca(OH)2, more preferably Ca(OH)2.
- the precipitant is preferably Ca(OH)2 as the solubility of calcium oxalate is the lowest of alkaline earth oxalates.
- the precipitant is added in the precipitation step as an aqueous solution.
- the precipitant may be added in the precipitation step as a solid.
- the precipitant is added in sufficient volume to cause precipitation of the organic conjugate base anions as an insoluble salt.
- the precipitate may be separated from the supernatant solution by any suitable means, for example, gravity separation, filtration, centrifugation, hydrocyclonic separation and the like.
- the solution of lithium hydroxide may be subjected to an isolation to produce solid lithium hydroxide.
- the lithium hydroxide may be isolated as the monohydrate (LiOH-H2O) or the anhydrate (LiOH) through evaporation of the liquid or by crystallisation.
- Suitable crystallisation techniques include antisolvent crystallisation wherein lithium hydroxide precipitates from solution upon addition of a suitable organic solvent such as acetone. The antisolvent may then be recovered after separation of the solid lithium hydroxide by, for example, distillation.
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Abstract
Described is a method of direct lithium extraction from a lithium-containing feedstock, the method comprising extraction, release and precipitation steps. In the release step, in which a release solution comprising a protic acid is contacted with the lithium-ion-exchange material, whereby lithium ions are released from the lithium-ion-exchange material into the release solution, the protic acid is an organic acid. In the precipitation step, in which a precipitant is mixed with the lithium-enriched release solution, the precipitant is a non-lithium containing alkali.
Description
Lithium Extraction
Field of the Invention
The present invention relates to a method of processing lithium-containing solutions to extract or recover lithium, in the form of lithium hydroxide, for further use. More particularly, the invention provides a method of extracting lithium through direct lithium extraction.
Background
Lithium hydroxide (specifically, lithium hydroxide monohydrate) is one of two main forms of lithium used for the production of lithium-ion batteries. The demand for lithium hydroxide is growing exponentially due to the increased demand for electric vehicles. However, the production of lithium hydroxide requires energy-intensive electrolytic methods or additional precipitation steps compared to the second main form, lithium carbonate.
Direct Lithium Extraction (DLE) is a process involving the selective extraction of lithium from aqueous sources such as natural brines, seawater or industrial wastewaters. This can be achieved in various ways including adsorption, ion exchange, electrodialysis, nanofiltration or others.
Of these, ion exchange represents an energy-efficient process that is driven by adjustments in pH rather than applied pressure or electrical current. When flowing a lithium-containing feedstock solution such as brine over lithium-selective ion exchange media (in an extraction step), lithium ions migrate into the selective media (that is, are extracted or leeched from the feedstock), leaving other components in the feedstock, to replace ions already present. Once the lithium has been taken up by the media, the remaining feedstock can be removed. By then flowing a dilute acid solution (release solution) through the media (in a release step), protons from the acid exchange with the lithium ions held in the media (releasing the lithium ions into the release solution). The lithium-rich release solution that is created from this process can then undergo further concentration and crystallisation stages to produce salts such as lithium hydroxide or lithium carbonate. These two salts are the main form of lithium used in the manufacture of lithium-ion batteries.
Such lithium-selective ion exchange media are sometimes referred to as Lithium-Ion Sieves (LISs).
Typically, the acid used to release the lithium ions from the lithium-selective ion exchange medium is hydrochloric acid. When hydrochloric acid is introduced into the column, lithium ions are removed and the enriched release solution that is formed comprises lithium chloride (typically with small amounts of impurities).
That lithium chloride still needs to be converted into lithium carbonate or more preferably lithium hydroxide in order to be used in battery production.
Lithium carbonate can be produced from the lithium chloride-containing release solution by way of addition of sodium carbonate as per equation (1 ):
2LICI (aq) + Na2CO3 (aq) — » I 2CO3 (s) + 2NaCI (aq) (1 )
The lower solubility of lithium carbonate compared to sodium carbonate results in its precipitation out of solution, where it can be separated from the remaining sodium chloride solution.
In order to then produce lithium hydroxide, an additional processing step is required, treating the lithium carbonate with calcium hydroxide as per equation (2). This forms a precipitate of calcium carbonate, leaving a lithium hydroxide solution which can then be crystallised through evaporation or antisolvent addition.
LI2CO3 (s) + Ca(OH)2 (aq) — » 2LIOH (aq) + CaCOs (s) (2)
In this case, the low solubility of calcium carbonate results in its precipitation, leaving the lithium hydroxide in solution.
However, the conversion of lithium chloride to lithium carbonate in equation (1) results in some lithium remaining in solution, given that lithium carbonate has moderate solubility in water (12.9 g/L at 25°C). Therefore the inventors have found that this methodology has some efficiency detriment.
Furthermore, while this methodology is possible, the need for both sodium carbonate and calcium hydroxide reagents to perform the two steps adds cost and complexity to the process. This is especially true as each step requires its own solid-liquid separation process, which can result in losses of the desired product(s) and will incur additional energy costs.
The present invention has been devised in the light of the above considerations.
Summary of the Invention
The present inventors sought to provide an improved and more environmentally friendly process for DLE of lithium from lithium-containing solutions such as geothermal brines. In doing so the inventors have found that by replacing hydrochloric acid with an organic acid (such as oxalic acid or citric acid) in the release step, a solution of the lithium salt of the organic acid is produced and hence included in the lithium-enriched release solution. This solution can be reacted with a suitable precipitant, in the form of an alkali (suitably a non-lithium metal hydroxide) to produce lithium hydroxide, without having to first produce lithium carbonate.
So, rather than first precipitating lithium carbonate and then adding a non-lithium metal hydroxide (such as calcium hydroxide), the non-lithium metal hydroxide can be added directly to the solution of the lithium salt of the organic acid (i.e. the lithium enriched release solution). For example, calcium hydroxide may be added to a solution of lithium oxalate as per equation (3) for lithium oxalate.
IJ2C2O4 (aq) + Ca(OH)2 (aq) — ♦ 2LIOH (aq) + CaC2O4 (s) (3)
In this reaction, the insoluble calcium oxalate precipitates out of solution, leaving the lithium hydroxide (which is highly soluble) in solution. This solution may be further processed to produce solid lithium hydroxide via methods such as evaporative crystallisation or antisolvent crystallisation which are well known in the art.
Other organic acids and non-lithium metal hydroxides may be used for which the non-lithium metal cation of the hydroxide and the organic conjugate base anion of the organic acid yields a product that is insoluble or has low solubility in water.
Accordingly, in a first aspect, the invention provides a method of direct lithium extraction from a lithium- containing feedstock, the method comprising:
(i) an extraction step, in which the lithium-containing feedstock solution is contacted with a lithium-ion-exchange material, whereby the lithium-ion-exchange material is loaded with lithium ions;
(ii) a release step, in which a release solution comprising a protic acid is contacted with the lithium-ion-exchange material, whereby lithium ions are released from the lithium-ion-exchange material into the release solution; and
(iii) a precipitation step, in which a precipitant is mixed with the lithium-enriched release solution; wherein the protic acid is an organic acid; and the precipitant is a non-lithium containing alkali.
In the release step, the lithium ions enter the release solution to form the lithium salt of the organic acid, to be replaced in the lithium-ion-exchange material by protons. Then, in the precipitation step, by a further ion exchange lithium hydroxide is formed along with the non-lithium metal salt of the organic acid. That non-lithium metal salt of the organic acid precipitates out of the solution, leaving a solution of lithium hydroxide.
It will be recognised that non-lithium containing alkali means an alkali which does not contain lithium. Alkali as used herein means any base that is soluble in water and forms hydroxide ions, or the solution of a base in water. The alkali therefore is necessarily a source of hydroxide ions, as is necessary for the desired ion exchange to form lithium hydroxide, and the consequent precipitation. Suitably a non-lithium metal hydroxide is used.
The organic acid is suitably chosen to release lithium ions in the release step; it is therefore a protic acid. The non-lithium metal hydroxide is chosen such that the salt of its metal with the organic acid is not soluble in water to an appreciable degree (<1 mg/mL, suitably <0.5 mg/mL, more suitably <0.1 mg/mL), so that it precipitates in the precipitation step.
The organic acid may suitably be, for example, citric acid or oxalic acid. Of these oxalic acid may be preferred.
The precipitant may preferably be, for example, calcium hydroxide, magnesium hydroxide or barium hydroxide. Of these calcium hydroxide may be preferred.
In the extraction step, a lithium-containing feedstock has lithium ions ‘removed’ from it by the lithium-ion- exchange material. Those are replaced by, generally, protons. This extraction step is therefore characterised as a first ion exchange.
In the release step, a release solution is used to perform the equivalent ion exchange, in reverse. That is, protons from the release solution exchange with lithium ions and release the lithium ions into the release solution.
The depleted feedstock is suitably removed after the extraction step. It may then be, for example, subject to further processing; or recycled back into the feed to act as a ‘new’ feedstock for lithium ion extraction.
A single aliquot of feedstock may be subject to the above extraction and release steps multiple times (cycles), gradually reducing the lithium content each time.
In some embodiments, after the depleted feedstock is removed, there is a first washing step in which the lithium-ion-exchange material is washed with water (suitably deionised water). The first washing step may be conducted for, for example, about 10-120 minutes.
In the extraction step, it will be appreciated that the desired ion exchange (lithium in the feedstock switching with protons in the lithium-ion-exchange material) can be driven by using a feedstock of raised pH (i.e. a proton-poor environment). Therefore, the feedstock used in the extraction step may suitably have a pH of greater than 7, for example greater than 8 or greater than 9. This may be achieved in a step, before the extraction step, of increasing the pH of the feedstock by addition of an alkaline solution or basic compound, for example NaOH, in the amount required to raise the pH to the desired level.
The extraction step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C. Where geothermal brines are used as the feedstock, they are often naturally of elevated temperature (for example about 40-70°C) and hence the extraction step necessarily proceeds at above room temperature where such a feedstock is used directly from the ground source.
In the release step, it will similarly be appreciated that the desired ion exchange (lithium in the lithium-ion- exchange material switching with protons in the release solution) can be driven by using a release solution of reduced pH (i.e. a proton-rich environment); hence the inclusion of protic acid in the release solution. The release solution may suitably have a pH of less than 7, for example less than 6 or less than 5.
For example, a suitable choice of release solution is an acidic solution such as citric acid, for example a 0.2 M citric acid solution. With such a release solution, after the release step a lithium citrate solution is obtained. This can be processed to extract lithium citrate (for example by crystallisation, precipitation etc.). Lithium citrate can then be processed to form, for example, lithium hydroxide as described above.
The release step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C.
The lithium-ion-exchange material may suitably comprise a lithium-ion selective material (lithium-ion sieve) and a matrix material.
The lithium-ion-exchange material may suitably be provided in the form of beads or hollow fibers, with hollow fibers being preferred.
The hollow fibers themselves comprise (that is, preferably are in the form of) membranes, comprising a matrix material and an ion selective material.
In the lithium-ion-exchange material, preferably the matrix material comprises or consists of PES. In some embodiments, lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material. Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
Preferably the ion selective material comprises LTO or HTO derived from LTO. That is particularly the case where the matrix material is PES.
Before the extraction step, the selective material may be subjected to a priming step, wherein it (especially, LTO or LMO contained within it) is contacted with a priming solution (which may have the same properties as the release solution discussed herein, especially it may be a protic acid). This extracts lithium ions from the LTO or LMO, leaving spaces which are filled with protons from the priming solution. This generates HTO (derived from LTO) or HMO (derived from LMO). Then, during the extraction step, the HTO (derived from HTO) or HMO (derived from LMO) selectively ion exchanges its protons for lithium ions from the feedstock. The spaces remain the right size for lithium ions because of the LTO-derivation of the HTO and the LMO-derivation of the HMO; accordingly HTO derived from LTO or HMO derived from LMO can act as a selective sieve or adsorbent for lithium ions.
The inventors observe that the use of organic acids in the adsorption-desorption DLE process may have the following advantages: (a) the process comprises one fewer steps than the conventional method; (b) the process reduces impurities in the lithium enriched solution produced in the second step; and (c) the overall yield may be increased due to the lower solubility of the precipitated organic acid salts when compared to lithium carbonate.
As the above described ion exchange steps are highly selective for lithium, the precipitate from the (iii) precipitation step comprises a salt of the organic acid with few impurities. This allows for further processing or re-sale of the precipitate, making the process more environmentally friendly.
The claimed processes are advantageous when compared to the known methods of the prior art which comprise multiple solid-liquid separations and non-zero solubility of by-products results in expensive and contaminated lithium hydroxide. This can detrimentally affect the economics of the process and produces more waste.
The invention includes the combination of the aspects and preferred features described except where such a combination is clearly impermissible or expressly avoided.
Detailed Description of the Invention
Aspects and embodiments of the present invention will now be discussed with reference to the accompanying figures. Further aspects and embodiments will be apparent to those skilled in the art. All documents mentioned in this text are incorporated herein by reference.
Direct Lithium Extraction
Direct lithium extraction (DLE) is a process where lithium is selectively extracted from impure solutions containing large amounts of multiple ionic species, wherein the majority of other components are left in solution. There are a number of DLE techniques known in the art, including electrodialysis, nanofiltration, adsorption and ion-exchange. The latter two approaches hold the most promise in terms of lithium selectivity, energy consumption and cost. DLE represents an alternative to conventional lithium brine extraction processes which utilise successive crystallisation stages (often with the use of evaporation ponds) which remove impurity compounds such as sodium chloride and leave the lithium in solution.
General DLE methods are well known in the art and will not be discussed in great detail here.
For example, the selective material may be provided as beads in a column, with the feedstock poured into/through the column; or it may be provided in the form of hollow fibers, with the feedstock fed through or over the fibers. This facilitates the uptake of the lithium and replaces protons in the material. This initial contact, removing the lithium from the feedstock and ‘storing’ it in the selective material, can be termed an ‘extraction step’ of the DLE process.
In order to conserve charge, clearly, in order to desorb (release) the lithium ions they must be replaced with a suitable cation; this is often a proton as suitable protic acidic solutions are readily available.
Similarly, using basic solutions encourages the adsorption (take up) of lithium from solution, by removing protons from the lithium-ion sieve material. By varying pH, the selective ‘adsorption’ (take up) and ‘desorption’ (release) of lithium can be carefully controlled. A more basic feedstock solution provides the fastest lithium extraction rate; a more acidic release solution provides the fastest lithium release rate.
However, rate must also be balanced against other factors such as acid/base safety and toxicity, additional cost and so on.
Lithium selective material
A lithium selective material (Lithium-Ion Sieve, LIS) is needed for the desired ion exchanges to occur in the extraction and release steps.
It may be for example a metal organic framework, a zeolite, a layered double hydroxides or a metal oxide. Lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material. Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from LMO, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
[It will be recognised that, of course, during the ion exchange reaction a compound such as lithium manganese oxide (LMO) will be converted, to at least some degree, to hydrogen manganese oxide (HMO) on contact with the release solution; it will convert back when it leeches lithium ions from a suitable feedstock. Accordingly the ion selective material may be accurately described as both LMO and HMO derived from LMO depending on its state of lithium ion loading. The applies equally to LTO and HTO derived from LTO, of course.]
Typically, the lithium selective material is not used in the pure form, but it is rather contained within or embedded in a matrix.
The matrix used here is not particularly limited given that it has good chemical and thermal stability. Suitable matrix materials include ceramics and polymers. Suitable ceramics include oxides such as alumina, zirconia and titania. Suitable polymers include both thermoplastics and thermosetting plastics. In some preferred embodiments the matrix material comprises one or more selected from: polysulfone (PSU), polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyimide. In some embodiments it consists of one of those. PES is particularly preferred. Therefore preferably the matrix material comprises or consists of PES.
The matrix is suitably porous; this increases the flow of the feedstock to the selective material (which may not necessarily be present on the outer surface of the matrix material) and facilitates transfer of lithium ions. The pores effectively increase the active surface area of the material. Accordingly larger pores, for example of an average pore size 0.1-2 pm, for example 0.5-1 pm, are preferable.
For the present lithium-ion-exchange material, a porosity of > 60% may be suitable, in particular > 80%. The pores may have a size (Dso) of 2 pm, for example < 1 pm.
The selective material may suitably be provided in the form of particles.
In some embodiments, the particle size of the selective material is < 50 pm, suitably < 25 pm, or < 10 pm. Most suitable is a particle size of < 5 pm, or < 3 pm.
On the other hand, the particles may suitably have a size of > 200 nm, for example > 400 nm, > 1 pm, or > 2 pm.
Lithium-ion-exchange material
As explained above, the present lithium-ion-exchange material includes a selective material and a matrix material. It may be provided in various morphologies; for example, it may be formed into beads (for example, substantially spherical beads of average diameter 0.01-10 mm) or, more suitably, into a membrane form.
Such a membrane might be a simple flat (e.g. cast) membrane, or have a more complex structure such as that of a hollow fiber. Hollow fiber membranes have been found by the inventors to have several advantages in DLE processes; in particular, a high useful surface area especially where the feedstock is flown in contact with the lithium-ion-exchange material.
Such hollow fibers are known in the art of water treatment; they are elongate, generally extruded members with a bore (hollow part) inside the substantially circular cross-section fiber.
A hollow fiber morphology of the material may be preferable as a feedstock brought into contact with the fiber has surface contact with a large active area. Hollow fibers can also be packed into a housing to form a membrane module; flow of feedstock through the module again allows high surface contact and hence efficient lithium extraction and release.
Suitable hollow fiber dimensions will be apparent to those skilled in the art. For example, a hollow fiber length of 0.2-2 m, an outer diameter of 0.4-5 mm, and a wall thickness of 10-200 pm may be used.
The hollow fibers themselves may have, for example, a length of about 1 m, an outer diameter of about 1 mm, and an inner (bore) diameter of about 0.9 mm.
Methods of making suitable beads or membranes will be apparent to those of skill in the art. Hollow fiber membranes are used often in water treatment technologies; general methods for their fabrication are also well know.
Extraction step
In the extraction step, the lithium-ion-exchange material is contacted to a lithium-containing solution (feedstock). Suitably this can be done batch-wise or using a continual flow of the lithium-containing solution.
Lithium-containing brines are a typical feedstock for DLE, typically containing from 50 to 4000 ppm lithium content. The brines typically also contain multiple other ionic species including Na+, K+, Ca2+, Mg2+, F’, Cl", Br, SO ', PO -, NO3-, CO3 2-, and HCO3‘.
Other sources of lithium-containing solutions suitable as a feedstock include the product of leeching lithium from solid materials such as lithium-rich ores, lithium-rich recycled material, lithium-containing anodes and the like. This is often done using sulfuric acid, resulting in acidic lithium-containing solutions.
Before use in feedstock solution used in the invention, the feedstock is preferably adjusted to a pH of >7, optionally the pH may be raised yet higher, for example >8, >9, >10 or >11 .
Suitable bases used to adjust the pH of the feedstock solution are not particularly limited as the lithium- ion sieve is highly selective for lithium ions. Suitable bases include NaOH, KOH, NaCO3, KCO3, NaHCO3, KHCO3, NH4OH, ammonium carbonate, ammonium persulfate, ammonia, Ca(OH)2 and Ba(OH)2 (and their associated oxides). In terms of cost, NaOH is preferred.
The extraction step, as well as suitably being conducted at raised pH, may also or instead suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
A temperature of 25-70°C, and particularly 50-70°C, may be preferred,
The length of time for which there is contact between the feedstock and the selective material depends on several factors, for example how the selective material is provided. If it is provided in fibers, or a column,
through which a feedstock is flown, the rate of flow is important. If the selective material is simply placed in contact with a stationary feedstock for some length of time, the time it is left is the relevant feature.
In some embodiments, the extraction step may be conducted for 10-150 minutes.
After a given time, the de-lithiated feedstock is suitably removed from contact with the selective material, and the selective material may be rinsed with fresh water. This can remove any impurities loosely bound to the lithium-ion-exchange material before the release step is carried out.
Release step
In order to release the lithium from the selective material, a protic acidic solution (release solution) is introduced; this replaces the lithium ions with protons. The lithium is released from the selective material, forming a lithium-rich solution which can be removed for further processing. This can be termed a ‘release step’ of the DLE process.
As mentioned above, the present invention uses an organic acid in the release step. Suitable acids include oxalic acid and citric acid. Citric acid is preferable as it is a relatively easily obtainable, low toxicity acid which provides lithium citrate solutions that are readily processed.
On the other hand, oxalic acid may be preferred due to the relatively lower solubility of metal oxalates (especially calcium oxalate, 6.1 mg/L at 20°C, where the precipitant is calcium hydroxide) than of metal citrates (especially calcium citrate, 850 mg/L at 18°C, where the precipitant is calcium hydroxide).
The pH of the release solution (which is generally aqueous) depends of course on the acid included in it and how much is included; generally, it has a pH <7, for example <6, <5, <4, or <3.
In the release step, the lithium-ion exchange material is exposed to a solution of an organic acid. Suitably this can be done batch-wise or using a continual flow of organic acid solution.
The organic acid may be one which comprises a carboxylic acid group. Optionally, the organic acid comprises two or more carboxylic acid groups.
The organic acid is not particularly limited, provided the solubility of its lithium salt is greater than that of another metal salt of the organic acid. Suitable organic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, malic acid, and tartaric acid. Of these, citric and especially oxalic acid are preferable as lithium oxalate is soluble in water whereas other oxalate salts are insoluble in water.
It is also noted by the inventors that calcium is a common impurity in some lithium-containing feedstock solutions; it sometimes is carried through to the release step. Therefore by using a release solution that generates an insoluble calcium salt, such as oxalic acid (calcium oxalate) this impurity can easily be removed in the present process.
The release step may suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
The release step may suitably be conducted at up to 70°C. A temperature above room temperature, for example around 25-70°C, suitably 50-70°C, may be preferred.
Precipitation step
In the precipitation step a precipitant is added to the lithium-enriched release solution in order to perform a double-displacement reaction to liberate lithium hydroxide and precipitate the organic conjugate base anions as an insoluble salt.
Suitably, the precipitant is an alkali (that is, produces an alkali solution upon addition to water; any base that is soluble in water and forms hydroxide ions, or the solution of a base in water). Suitably, the precipitant contains metal cations that form insoluble salts with organic acids such as oxalic acid and citric acid
Suitable precipitants for use in the precipitation step may include alkaline earth metal hydroxides such as Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2, alkaline earth metal oxides (which hydrate to provide alkaline earth metal hydroxides) such as MgO, CaO, SrO and BaO, or an alkali metal hydroxide such as NaOH or KOH.
Clearly the precipitant cannot be a lithium hydroxide or oxide.
In order to minimise cost, the precipitant is preferably Mg(OH)2 or Ca(OH)2, more preferably Ca(OH)2.
When the organic acid is oxalic acid, the precipitant is preferably Ca(OH)2 as the solubility of calcium oxalate is the lowest of alkaline earth oxalates.
In some embodiments, the precipitant is added in the precipitation step as an aqueous solution.
Alternatively the precipitant may be added in the precipitation step as a solid.
The precipitant is added in sufficient volume to cause precipitation of the organic conjugate base anions as an insoluble salt. After the precipitation step is complete, the precipitate may be separated from the supernatant solution by any suitable means, for example, gravity separation, filtration, centrifugation, hydrocyclonic separation and the like.
After the precipitation step is complete, the solution of lithium hydroxide may be subjected to an isolation to produce solid lithium hydroxide.
The lithium hydroxide may be isolated as the monohydrate (LiOH-H2O) or the anhydrate (LiOH) through evaporation of the liquid or by crystallisation. Suitable crystallisation techniques include antisolvent crystallisation wherein lithium hydroxide precipitates from solution upon addition of a suitable organic solvent such as acetone. The antisolvent may then be recovered after separation of the solid lithium hydroxide by, for example, distillation.
***
The features disclosed in the foregoing description, or in the following claims, or in the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function,
or a method or process for obtaining the disclosed results, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.
While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth above are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the spirit and scope of the invention.
For the avoidance of any doubt, any theoretical explanations provided herein are provided for the purposes of improving the understanding of a reader. The inventors do not wish to be bound by any of these theoretical explanations.
Any section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.
Throughout this specification, including the claims which follow, unless the context requires otherwise, the word “comprise” and “include”, and variations such as “comprises”, “comprising”, and “including” will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by the use of the antecedent “about,” it will be understood that the particular value forms another embodiment. The term “about” in relation to a numerical value is optional and means for example +/- 10%.
Claims
1. A method of direct lithium extraction from a lithium-containing feedstock, the method comprising:
(i) an extraction step, in which the lithium-containing feedstock solution is contacted with a lithium-ion-exchange material, whereby the lithium-ion-exchange material is loaded with lithium ions;
(ii) a release step, in which a release solution comprising a protic acid is contacted with the lithium-ion-exchange material, whereby lithium ions are released from the lithium-ion-exchange material into the release solution; and
(iii) a precipitation step, in which a precipitant is mixed with the lithium-enriched release solution; wherein the protic acid is an organic acid; and the precipitant is a non-lithium containing alkali.
2. The method according to claim 1 wherein the release solution comprises oxalic acid and/or citric acid.
3. The method according to claim 2 wherein the release solution is a 0.2 M citric acid solution.
4. The method according to claim 2 wherein the release solution is a 0.2 M oxalic acid solution.
5. The method of any one of the preceding claims wherein the precipitant is calcium hydroxide, magnesium hydroxide, or barium hydroxide.
6. The method of any one of the preceding claims wherein the lithium-ion-exchange material comprises lithium titanium oxide and/or hydrogen titanium oxide derived from lithium titanium oxide.
7. The method according to claim 6 wherein the lithium-ion-exchange material further comprises polyethersulfone.
8. The method of any one of the preceding claims further comprising a washing step after the extraction step and/or a washing step after the release step.
9. The method of any one of the preceding claims wherein the feedstock solution is adjusted to a pH >7 before the extraction step.
10. The method of any one of the preceding claims wherein the extraction step is performed at a temperature from 25 °C to 70 °C.
11. The method of any one of the preceding claims wherein the release step is performed at a temperature from 25 °C to 70 °C.
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