US20220169521A1 - Processing of lithium containing material including hcl sparge - Google Patents
Processing of lithium containing material including hcl sparge Download PDFInfo
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- US20220169521A1 US20220169521A1 US17/671,767 US202217671767A US2022169521A1 US 20220169521 A1 US20220169521 A1 US 20220169521A1 US 202217671767 A US202217671767 A US 202217671767A US 2022169521 A1 US2022169521 A1 US 2022169521A1
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- lithium
- hcl
- leach
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 78
- 230000008569 process Effects 0.000 claims abstract description 73
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 62
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 63
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 229910052643 α-spodumene Inorganic materials 0.000 claims description 12
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 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 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 51
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 34
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 34
- 239000000047 product Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 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
- 230000000694 effects Effects 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 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
- 238000003801 milling Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
-
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- 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 the treatment of lithium containing material.
- the present invention relates to a process for the treatment of a lithium containing material and the production of lithium hydroxide and/or lithium carbonate, wherein an HCl sparge is utilised as an impurity removal step.
- the process utilises the electrolysis of a lithium chloride solution.
- the process of the present invention is intended to provide a high purity or battery grade lithium hydroxide and lithium carbonate product.
- the process of the present invention may further provide a hydrochloric acid product. Further, the process of the present invention, in one form, utilises precious metal containing mixed metal oxide (MMO) electrodes to heighten the efficiency of an electrochemical portion of the process. Still further, the use of the HCl sparge as an impurity removal step is believed to provide benefits when compared with other impurity removal methods.
- MMO mixed metal oxide
- Known processes for the production of lithium carbonate from lithium containing ores or concentrates typically utilise the thermal treatment of an alpha-spodumene ore or concentrate.
- This thermal treatment can be referred as decrepitation and transforms the alpha-spodumene to beta-spodumene which is in turn able to be solubilised by acid.
- the step in which the beta-spodumene is solubilised in acid takes place in a kiln and produces soluble lithium salt.
- the lithium salt is passed to one or more tanks in which the lithium salt is purified. Leached crude lithium salt is subsequently passed to a step in which the pH of the slurry is adjusted, whereby certain impurities, including iron and magnesium are intended to be precipitated.
- purified lithium salt is treated with soda ash to produce lithium carbonate.
- This lithium carbonate can be further treated with hydrated lime to produce lithium hydroxide.
- Processes for the production of lithium carbonate and lithium hydroxide from brines typically involves the use of evaporation ponds to increase the concentration of the salts contained therein before being passed to a series of steps aimed to reduce the impurities present.
- the Applicant has previously developed a process for the production of lithium hydroxide and lithium carbonate as described in International Patent Application PCT/AU2013/000857 (WO 2014/026217). Whilst being beneficial when compared with the prior art, the process described therein utilises a concentration step and a fractional crystallisation step for the removal of sodium and potassium impurities, prior to a further ion exchange step for the removal of remaining multivalent cations.
- the concentration step is problematic, utilising a solvent extraction method, using isopropanol to extract lithium chloride, leaving sodium and potassium behind to be filtered out. The isopropanol then needs to be distilled off, leaving a substantially pure 99.9% lithium chloride solution. Such a concentration step suffers from the relatively high cost of reagents and their flammability.
- the process of the present invention has as one object thereof to overcome substantially one or more of the above mentioned problems associated with prior art processes, including those of the Applicant, or to at least provide a useful alternative thereto.
- battery grade lithium carbonate refers to a product having a purity of about 99.5% or higher.
- battery grade lithium hydroxide refers to a product having a purity of about 99% or higher.
- the lithium hydroxide solution produced in step (iii) is carbonated by passing compressed carbon dioxide through the solution, thereby producing a lithium carbonate precipitate.
- the process solution of step (i) is prepared in the form of a pregnant leach solution.
- the pregnant leach solution is formed by passing a lithium containing material to a leach step in which the material is leached with hydrochloric acid.
- the lithium containing material is an alpha-spodumene ore or ore concentrate and the process further comprises a first step in which that alpha-spodumene ore or ore concentrate is calcined to produce beta-spodumene.
- the HCl sparging step of step (ii) comprises the sparging of HCl gas into the process solution whereby the HCl concentration thereof increases to a point at which a substantial proportion of any sodium and potassium present precipitates.
- the HCl concentration of the process solution is preferably increased to at least about 30% w/w, still preferably to at least about 36% w/w.
- the HCl sparging step is followed by a filtration step to remove the precipitated sodium and potassium, preferably in the form of a precipitated salt.
- the HCl sparging and filtration steps are followed by an HCl recovery step.
- the HCl recovery step may be provided in the form of a distillation.
- the lithium hydroxide solution produced in step (iii) may be thickened by evaporation of water to provide lithium hydroxide monohydrate crystals.
- a first portion of the lithium hydroxide solution produced in step (iii) is thickened by evaporation/crystallisation to provide lithium hydroxide monohydrate crystals and a second portion thereof is carbonated by passing compressed carbon dioxide through the solution, thereby producing a lithium carbonate precipitate.
- the impurity removal steps of step (ii) further include one or more of hyrdropyrolysis of Al and Fe chlorides, pH increase to precipitate hydroxides of Al, Fe, Mg and Mn, and lithium carbonate precipitation for removal of Ca.
- the impurity removal steps preferably further comprises an ion exchange step.
- the ion exchange step removes substantially all calcium, magnesium and other multivalent cations remaining in the pregnant leach solution. Still preferably, such multivalent cations are removed to a level of less than about 10 ppm.
- the beta-spodumene is cooled and milled prior to the leach step.
- the beta-spodumene is preferably milled to less than about 300 ⁇ m. Still preferably, the beta-spodumene is milled to a P 80 of about 75 ⁇ m.
- the leach step is conducted at elevated temperature.
- the hydrochloric acid solution used in the leach step is preferably about 20% HCl w/w.
- the elevated temperature of the leach step is about the boiling point of the hydrochloric acid solution used in the leach step.
- the leach step is preferably conducted at atmospheric pressure.
- the leach step is conducted in a chlorination kiln at about 108° C. over a residence time of about 6 to 10 hours.
- the residence time is about 8 hours.
- FIG. 1 is a schematic flow-sheet depicting a process for the treatment of a lithium containing material in accordance with a first embodiment of the present invention in which the lithium containing material is an alpha-spodumene concentrate;
- FIG. 2 is a graph representing the precipitation of NaCl from a LiCl solution in an HCl sparging step as used in the process of the present invention and depicted in FIG. 1 .
- FIG. 1 there is shown a process 10 for the treatment of a lithium containing material in accordance with a first embodiment of the present invention in which embodiment the lithium containing material is provided in the form of an alpha-spodumene concentrate.
- An alpha-spodumene concentrate 12 is passed to a calcining step in which the concentrate 12 is calcined in a calcining furnace 14 at a temperature of between about 1050° C. to 1100° C., for about 0.5 hours, to convert the alpha-spodumene to leachable beta-spodumene.
- Off-gases from the calciner are directed through a cyclone (not shown) and an electrostatic precipitator (not shown) specified to comply with known environmental emissions limits.
- the resulting hot calcine is passed to a cooler 16 and indirectly cooled to about 80° C. It is then dry-milled to less than 300 ⁇ m, for example to a P 80 of about 212 ⁇ m, in a mill, for example a closed circuit ball mill 18 .
- the milled beta-spodumene is mixed with at least a 40 to 300% stoichiometric excess of 20% w/w hydrochloric acid 20 in a slurrying step.
- the slurrying step feeds a leach step, for example a leach circuit 22 , comprising a first leach stage 24 and a second leach stage 26 .
- the leach step is conducted at about 106° C., being the boiling point of the hydrochloric acid leach solution added in the slurrying step, for a period of about 6 to 12 hours, for example about 8 hours, in continuous leach tanks.
- a pulp density of about 40% is used in the leach circuit 22 to maximise the leach concentration and to ensure that the solubility limit of lithium chloride during leaching is not exceeded.
- Off-gases are cleaned in a wet scrubber (not shown).
- the leach step 22 produces a residue slurry and a process solution, for example a pregnant leach solution.
- the lithium and the aluminosilicate in the beta-spodumene leaches into solution with other impurities to give a sub-saturated concentration of lithium chloride in the pregnant leach liquor.
- the pregnant leach solution from the leach circuit 22 is passed to a thickening circuit 28 , preferably comprising two stages 28 a and 28 b aligned with the stages 24 and 26 of the leach circuit 22 .
- An overflow from the thickening circuit 28 is directed to a belt filter 28 c and in turn the pregnant leach solution is directed first to distillation step 29 , in which excess HCl is recovered, and second to a pyrohydrolysis step 30 , operating at about 300° C., and in which chlorides of Al and Fe present in the pregnant leach solution, for example AlCl 3 .6H 2 O and FeCl 3 .6H 2 O, are converted into their respective insoluble oxides 32 . Any residual HCl is also recovered from pyrohydrolysis to a HCl tank 34 .
- impurity removal steps 36 further include a pH modification step 38 through the addition of LiOH 40 to raise the pH to about 9.
- the product of step 38 is passed to a belt filter 42 from which Al, Fe, Mn and Mg containing precipitates 43 are recovered.
- the impurity removal steps 36 further include a calcium precipitation step 44 with the addition of either sodium carbonate (soda ash) or lithium carbonate 46 and oxalate, producing a magnesium, manganese and/or calcium containing precipitate 48 from a further belt filter 50 .
- a thickener underflow product 52 of the second thickening step 28 b is passed to a drying step 54 before passing to waste 56 and subsequent disposal.
- the liquid product of the belt filter 50 is passed to an HCl sparging step 58 in which HCl gas 60 is sparged into the LiCl solution.
- HCl gas 60 is sparged into the LiCl solution.
- this sparging with HCl gas allows an HCl concentration of greater than 30% w/w, for example 36% w/w, to be achieved.
- any NaCl and/or KCl present have near zero solubility, allowing such to be removed in a filtration step, utilising for example a belt filter 62 .
- the liquid product of the belt filter 56 is in turn passed to a distillation step 64 for the recovery of HCl gas 65 through distillation at about 106° C.
- the distillation step 64 provides pure LiCl crystals 66 that are in turn dissolved in water to provide a LiCl solution 67 having a LiCl concentration of about 35% w/w.
- the lithium chloride solution 67 is passed through an ion exchange step 68 , comprising an Ion Exchange (IX) column by which substantially all of any residual calcium, manganese, magnesium and other multivalent cations are removed to a level of less than about 10 ppm, for example 1 ppm.
- IX Ion Exchange
- the further purified lithium chloride solution is first stored 69 and then heated to 90° C. and pumped to an electrolysis step 70 comprising a number of electrolysers, for example 6 to 20 electrolysers, in which lithium chloride and water are consumed to produce lithium hydroxide, chlorine and hydrogen.
- the weak or depleted lithium chloride solution contains dissolved chlorine gas.
- the dissolved chlorine is removed in two stages. In a first stage hydrochloric acid is added to the lithium chloride solution to reduce the pH to ⁇ 5 which forces some of the chlorine gas out of solution. The remaining dissolved chlorine gas is then removed by air stripping the solution (not shown).
- Chlorine and hydrogen produced as by-products of the electrolysis step 70 are combined to produce HCl acid which is used in the slurrying step and leaching circuit 22 , as is recovered HCl from distillation step 29 , pyrohydrolysis step 30 and the distillation step 64 .
- This recycle stream is shown as recycle 71 in FIG. 1 .
- the lithium hydroxide solution obtained from the electrolysis step 70 is passed firstly to a holding tank 72 , from which it can either be (i) evaporated and crystallised to produce lithium hydroxide monohydrate crystals, or (ii) sent to carbonation step to convert into lithium carbonate, as clearly shown in FIG. 1 .
- the lithium hydroxide in solution is crystallised in, for example, a vacuum evaporative crystalliser 80 (Oslo type) operating at a temperature of about 80° C. and pressure of about 45 kPa(a).
- the residence time is about 60 minutes so as to achieve a coarse crystal product.
- the resulting water vapour is recompressed, combined with make-up steam and used as the heating medium for the crystalliser 80 .
- Lithium hydroxide crystals are washed by cold water (not shown) achieving a wash efficiency of 99%.
- the resulting wash solution is recycled back to the leach circuit 22 as noted above.
- Solids from the centrifuge are fed to an indirect-fired kiln or dryer 82 , operating at about 120° C., which dries the crystals.
- the crystal product being battery grade LiOH.H 2 O, is pneumatically conveyed to product bins 84 , and cooled to 50° C. in a jacketed screw conveyer 86 as it is conveyed ultimately to bagging stations (not shown).
- lithium carbonate may be produced by carbonation of lithium hydroxide solution by passing compressed carbon dioxide gas 88 though the solution of lithium hydroxide in a carbonation vessel 90 in which lithium carbonate is precipitated.
- This slurry is fed to a washer/centrifuge 92 by way of a filter 94 , after which wash water is recycled with any remaining lithium hydroxide solution or mother liquor to electrolysis 70 .
- Wet lithium carbonate crystals are fed to a dryer 96 in which hot air is used to dry the crystals. Medium pressure air is used to heat the air. After drying the battery grade lithium carbonate may be micronized to a particle size requested by a customer prior to passing to storage bins 98 and subsequent bagging (not shown).
- Condensate throughout the process is used as make-up water for hot process water, cold process water and cooling water. As the process does not return condensate there is an overall positive water balance and about 1/10 th of the process water is discharged to a sewerage system (not shown).
- tantalite and alumina may also be recovered using the process of the present invention.
- the filter cake from the thickening step may be discharged to a tantalite recovery plant (not shown). Discharge from the tantalite recovery plant may be fed onto a belt filter to remove water, which is returned to the tantalite recovery plant.
- the filter does not use washing and has a filtration are of 19 m 2 .
- the filter cake from the belt filter is dried in a direct-fired kiln.
- the dry alumina silicate is cooled to 50° C. in a jacketed screw conveyor and then pneumatically conveyed to a storage bin prior to dispatch.
- the lithium containing material may be provided in the form of a lithium containing brine.
- Brines do not require the calcining, cooling, milling and leach steps as described for the first embodiment of the present invention but it is envisaged that the remainder of the process will be substantially similar to that of the first embodiment described above.
- HCl sparging step 58 sufficient HCl gas was sparged into a 20% solution of LiCl having the above composition such that the HCl concentration achieved 36% w/w. This was operated over several temperatures ranging from 20° C. (room temperature) to 60° C. No change in precipitation pattern was noted over this temperature range.
- the process of the present invention provides a process by which a high purity or battery grade lithium hydroxide and lithium carbonate products may be obtained from an alpha-spodumene ore or concentrate, or from a lithium containing brine, whilst also allowing the production of a hydrogen chloride gas product.
- the process of the present invention overcomes the need for a concentration step and a fractional crystallisation step for the removal of sodium and potassium impurities, prior to the ion exchange step for the removal of remaining multivalent cations.
- the concentration step of the prior art is significantly problematic, utilising a solvent extraction method, using isopropanol to extract lithium chloride, leaving sodium and potassium behind to be filtered out.
- the isopropanol then needs to be distilled off, leaving a substantially pure 99.9% lithium chloride solution.
- Such a concentration step suffers from the relatively high cost of reagents and from their flammability.
- the on-going operation cost of the HCl sparge utilised in the present invention is, as a hydrometallurgical unit operation, lower than that of the prior art method utilising isopropanol.
- the recovery of HCl acid in the process of the present invention is ideally greater than 99% whilst the recovery of isopropanol in the prior art method is at best 95%.
- the leach circuit 22 may comprise only a single leach stage/operation without departing from the scope of the present invention.
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Abstract
Description
- This application/patent is a continuation application of co-pending U.S. patent application Ser. No. 15/546,560, filed on Jul. 26, 2017, and entitled “PROCESSING OF LITHIUM CONTAINING MATERIAL INCLUDING HCL SPARGE,” which is a U.S. national stage entry under 35 U.S.C. 371 of International Application No. PCT/AU2015/000650 filed on Oct. 30, 2015, which claims priority to Australian Patent Application No. 201590022 filed on Jan. 27, 2015, the contents of which are incorporated herein by reference in their entireties.
- The present invention relates to the treatment of lithium containing material.
- More particularly, the present invention relates to a process for the treatment of a lithium containing material and the production of lithium hydroxide and/or lithium carbonate, wherein an HCl sparge is utilised as an impurity removal step. The process utilises the electrolysis of a lithium chloride solution. In one form, the process of the present invention is intended to provide a high purity or battery grade lithium hydroxide and lithium carbonate product.
- The process of the present invention may further provide a hydrochloric acid product. Further, the process of the present invention, in one form, utilises precious metal containing mixed metal oxide (MMO) electrodes to heighten the efficiency of an electrochemical portion of the process. Still further, the use of the HCl sparge as an impurity removal step is believed to provide benefits when compared with other impurity removal methods.
- Known processes for the production of lithium carbonate from lithium containing ores or concentrates typically utilise the thermal treatment of an alpha-spodumene ore or concentrate. This thermal treatment can be referred as decrepitation and transforms the alpha-spodumene to beta-spodumene which is in turn able to be solubilised by acid. The step in which the beta-spodumene is solubilised in acid takes place in a kiln and produces soluble lithium salt. The lithium salt is passed to one or more tanks in which the lithium salt is purified. Leached crude lithium salt is subsequently passed to a step in which the pH of the slurry is adjusted, whereby certain impurities, including iron and magnesium are intended to be precipitated. Thus purified lithium salt is treated with soda ash to produce lithium carbonate. This lithium carbonate can be further treated with hydrated lime to produce lithium hydroxide.
- Processes for the production of lithium carbonate and lithium hydroxide from brines typically involves the use of evaporation ponds to increase the concentration of the salts contained therein before being passed to a series of steps aimed to reduce the impurities present.
- The above described processes of the prior art are relatively inefficient in the removal of impurities remaining in the pregnant leach solution, which results in a relatively impure lithium hydroxide and lithium carbonate product. This is particularly problematic when attempting to produce high quality or battery grade lithium hydroxide and lithium carbonate products.
- The Applicant has previously developed a process for the production of lithium hydroxide and lithium carbonate as described in International Patent Application PCT/AU2013/000857 (WO 2014/026217). Whilst being beneficial when compared with the prior art, the process described therein utilises a concentration step and a fractional crystallisation step for the removal of sodium and potassium impurities, prior to a further ion exchange step for the removal of remaining multivalent cations. The concentration step is problematic, utilising a solvent extraction method, using isopropanol to extract lithium chloride, leaving sodium and potassium behind to be filtered out. The isopropanol then needs to be distilled off, leaving a substantially pure 99.9% lithium chloride solution. Such a concentration step suffers from the relatively high cost of reagents and their flammability.
- The process of the present invention has as one object thereof to overcome substantially one or more of the above mentioned problems associated with prior art processes, including those of the Applicant, or to at least provide a useful alternative thereto.
- The preceding discussion of the background art is intended to facilitate an understanding of the present invention only. This discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application.
- Throughout the specification and claims, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
- The term “battery grade lithium carbonate” refers to a product having a purity of about 99.5% or higher. Similarly, the term “battery grade lithium hydroxide” refers to a product having a purity of about 99% or higher.
- In accordance with the present invention there is provided a process for the treatment of a lithium containing material, the process comprising the steps of:
-
- (i) Preparing a process solution from the lithium containing material;
- (ii) Passing the process solution from step (i) to a series of impurity removal steps, one of which is an HCl sparging step, thereby providing a substantially purified lithium chloride solution; and
- (iii) Passing the purified lithium chloride solution of step (ii) to an electrolysis step thereby producing a lithium hydroxide solution,
- wherein the process solution is not subjected to a concentration step prior to the series of impurity removal steps of step (ii).
- In one form of the present invention, the lithium hydroxide solution produced in step (iii) is carbonated by passing compressed carbon dioxide through the solution, thereby producing a lithium carbonate precipitate.
- Preferably, the process solution of step (i) is prepared in the form of a pregnant leach solution. Still preferably, the pregnant leach solution is formed by passing a lithium containing material to a leach step in which the material is leached with hydrochloric acid.
- In a further form, the lithium containing material is an alpha-spodumene ore or ore concentrate and the process further comprises a first step in which that alpha-spodumene ore or ore concentrate is calcined to produce beta-spodumene.
- Preferably, the HCl sparging step of step (ii) comprises the sparging of HCl gas into the process solution whereby the HCl concentration thereof increases to a point at which a substantial proportion of any sodium and potassium present precipitates. The HCl concentration of the process solution is preferably increased to at least about 30% w/w, still preferably to at least about 36% w/w.
- Still preferably, the HCl sparging step is followed by a filtration step to remove the precipitated sodium and potassium, preferably in the form of a precipitated salt.
- Still further preferably, the HCl sparging and filtration steps are followed by an HCl recovery step. The HCl recovery step may be provided in the form of a distillation.
- The lithium hydroxide solution produced in step (iii) may be thickened by evaporation of water to provide lithium hydroxide monohydrate crystals.
- In a still further form of the present invention a first portion of the lithium hydroxide solution produced in step (iii) is thickened by evaporation/crystallisation to provide lithium hydroxide monohydrate crystals and a second portion thereof is carbonated by passing compressed carbon dioxide through the solution, thereby producing a lithium carbonate precipitate.
- Preferably, the impurity removal steps of step (ii) further include one or more of hyrdropyrolysis of Al and Fe chlorides, pH increase to precipitate hydroxides of Al, Fe, Mg and Mn, and lithium carbonate precipitation for removal of Ca.
- The impurity removal steps preferably further comprises an ion exchange step. Preferably, the ion exchange step removes substantially all calcium, magnesium and other multivalent cations remaining in the pregnant leach solution. Still preferably, such multivalent cations are removed to a level of less than about 10 ppm.
- Preferably, the beta-spodumene is cooled and milled prior to the leach step. The beta-spodumene is preferably milled to less than about 300 μm. Still preferably, the beta-spodumene is milled to a P80 of about 75 μm.
- Preferably, the leach step is conducted at elevated temperature.
- The hydrochloric acid solution used in the leach step is preferably about 20% HCl w/w.
- Still preferably, the elevated temperature of the leach step is about the boiling point of the hydrochloric acid solution used in the leach step.
- The leach step is preferably conducted at atmospheric pressure.
- In one form of the present invention the leach step is conducted in a chlorination kiln at about 108° C. over a residence time of about 6 to 10 hours. Preferably, the residence time is about 8 hours.
- The process of the present invention will now be described, by way of example only, with reference to one embodiment thereof and the accompanying drawing, in which:—
-
FIG. 1 is a schematic flow-sheet depicting a process for the treatment of a lithium containing material in accordance with a first embodiment of the present invention in which the lithium containing material is an alpha-spodumene concentrate; and -
FIG. 2 is a graph representing the precipitation of NaCl from a LiCl solution in an HCl sparging step as used in the process of the present invention and depicted inFIG. 1 . - In
FIG. 1 there is shown aprocess 10 for the treatment of a lithium containing material in accordance with a first embodiment of the present invention in which embodiment the lithium containing material is provided in the form of an alpha-spodumene concentrate. - All of the unit operations embodied in the
process 10 are intended to operate continuously with full process instrumentation and control being provided for. - An alpha-
spodumene concentrate 12 is passed to a calcining step in which theconcentrate 12 is calcined in a calcining furnace 14 at a temperature of between about 1050° C. to 1100° C., for about 0.5 hours, to convert the alpha-spodumene to leachable beta-spodumene. Off-gases from the calciner are directed through a cyclone (not shown) and an electrostatic precipitator (not shown) specified to comply with known environmental emissions limits. The resulting hot calcine is passed to a cooler 16 and indirectly cooled to about 80° C. It is then dry-milled to less than 300 μm, for example to a P80 of about 212 μm, in a mill, for example a closed circuit ball mill 18. - After storage in a surge bin (not shown), the milled beta-spodumene is mixed with at least a 40 to 300% stoichiometric excess of 20% w/
w hydrochloric acid 20 in a slurrying step. The slurrying step feeds a leach step, for example aleach circuit 22, comprising a first leach stage 24 and asecond leach stage 26. - The leach step is conducted at about 106° C., being the boiling point of the hydrochloric acid leach solution added in the slurrying step, for a period of about 6 to 12 hours, for example about 8 hours, in continuous leach tanks. A pulp density of about 40% is used in the
leach circuit 22 to maximise the leach concentration and to ensure that the solubility limit of lithium chloride during leaching is not exceeded. Off-gases are cleaned in a wet scrubber (not shown). Theleach step 22 produces a residue slurry and a process solution, for example a pregnant leach solution. The lithium and the aluminosilicate in the beta-spodumene leaches into solution with other impurities to give a sub-saturated concentration of lithium chloride in the pregnant leach liquor. - The pregnant leach solution from the
leach circuit 22 is passed to a thickeningcircuit 28, preferably comprising two stages 28 a and 28 b aligned with thestages 24 and 26 of theleach circuit 22. An overflow from the thickeningcircuit 28 is directed to a belt filter 28 c and in turn the pregnant leach solution is directed first todistillation step 29, in which excess HCl is recovered, and second to apyrohydrolysis step 30, operating at about 300° C., and in which chlorides of Al and Fe present in the pregnant leach solution, for example AlCl3.6H2O and FeCl3.6H2O, are converted into their respective insoluble oxides 32. Any residual HCl is also recovered from pyrohydrolysis to a HCl tank 34. - In addition to the Al and Fe described immediately above as being recovered using the
pyrohydrolysis step 30, remaining soluble iron, aluminium and magnesium are removed in large part from the leach liquor through a series of impurity removal steps, indicated in a broad sense by impurity removal steps 36 inFIG. 1 . The impurity removal steps 36 further include apH modification step 38 through the addition ofLiOH 40 to raise the pH to about 9. The product ofstep 38 is passed to a belt filter 42 from which Al, Fe, Mn and Mg containing precipitates 43 are recovered. The impurity removal steps 36 further include a calcium precipitation step 44 with the addition of either sodium carbonate (soda ash) orlithium carbonate 46 and oxalate, producing a magnesium, manganese and/or calcium containing precipitate 48 from a further belt filter 50. - A thickener underflow product 52 of the second thickening step 28 b is passed to a drying step 54 before passing to waste 56 and subsequent disposal.
- The liquid product of the belt filter 50, being largely LiCl solution having as its major contaminants sodium and potassium, is passed to an HCl sparging step 58 in which
HCl gas 60 is sparged into the LiCl solution. By way of the ‘common ion effect’ this sparging with HCl gas allows an HCl concentration of greater than 30% w/w, for example 36% w/w, to be achieved. At this concentration of HCl any NaCl and/or KCl present have near zero solubility, allowing such to be removed in a filtration step, utilising for example a belt filter 62. - The liquid product of the
belt filter 56 is in turn passed to a distillation step 64 for the recovery of HCl gas 65 through distillation at about 106° C. The distillation step 64 provides pure LiCl crystals 66 that are in turn dissolved in water to provide a LiCl solution 67 having a LiCl concentration of about 35% w/w. - After the removal of substantially all impurities as described above, the lithium chloride solution 67 is passed through an ion exchange step 68, comprising an Ion Exchange (IX) column by which substantially all of any residual calcium, manganese, magnesium and other multivalent cations are removed to a level of less than about 10 ppm, for example 1 ppm.
- The further purified lithium chloride solution is first stored 69 and then heated to 90° C. and pumped to an electrolysis step 70 comprising a number of electrolysers, for example 6 to 20 electrolysers, in which lithium chloride and water are consumed to produce lithium hydroxide, chlorine and hydrogen.
- After passing through the electrolysers, the weak or depleted lithium chloride solution contains dissolved chlorine gas. Before this weak lithium chloride solution is recycled to the slurrying step immediately prior to the
leach circuit 22, the dissolved chlorine is removed in two stages. In a first stage hydrochloric acid is added to the lithium chloride solution to reduce the pH to <5 which forces some of the chlorine gas out of solution. The remaining dissolved chlorine gas is then removed by air stripping the solution (not shown). - Chlorine and hydrogen produced as by-products of the electrolysis step 70 are combined to produce HCl acid which is used in the slurrying step and leaching
circuit 22, as is recovered HCl fromdistillation step 29,pyrohydrolysis step 30 and the distillation step 64. This recycle stream is shown as recycle 71 inFIG. 1 . - The lithium hydroxide solution obtained from the electrolysis step 70 is passed firstly to a
holding tank 72, from which it can either be (i) evaporated and crystallised to produce lithium hydroxide monohydrate crystals, or (ii) sent to carbonation step to convert into lithium carbonate, as clearly shown inFIG. 1 . - In the first of these options, the lithium hydroxide in solution is crystallised in, for example, a vacuum evaporative crystalliser 80 (Oslo type) operating at a temperature of about 80° C. and pressure of about 45 kPa(a). The residence time is about 60 minutes so as to achieve a coarse crystal product. The resulting water vapour is recompressed, combined with make-up steam and used as the heating medium for the
crystalliser 80. - Lithium hydroxide crystals are washed by cold water (not shown) achieving a wash efficiency of 99%. The resulting wash solution is recycled back to the
leach circuit 22 as noted above. Solids from the centrifuge are fed to an indirect-fired kiln ordryer 82, operating at about 120° C., which dries the crystals. The crystal product, being battery grade LiOH.H2O, is pneumatically conveyed to product bins 84, and cooled to 50° C. in a jacketed screw conveyer 86 as it is conveyed ultimately to bagging stations (not shown). - In the second option noted above, lithium carbonate may be produced by carbonation of lithium hydroxide solution by passing compressed
carbon dioxide gas 88 though the solution of lithium hydroxide in acarbonation vessel 90 in which lithium carbonate is precipitated. This slurry is fed to a washer/centrifuge 92 by way of a filter 94, after which wash water is recycled with any remaining lithium hydroxide solution or mother liquor to electrolysis 70. Wet lithium carbonate crystals are fed to a dryer 96 in which hot air is used to dry the crystals. Medium pressure air is used to heat the air. After drying the battery grade lithium carbonate may be micronized to a particle size requested by a customer prior to passing to storage bins 98 and subsequent bagging (not shown). - Condensate throughout the process is used as make-up water for hot process water, cold process water and cooling water. As the process does not return condensate there is an overall positive water balance and about 1/10th of the process water is discharged to a sewerage system (not shown).
- It is envisaged that tantalite and alumina may also be recovered using the process of the present invention. The filter cake from the thickening step may be discharged to a tantalite recovery plant (not shown). Discharge from the tantalite recovery plant may be fed onto a belt filter to remove water, which is returned to the tantalite recovery plant. The filter does not use washing and has a filtration are of 19 m2. The filter cake from the belt filter is dried in a direct-fired kiln. The dry alumina silicate is cooled to 50° C. in a jacketed screw conveyor and then pneumatically conveyed to a storage bin prior to dispatch.
- In accordance with a second embodiment of the present invention the lithium containing material may be provided in the form of a lithium containing brine. Brines do not require the calcining, cooling, milling and leach steps as described for the first embodiment of the present invention but it is envisaged that the remainder of the process will be substantially similar to that of the first embodiment described above.
- The process of the present invention may be better understood with reference to the following non-limited example.
- The
process 10 for the treatment of a lithium containing material as described above in accordance with the first embodiment of the present invention, in which the lithium containing material is an alpha-spodumene concentrate, was operated such that immediately prior to the HCl sparging step 58 the LiCl solution had the composition set out in Table 1 below: -
TABLE 1 AlCl3 CaCl2 FeCl3 KCl LiCl MgCl2 MnCl2 NaCl % w/w mg/L mg/L mg/L mg/L mg/L mg/L mg/L 0.00 0.00 0.00 0.47 19.67 0.00 0.00 1.01 - In the HCl sparging step 58 sufficient HCl gas was sparged into a 20% solution of LiCl having the above composition such that the HCl concentration achieved 36% w/w. This was operated over several temperatures ranging from 20° C. (room temperature) to 60° C. No change in precipitation pattern was noted over this temperature range.
- The results of the HCl sparging step 58 are presented in
FIG. 2 . It is evident from the results that >92% NaCl was precipitated and removed from the LiCl solution. At the same time, no discernible LiCl was precipitated. Also apparent was the inability to precipitate KCl at the given HCl acid sparge conditions and at room temperature. The Applicants expect it will be required to conduct similar testing at lower temperatures, such as close to 0° C. to remove KCl from the LiCl solution. The solubility of KCl decreases tremendously at lower temperatures in presence of HCl acid at 36% w/w strength, and hence it believed to be possible to remove all KCl at lower temperature, such as at or about 0° C. - As can be seen from the above, the process of the present invention provides a process by which a high purity or battery grade lithium hydroxide and lithium carbonate products may be obtained from an alpha-spodumene ore or concentrate, or from a lithium containing brine, whilst also allowing the production of a hydrogen chloride gas product. Further, the process of the present invention overcomes the need for a concentration step and a fractional crystallisation step for the removal of sodium and potassium impurities, prior to the ion exchange step for the removal of remaining multivalent cations. As described hereinabove, the concentration step of the prior art is significantly problematic, utilising a solvent extraction method, using isopropanol to extract lithium chloride, leaving sodium and potassium behind to be filtered out. The isopropanol then needs to be distilled off, leaving a substantially pure 99.9% lithium chloride solution. Such a concentration step suffers from the relatively high cost of reagents and from their flammability. The on-going operation cost of the HCl sparge utilised in the present invention is, as a hydrometallurgical unit operation, lower than that of the prior art method utilising isopropanol. The recovery of HCl acid in the process of the present invention is ideally greater than 99% whilst the recovery of isopropanol in the prior art method is at best 95%.
- Modifications and variations such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention. For example, it is envisaged that the
leach circuit 22 may comprise only a single leach stage/operation without departing from the scope of the present invention.
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WO2018089932A1 (en) | 2016-11-14 | 2018-05-17 | Lilac Solutions, Inc. | Lithium extraction with coated ion exchange particles |
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CA2974666A1 (en) | 2016-08-04 |
US11286170B2 (en) | 2022-03-29 |
AR100672A1 (en) | 2016-10-26 |
US20180016153A1 (en) | 2018-01-18 |
MX2017009578A (en) | 2018-01-23 |
AU2015380289A1 (en) | 2017-08-10 |
CL2017001910A1 (en) | 2018-04-27 |
CA2974666C (en) | 2023-02-28 |
KR102545219B1 (en) | 2023-06-19 |
MY195100A (en) | 2023-01-10 |
CN107454916A (en) | 2017-12-08 |
AU2015380289B2 (en) | 2020-12-17 |
EP3250720A1 (en) | 2017-12-06 |
EP3250720A4 (en) | 2018-08-01 |
KR20170107546A (en) | 2017-09-25 |
CN115323196A (en) | 2022-11-11 |
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JP6889115B2 (en) | 2021-06-18 |
WO2016119003A1 (en) | 2016-08-04 |
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