WO2022241518A1 - Cellule d'électrodialyse - Google Patents
Cellule d'électrodialyse Download PDFInfo
- Publication number
- WO2022241518A1 WO2022241518A1 PCT/AU2022/050484 AU2022050484W WO2022241518A1 WO 2022241518 A1 WO2022241518 A1 WO 2022241518A1 AU 2022050484 W AU2022050484 W AU 2022050484W WO 2022241518 A1 WO2022241518 A1 WO 2022241518A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- anodic
- cathodic
- fluid distribution
- compartment
- Prior art date
Links
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 89
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 62
- 239000012530 fluid Substances 0.000 claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000009826 distribution Methods 0.000 claims abstract description 53
- 239000012528 membrane Substances 0.000 claims abstract description 38
- 125000006850 spacer group Chemical group 0.000 claims abstract description 34
- 238000005341 cation exchange Methods 0.000 claims abstract description 27
- -1 lithium cations Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000013508 migration Methods 0.000 claims abstract description 8
- 230000005012 migration Effects 0.000 claims abstract description 8
- 238000004891 communication Methods 0.000 claims description 4
- 210000004027 cell Anatomy 0.000 description 49
- 239000000243 solution Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003010 cation ion exchange membrane Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- 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 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/50—Stacks of the plate-and-frame type
-
- 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
- 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
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
Definitions
- the present disclosure relates to an electrodialysis cell, in particular an electrodialysis cell for producing lithium hydroxide from a lithium-bearing solution.
- Lithium hydroxide is generally produced via an aqueous causticisation reaction between lithium carbonate (U2CO3) and slaked lime (Ca(OH) 2 ). It is subsequently recovered as a monohydrate salt via evaporative crystallization as a final product.
- U2CO3 lithium carbonate
- Ca(OH) 2 slaked lime
- a multi-compartment electrodialysis (ED) cell having alternating cation and anion exchange membranes has become a standard configuration for such processes.
- the ED cell consists of stacks of flat, rectangular membranes and flow channels sandwiched between two or more electrodes.
- the membrane stack may be oriented in either a horizontal or vertical position.
- the flow channels may be created by spacers (i.e. electrically inert plastic separators) interposed between the membranes.
- the spacers support the stack and determine the geometry of the flow channel defined between the membranes.
- Spacers are an important cell component that affects cell performance.
- a well performing spacer provides a small inter-electrode distance, adequate means for maintaining the dimensions of the cell, uniform fluid distribution and promotion of efficient mass transport.
- Tortuous spacers provide long flow channels which enable a single-pass flow to be achieved. This avoids the need to apply series of stacks which would result in higher pressure drop across the stacks, constructional difficulty due to multistage arrangement, lower reliability of the system caused by inlet pressure differences of feed and product at the stages, and possible internal leakages.
- the spacer should promote turbulent solution flow.
- Solution flowing through the channel filled by the sheet spacer may follow a so called zig-zag flow pattern.
- This flow pattern increases the mass transfer coefficients from the solution bulk to the membrane surface and reduces a concentration polarization phenomena occurring in the diffusion layer at the membrane surface.
- a highly knitted and low porosity spacer may have a significant effect on the stack resistance, also known as a spacer shadow effect. This is likewise the case for a spacer with a large thickness.
- the assembly of electrodes, membranes and spacers is generally held in compression by a pair of end plates, thereby preventing leakage inside the stack. Additional stacks may be added in series to achieve the desired electrodialysis performance.
- the assembly may be readily disassembled for cleaning and maintenance.
- the present disclosure provides an electrodialysis cell, in particular an electrodialysis cell for producing lithium hydroxide from a lithium-bearing solution.
- an electrodialysis cell for producing lithium hydroxide from a lithium-bearing solution
- the electrodialysis cell comprising: an anodic compartment and a cathodic compartment separated by a cation exchange membrane configured, in use, to allow migration of lithium cations therethrough from the anodic compartment to the cathodic compartment;
- the anodic compartment comprising an anode and a first fluid distribution member having an inlet to receive a feedstream of a lithium-bearing solution into the anodic compartment and an outlet to remove a lithium-depleted solution therefrom;
- the cathodic compartment comprising a cathode and a second fluid distribution member having an inlet to receive a lithium hydroxide solution into the cathodic compartment and an outlet to remove a lithium-enriched hydroxide solution therefrom;
- the first and second fluid distribution members being interposed between the cation exchange membrane and said respective anode and cathode, wherein said fluid distribution members comprise a frame configured to support
- the respective inlets and outlets of the first and second fluid distribution members comprise passages through the frames thereof.
- the one or more permeable spacer sheets are disposed at or proximal to a side of the frame adjacent to the cation exchange membrane.
- a respective gasket is interposed between:
- a respective gasket may be interposed between the anode and one of the end plates, and the cathode and the other of the end plates.
- the opposing end plates are provided with correspondingly aligned apertures to receive fasteners therethrough.
- the cathode and the anode are provided with respective tabs configured, in use, to be electrically coupled to an electric current supply.
- an assembly of electrodialysis cells for producing lithium hydroxide from a lithium-bearing solution comprising: a plurality of alternately arranged anodic and cathodic compartments separated by respective cation exchange membranes configured, in use, to allow migration of lithium cations therethrough from the anodic compartments to the cathodic compartments; each anodic compartment comprising an anode and a first fluid distribution member having an inlet to receive a feedstream of a lithium-bearing solution into the anodic compartment and an outlet to remove a lithium-depleted solution therefrom; each cathodic compartment comprising a cathode and a second fluid distribution member having an inlet to receive a lithium hydroxide solution into the cathodic compartment and an outlet to remove a lithium-enriched hydroxide solution therefrom; the first and second fluid distribution members being interposed between the cation exchange membrane and said respective anode and cathode, wherein said fluid distribution members comprise
- the first and second fluid distribution members are provided with correspondingly aligned male and female fasteners to facilitate alignment and assembly of the alternately arranged anodic and cathodic compartments.
- the respective feed streams for the anodic and cathodic compartments may be manifolded together and delivered to respective inlets of first and second fluid distribution members via respective anodic and cathodic inlet manifolds and the respective product streams of the anodic and cathodic compartments may be manifolded and collected from respective outlets of the first and second fluid distribution members via anodic and cathodic outlet manifolds.
- the electrodialysis cell assembly may further comprise a support frame configured to support said assembly and allow the number of electrolytic cells in the electrodialysis cell assembly to be varied.
- the electrodialysis cell assembly may further comprise a support frame configured to support said assembly, the anodic and cathodic inlet manifolds, and the anodic and cathodic outlet manifolds.
- a system for producing a lithium hydroxide solution from a lithium-bearing solution comprising: an electrodialysis cell assembly as defined above; a source of the lithium-bearing solution in fluid communication with the inlet(s) of the anodic compartment(s); and, an electric current supply associated with the anodes and the cathodes whereby supply of electric current causes lithium cations to migrate from the anodic compartment(s) to the cathodic compartment(s) to produce a lithium-enriched hydroxide solution therein.
- Figure 1 is an expanded view of one embodiment of an electrodialysis cell as described herein;
- Figure 2 is a representative view of the electrodialysis cell as shown in Figure 1 ;
- Figure 3 is an expanded view of one embodiment of an assembly of electrodialysis cells as described herein;
- Figure 4 is a perspective view of a manifold for delivery or collection of respective solutions from anodic and cathodic compartments of the assembly as shown in Figure 3;
- Figure 5 is a perspective view of a frame to support the assembly of electrodialysis cells as shown in Figure 3;
- Figure 6 is a perspective view of one embodiment of the assembly of electrodialysis cells supported by the frame as shown in Figure 5;
- Figure 7 is a graphical representation of free acid and free base concentrations in respective anodic and cathodic compartments as a function of time in an example of operation of the electrodialysis cell as described herein;
- Figure 8 is a graphical representation of lithium concentration of the anolyte and catholyte sampled from respective anodic and cathodic compartments as a function of time in an example of operation of the electrodialysis cell as described herein.
- the present disclosure relates to an electrodialysis cell, in particular to an electrodialysis cell for producing lithium hydroxide from a lithium-bearing solution.
- first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
- Spatially relative terms such as “inner,” “outer,” “beneath”, “below”, “lower”, “above”, “upper” and the like, may be used herein for ease of description to describe one element or feature’s relationship to another element(s) or feature(s) as illustrated in the figures.
- Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features.
- the example term “below” can encompass both an orientation of above and below.
- the device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
- the lithium-bearing solution may be an aqueous solution of a lithium compound, such as lithium sulfate, lithium chloride, lithium fluoride, lithium bicarbonate, lithium carbonate, lithium nitrate, lithium acetate, lithium stearate or lithium citrate.
- the lithium-bearing solution may be a lithium- containing brine or a leachate produced by a process for extracting lithium from a lithium-containing ore.
- the lithium-bearing solution may be derived from a process which extracts lithium from secondary sources, such as recycled lithium batteries.
- the electrodialysis cell 10 includes an anodic compartment 12 and a cathodic compartment 14 separated by a cation exchange membrane 16.
- the cation exchange membrane 16 may be any suitable semi-permeable ion exchange membrane capable of selectively allowing migration of lithium cations therethrough from the anodic compartment 12 to the cathodic compartment 14. Examples of suitable semi- permeable ion exchange membranes include, but are not limited to, National.
- the anodic compartment 12 includes an anode 18 and a first fluid distribution member 20 interposed between the anode 18 and the cation exchange membrane 16.
- the first fluid distribution member 20 has an inlet 22 to receive a feedstream lithium bearing solution into the anodic compartment 12 and an outlet 24 to remove a lithium- depleted solution therefrom. It will be appreciated that the lithium-depleted solution has a lower lithium concentration than the feedstream lithium-bearing solution.
- the cathodic compartment 14 includes a cathode 26 and a second fluid distribution member 28 interposed between the cathode 26 and the cation exchange membrane 16.
- the second fluid distribution member 28 has an inlet 30 to receive a dilute lithium hydroxide solution and an outlet 32 to remove a lithium-enriched hydroxide solution therefrom. It will be appreciated that the lithium-enriched hydroxide solution has a higher lithium concentration than the dilute lithium hydroxide solution.
- the first and second fluid distribution members 20, 28 include a rectangular frame 34 and a permeable spacer sheet 36 mounted therein.
- the frame 34 may be fabricated from a rigid plastic material such as PTFE, PP, PVDF.
- the thickness of the frame 34 is preferably as low as practically possible to minimise the spacing or gap between the anode 18 and the cathode 26.
- the permeable spacer sheet 36 is a woven polymeric material of polypropylene or silicone with a 45° diamond pattern.
- the permeable spacer sheet 36 has a thickness of about 250 pm to about 600 pm, in particular about 450 pm.
- the permeable spacer sheet 36 may be provided as a regular arrangement of panels thereof mounted within the rectangular frame 34.
- the permeable spacer sheet 36 is disposed at or proximal to a facing side 38 of the frame 34 adjacent to the cation exchange membrane 16. In this way, although the same type of permeable spacer sheet 36 may be mounted in the first and second fluid distribution members 20, 28, the permeable spacer sheet 36 mounted in the first fluid distribution member 20 in the anodic compartment 12 will be oriented 180° relative to the permeable spacer sheet 36 mounted in the second fluid distribution member 28 in the cathodic compartment 14.
- the permeable spacer sheet 36 mounted in the first fluid distribution member 20 in the anodic compartment 12 will allow the lithium-bearing solution to flow across a surface of said membrane 16, whereas the permeable spacer sheet 36 mounted in the second fluid distribution member 28 in the cathodic compartment 14 will allow lithium-enriched hydroxide solution to flow across the surface of said membrane 15.
- Respective inlets 22, 30 of first and second fluid distribution members 20, 28 are disposed in a lower portion 38 of a side wall 40 of the frame 34, whereas respective outlets 24, 32 of the first and second fluid distribution members 20, 28 are disposed in an upper portion 42 of an opposing side wall 44 of the frame 34.
- the inlets 22, 32 and outlets 24, 32 include a passage 46 through the side wall 40 or the opposing side wall 44, respectively, and a laterally extending spigot 48.
- the laterally extending spigot 48 may be operatively connected by one or more conduits, manifolds, valves and the like for transfer of said solutions into and out of the anodic and cathodic compartments 12, 14 of the electrodialysis cell 10.
- a conduit is any pipe, tube, passageway or the like through which said solutions may be conveyed.
- An intermediate device, such as a pump or heat exchanger may be connected inline which the one or more conduits.
- a plurality of gaskets 50 are interposed between adjacent components of the electrolysis cell 10 to provide a fluid-tight seal in the anodic and cathodic compartments 12, 14 and prevent fluid leakage therefrom.
- Each gasket 50 generally corresponds in shape and dimensions to the frame 34 of the first and second fluid distribution members 20, 28.
- the gasket 50 shown in Figures 1 and 2 is rectangular.
- the gasket 50 has a thickness of about 1 mm to reduce a gap between the anode and cathode as much as practically possible.
- the gasket 50 may be fabricated from Gore-Tex GRTM, EPDM, PTFE or FPM (VitonTM).
- the electrodialysis cell 10 also includes a pair of opposing end plates 52 to clamp the anodic and cathodic compartments 12, 14 therebetween. It will be appreciated that a respective gasket 50 may be interposed between the anode 18 and one of the adjacently disposed end plates 52, and the cathode 26 and the other of the adjacently disposed end plates 52 to provide a fluid-tight seal and prevent leaks.
- the opposing end plates 52 may be provided with correspondingly aligned apertures 54 to receive fasteners therethrough, thereby guiding assembly of the anodic and cathodic compartments 12, 14 and allowing addition (or removal) of further anodic and cathodic compartments 12, 14 as desired.
- Suitable fasteners include stainless steel bolt nuts and washers.
- the opposing end plates 52 are generally of larger dimensions than the anodic and cathodic compartments 12, 14 and the apertures 54 may be disposed proximal to the edges of the opposing end plates 52 so that the fasteners do not interfere with or compromise the fluid-tight seals of the anodic and cathodic compartments 12, 14.
- the end plates 52 may be fabricated from stainless steel rather than a rigid plastic material to provide sufficient mechanical strength when clamping the anodic and cathodic compartments 12, 14 and their respective elements together.
- the end plates may be about 20 mm thick and a layer of insulation may be provided adjacent to the end plate 52 to prevent any current runaway.
- Adjacent frame members 34 of the first and second fluid distribution members 20, 28 may have corresponding male and female tabs to facilitate alignment and assembly of the plurality of anodic and cathodic compartments 12, 14 in said assembly 10’.
- the arrangement is such that the respective feed streams for the anodic and cathodic compartments 12, 14 may be manifolded together and delivered to respective inlets 22, 30 of first and second fluid distribution members 20, 28 via respective anodic and cathodic inlet manifolds 54, 56 and the respective product streams of the anodic and cathodic compartments 12,
- said manifolds 54, 56, 58, 60 may comprise a generally cylindrical body 62 having a plurality of ports 64 regularly spaced along the length of the body 62 to allow ingress or egress of fluid thereto. Each port 64 is configured to facilitate attachment of one end of a conduit 66, such as a flexible hose. The other end of the conduit 66 is attached to one of the inlets 22, 30 or outlets 24, 32 of the first and second fluid distribution members 20, 28 to provide fluid communication between the manifolds 54, 56, 58, 60 and the anodic and cathodic compartments 12, 14.
- the body 62 is further provided with a port 68 to allow ingress of fluid from an external source via a conduit (not shown) or egress of fluid via a conduit to an external collection site.
- the port 68 is disposed equidistantly spaced from opposing ends of the body 62 on a lateral side thereof. It will be appreciated, however, that the port 68 may be disposed at or proximal to either of the opposing ends of the body 62 or an underside of the body 62.
- a flange 70 may be disposed on an opposing lateral side of the body 62.
- the flange 70 may have two or more through holes 72 by which the flange 70 and therefore the body 62 of the manifold 54-60 may be supported, as will be described later.
- the frame 74 includes a pair of opposing Fl-frames 76 having an upper web member 78 laterally extending between the uppermost ends 80 of opposing upright members 82 of the FI-frame 76 and a lower web member 84 laterally extending between the opposing upright members 82 spaced below a cross member 86 of the FI-frame 76.
- a pair of laterally extending cross members 88 interconnect the corresponding upright members 80 of the opposing Fl-frames 76.
- the cross members 88 are disposed at a similar effective height as the cross member 86 of the FI-frame 76 so as to provide a generally rectangular frame configured to support a base plate 90.
- the base plate 90 is configured to support the electrodialysis cell assembly 10’ as shown in Figure 6.
- the base plate 90 may have a plurality of slots 92 which are configured, in use, to accommodate the fasteners of the end plates 52.
- the slots 92 may be elongate to allow for the number of electrolytic cells 10 in the electrodialysis cell assembly 10’ to be varied according to requirements.
- the upper and lower web members 76, 82 are provided with two or more through holes which are spaced to correspond with the through holes 70 of the flange 68 of the manifold body 62.
- the flange 68 of manifold 54, 58 may be attached to an underside of the upper web member 76 with fasteners, such as nuts and bolts, and the flange 68 of manifold 56, 60 may be attached to an upper surface of the lower web member 82 with similar fasteners.
- the anode 18 and the cathode 26 are generally rectangular sheets arranged in facing parallel alignment with each other and the cation exchange membrane 16. Generally the rectangular sheets are about 1 mm thickness.
- the anode 18 and the cathode 26 may be fabricated from an electrically conductive material that is inert or insoluble under the electrodialysis conditions.
- the anode 18 may be fabricated from an electrically conductive material having an acceptable oxygen overvoltage and minimum side reactions.
- Suitable examples of electrically conductive materials from which the anode may be fabricated include, but are not limited to, or a mixed metal oxide, such as an iridium or ruthenium coated mixed metal oxide, or a dimensionally stable anode (DSA).
- Dimensionally stable anodes comprise a substrate, such as a titanium plate or mesh, with a plurality of metal oxides coated thereon.
- the cathode 26 may be fabricated from an electrically conductive material having a high hydrogen overvoltage and minimum side reactions. Suitable examples of electrically conductive materials from which the cathode 26 may be fabricated include, but are not limited to, metals such as titanium including platinum coated titanium, nickel, niobium, tantalum, zinc tin, lead, platinum, graphite or metal alloys such as stainless steel, in particular 316 stainless steel and Hastelloy.
- the term ‘Hastelloy’ refers to a group of corrosion-resistant nickel alloys, namely the Ni-Mo and the Ni-Cr-Mo alloys. Hastelloy electrodes are characterized by high resistance to hydrochloric, sulfuric, phosphoric, acetic and formic acids, media containing chloride and fluoride ions.
- Each of the anode 18 and the cathode 26 are provided with laterally extending tabs 18a, 26a.
- a power supply may be configured in electrical communication with the tabs 18a, 26a of the anode 18 and the cathode 26 to supply a cell potential of from about 4.0 V to about 7.0 V to the electrodialysis cell 10 to maintain a current density of less than 4 kA/m 2 .
- the power supply may be a direct current rectifier unit supplied with an amp meter and a volt meter to monitor the voltage a current applied to the electrolysis cell 10.
- the primary electrochemical reaction at the anode 18 is oxygen evolution, although this may differ depending on the composition of the lithium-bearing solution.
- the presence of chloride in the lithium bearing solution may mean that chlorine gas would be generated at the anode 18.
- the primary electrochemical reaction at the cathode 26 is hydrogen evolution. It will be appreciated that the reaction gases are drawn from the anodic and cathodic compartments 12, 14 through the respective outlets 24, 32 in the frames 34 of the first and second fluid distribution members 20, 28.
- An anodic feed solution of 1.5 M U 2 SO 4 was supplied to the anodic compartment 12 via inlet 22 and a cathodic feed solution of 0.5 M LiOH was supplied to the cathodic compartment 14 via inlet 30, from respective feed reservoirs.
- Spent anolyte and lithium-enriched catholyte were withdrawn from the anodic and cathodic compartments 12, 14, via respective outlets 24, 32 and recirculation tubing to feed reservoirs.
- a moderately high circulation flow rate was applied via a peristaltic pump to ensure good mixing within said compartments 12, 14 and respective feed reservoirs.
- the temperature of the feed solutions was maintained between about 25 °C and about 27 °C.
- a current density of 1000 A/m 2 was directly applied to the electrodialysis cell 10 and the cell potential between anode 18 and cathode 26 was measured at regular intervals over a 4 h period.
- Cell potential gradually decreased from 6.9 V to 4.7 V, whereas the cathode and anode potential were relatively constant over a range of 0.7- 0.8 V throughout the 4 h test period.
- Figure 7 shows the change in concentration of acid and base concentrations in the anode and cathode compartments 12, 14, respectively.
- the free acid concentration in the anodic compartment 12 increases with time because hydrogen ions are generated at the anode 18.
- the free base concentration in the cathodic compartment 14 increases with time indicating that hydroxide anions are being generated at the cathode 26.
- Figure 8 shows the change in respective lithium concentrations in the anolyte and the catholyte.
- concentration of lithium in the lithium sulphate solution (anolyte) decreased over time, indicating migration of lithium cations from the anodic compartment 12 through the cation exchange membrane 16 to the cathodic compartment 14.
- the lithium hydroxide concentration of the catholyte increased in strength from 41.4 g/L (4.0 w/w%) from an initial LiOH concentration of 11 .7 g/L or 1.2 w/w%.
- the overall LiOH production rate was calculated to be 9.4 g/h.
- the final LiOH product liquor was analysed for sulphur (S) to examine the level of sulphate anions migration across the membrane and to determine the purity of the enriched LiOH catholyte.
- S sulphur
- the maximum concentration of sulphate impurity in a technical grade LiOH product is typically between 0.03-0.05 w/w %.
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- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Materials Engineering (AREA)
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Abstract
L'invention concerne un ensemble de cellules d'électrodialyse pour la production d'hydroxyde de lithium à partir d'une solution contenant du lithium. L'ensemble comprend une pluralité de compartiments anodiques et cathodiques disposés en alternance séparés par des membranes échangeuses de cations respectives qui permettent la migration de cations de lithium à travers celles-ci depuis les compartiments anodiques vers les compartiments cathodiques. Chaque compartiment anodique comprend une anode et un premier élément de distribution de fluide ayant un orifice d'entrée pour recevoir un courant d'alimentation d'une solution contenant du lithium dans le compartiment anodique et un orifice de sortie pour en éliminer une solution appauvrie en lithium. Chaque compartiment cathodique comprend une cathode et un second élément de distribution de fluide ayant un orifice d'entrée pour recevoir une solution d'hydroxyde de lithium dans le compartiment cathodique et un orifice de sortie pour en éliminer une solution d'hydroxyde enrichie au lithium. Les premier et second éléments de distribution de fluide sont interposés entre la membrane échangeuse de cations et ladite anode et ladite cathode respectives, lesdits éléments de distribution de fluide comprenant un cadre configuré pour le maintien d'au moins d'une ou de plusieurs feuille(s) d'espacement perméable(s) à proximité étroite de la membrane d'échange de cations. Une paire de plaques d'extrémité opposées enserrent la pluralité de compartiments anodiques et cathodiques disposés conjointement en alternance ensemble.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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AU2021901490A AU2021901490A0 (en) | 2021-05-19 | Electrodialysis Cell | |
AU2021901490 | 2021-05-19 |
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WO2022241518A1 true WO2022241518A1 (fr) | 2022-11-24 |
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PCT/AU2022/050484 WO2022241518A1 (fr) | 2021-05-19 | 2022-05-19 | Cellule d'électrodialyse |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1561956A (en) * | 1976-08-26 | 1980-03-05 | Diamond Shamrock Corp | Electrolysis apparatus |
EP0064608A1 (fr) * | 1981-04-28 | 1982-11-17 | Asahi Glass Company Ltd. | Cellule électrolytique du type filtre-presse |
US4402810A (en) * | 1980-05-15 | 1983-09-06 | Imperial Chemical Industries Limited | Bipolarly connected electrolytic cells of the filter press type |
US5593553A (en) * | 1992-11-20 | 1997-01-14 | Imperial Chemical Industries Plc | Electrolytic cell and electrode therefor |
US20120117789A1 (en) * | 2010-11-12 | 2012-05-17 | Siemens Pte. Ltd. | Methods of Making a Cell Stack for an Electrical Purification Apparatus |
US20150152563A1 (en) * | 2012-04-23 | 2015-06-04 | Nemaska Lithium Inc. | Processes for preparing lithium hydroxide |
WO2019228577A2 (fr) * | 2018-05-29 | 2019-12-05 | Membrain S.R.O. | Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédé |
-
2022
- 2022-05-19 WO PCT/AU2022/050484 patent/WO2022241518A1/fr active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1561956A (en) * | 1976-08-26 | 1980-03-05 | Diamond Shamrock Corp | Electrolysis apparatus |
US4402810A (en) * | 1980-05-15 | 1983-09-06 | Imperial Chemical Industries Limited | Bipolarly connected electrolytic cells of the filter press type |
EP0064608A1 (fr) * | 1981-04-28 | 1982-11-17 | Asahi Glass Company Ltd. | Cellule électrolytique du type filtre-presse |
US5593553A (en) * | 1992-11-20 | 1997-01-14 | Imperial Chemical Industries Plc | Electrolytic cell and electrode therefor |
US20120117789A1 (en) * | 2010-11-12 | 2012-05-17 | Siemens Pte. Ltd. | Methods of Making a Cell Stack for an Electrical Purification Apparatus |
US20150152563A1 (en) * | 2012-04-23 | 2015-06-04 | Nemaska Lithium Inc. | Processes for preparing lithium hydroxide |
WO2019228577A2 (fr) * | 2018-05-29 | 2019-12-05 | Membrain S.R.O. | Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédé |
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