EP3801842A2 - Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédé - Google Patents
Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédéInfo
- Publication number
- EP3801842A2 EP3801842A2 EP19750051.5A EP19750051A EP3801842A2 EP 3801842 A2 EP3801842 A2 EP 3801842A2 EP 19750051 A EP19750051 A EP 19750051A EP 3801842 A2 EP3801842 A2 EP 3801842A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- product
- forming
- exchange membrane
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- -1 lithium chemical compounds Chemical class 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 66
- 239000012528 membrane Substances 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000000047 product Substances 0.000 claims abstract description 42
- 238000005341 cation exchange Methods 0.000 claims abstract description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 25
- 239000006227 byproduct Substances 0.000 claims abstract description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 19
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 18
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 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 claims abstract description 14
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 10
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000005349 anion exchange Methods 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- 238000010573 double replacement reaction Methods 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005215 recombination Methods 0.000 claims description 2
- 230000006798 recombination Effects 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000012224 working solution Substances 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-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
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000009621 Solvay process Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013400 design of experiment Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- B01D61/44—Ion-selective 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
- B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
-
- 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
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- 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
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
Definitions
- the present invention describes a process to produce lithium chemical compounds, such as lithium hydroxide, bicarbonate or carbonate, using electrodialysis, which involves ion exchange between lithium sulfate solution (Li 2 S0 4 ) and sodium hydroxide solution (NaOH), sodium bicarbonate (NaHCOs) or sodium carbonate (Na 2 C0 3 ).
- the invention relates to an apparatus for performing out the method.
- Lithium hydroxide, lithium bicarbonate, or lithium carbonate are prepared by reacting lithium sulfate (L1 2 SO4) with any of the following species: sodium hydroxide (NaOH), sodium bicarbonate (NaHCOs), or sodium carbonate (Na 2 C0 3 ). Reactions are based on the following chemical equations:
- the first production option is double replacement reaction: chemical compound solutions are mixed in a reactor where they react together to precipitate the solid product, such as Li 2 C0 3 , using controlled heating and cooling and also neutralization principle.
- the solid product such as Li 2 C0 3
- Such a technical approach is the subject of the Chinese patent CN 1486931.
- the disadvantages of the said process are level of conversion, the formation of solid deposits on the reactor surface during crystallization, and the need to refine the product to a level of applicability for batteries like battery grade lithium carbonate.
- Electrodialytic concentrating lithium salt from primary resource where a concentrated lithium sulfate solution is mixed in a sodium carbonate solution in a reactor.
- bipolar electrodialysis driving force is the DC voltage.
- the cation exchange membranes, the bipolar membranes, and optionally the anion exchange membranes are in the electrodialysis stack.
- Lithium hydroxide is formed, and the principle of bipolar electrodialysis function also forms the corresponding acids like sulfuric, hydrochloric, or nitric.
- the lithium hydroxide production process is optimized according to the source of the raw material, such as salt lakes, or the hydrometallurgical treatment of the batteries.
- Electrodialysis metathesis method described in this invention helps to overcome the above-mentioned drawbacks of different electrodialysis concepts while maintaining the progressive features of the process for producing lithium chemical compounds such as lithium hydroxide, bicarbonate or carbonate.
- the invention involves the exchange of ions between the lithium sulfate solution (Li 2 S0 4 ) and the sodium hydroxide solution (NaOH), primary sodium bicarbonate (NaHCCb) or sodium carbonate (Na 2 COs), which takes place in an electric field on an ion exchange membrane system containing at least one anion exchange membrane and cation exchange membranes.
- the repeating sequence of ion exchange membranes form at least four intermembrane spaces.
- the basic repeating motif is visualized in Figure lb by hatching.
- the ions forming the main product are passing through the P-labeled membranes (see Figs la and lb).
- Lithium-ion is passing the cation exchange membrane CMP forming the main product.
- the hydroxide, bicarbonate or carbonate anions are passing anion exchange membrane AMP forming the main product.
- the sodium and sulfate ions are passing through the O-labeled membranes.
- ions are forming the by-product sodium sulfate solution stream after recombination - specifically through the cation exchange membrane CMO forming by-product cation and through the anion exchange membrane AMO forming by-product sulfate anion.
- a cation exchange membrane terminates the basic repeating motif including the four intermembrane spaces Cl, Dl, C2, D2. Source and product chemical compounds solutions flow on both sides of the membranes in the intermembrane compartments Cl, Dl, C2, D2.
- a solution of the by-product flows in the first intermembrane space Cl, from the positive electrode - anode + by interposing the first cation exchange product CMO forming the byproduct and the first anion-exchange AMO forming the by-product.
- the primary anion source solution e.g., sodium hydroxide, bicarbonate, and sodium carbonate flow in the fourth intermembrane space D2 from the positive electrode (anode +), between the second anion exchange membrane AMP forming the main product and the cation exchange membrane CMO forming by-product.
- a primary cation source solution e.g., lithium sulfate solution flows in the second intermembrane space Dl from the positive electrode (anode +), between the first anion exchange membrane AMO forming the by-product and the second cation exchange membrane CMP forming the main product.
- the concentration of the lithium sulfate, sodium hydroxide, primary source sodium bicarbonate, or sodium carbonate feed solutions is preferably in the range from 0.1 to 1.0 mol/L.
- the concentration of the obtained product solutions - sodium sulfate, lithium hydroxide, lithium bicarbonate, or lithium carbonate is higher than 0.1 mol/L.
- the temperature of the solutions in operation is preferably in the range from 10 to 60 °C, preferably in the range from 20 to 50 °C. Their solubility limits the final salt solution concentration.
- the apparatus for carrying out the method of the present invention is comprised of electrodes, between which an array of ion exchange membranes is included containing at least one sequence of anion exchange membranes AMP, AMO and cation exchange membranes CMP, CMO, alternating and forming at least four intermembrane spaces Cl, Dl, C2, D2 for solutions of input and output chemical compounds of electrodialysis double replacement reaction ion exchange system.
- the ion exchange membranes are preferable of the homogeneous or heterogeneous type in thickness from 0.1 to 1.0 mm and with a permselectivity more than 90%.
- Membrane spacers thickness is between 0.1 to 2.0 mm, and distributors are made from polymeric material providing solution equal distribution, source, and product solution mutual immiscibility and mechanical support of the intermembrane spaces.
- the voltage between the electrodes is preferably from 1.0 to 2.5 V per sequence of four membranes - a membrane quadruplet at a current density in the range from 30 to 300 A/m 2 .
- the main advantage of the lithium bicarbonate production using electrodialysis metathesis double replacement reaction process according to the invention is obtaining a straightforward first product solution - e.g., L1HCO3, which meets the purity application limits in batteries, at a high conversion rate.
- the conversion itself takes place in an electrodialysis device made of non-corrosive polymeric materials.
- the benefit of this technical solution is the preparation of a high concentration lithium bicarbonate/carbonate solution near saturation limit with very high purity for use in batteries.
- An analogy of the Solvay process used in the production of sodium carbonate can be utilized for the further production of a commodity chemical like Li 2 C0 3 . Formed lithium bicarbonate formed is converted to lithium carbonate by heating (calcination).
- Fig. la is a schematic diagram of an electrodialysis metathesis double replacement reaction method for producing lithium hydroxide, lithium bicarbonate or lithium carbonate by using one (simplest) ion exchange membrane sequence;
- Fig. lb is a representation of an electrodialysis metathesis double replacement reaction method basic repeating motif for producing lithium hydroxide, lithium bicarbonate, or lithium carbonate using one (hatched) ion exchange membrane sequence and one ending cation exchange membrane CMO;
- Figure 2 shows an exemplary arrangement of five series of four membranes - membrane quadruplets.
- the electrodialysis laboratory unit P EDR-Z/4x (producer company MemBrain) in electrodialysis-metathesis configuration was used for testing.
- the unit contained 5 tanks with a volume of 0.25 to 2.0 liters and 5 centrifugal pumps with a magnetic insert for circulation of solutions in the intermembrane spaces Cl, C2, Dl, D2 created by the anion exchange membranes of AMP, AMO and cation exchange membranes CMP, CMO (scheme of one primary sequence - see Figure lb) and also for electrode rinsing solution E.
- Electrode solution - sodium sulfate solution (Na 2 S0 4 ).
- EDM module was equipped with eleven pcs of cation exchange membranes RALEX ® (CM-PP) and with ten pcs of anion exchange membranes RALEX ® (AM-PP), alternating and forming five membrane sequences (quadruplets) - see scheme in Figure 2.
- CM-PP cation exchange membranes
- AM-PP anion exchange membranes
- Each of the membrane repeating sequence had the arrangement of the hatched part from Figure lb.
- One active membrane area was 64 cm 2 . The test was performed in a batch process.
- the EDM solutions were circulated at 0.5 L/min, and the temperature was kept at 30 °C.
- the working voltage was in the range from 6.7 to 12.0 V and the current was set at 1.28 A.
- 1000 mL of L1HCO3 solution main product was obtained in the third intermembrane space C2 of with concentration 0.69 mol/L and 1100 ml of the secondary product Na 2 S0 4 in the first intermembrane space Cl with concentration 0.38 mol/L in this design of experiment.
- the main product was dosed with demineralized water to prevent precipitation by reaching the solubility level.
- the sulfur content in the main product was 0.115 g/L, and the lithium content was 4.78 g/L.
- the product purity in terms of the molar content of lithium in the numerator relative to the sum of lithium and sulfur in the denominator was 99.5%.
- a sodium sulfate solution with 0.07 mol/L concentration was circulated in the electrode chambers during the experiment.
- Lithium chemical compounds production like lithium hydroxide, bicarbonate, or carbonate which are widely used in the battery industry.
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZ2018-250A CZ2018250A3 (cs) | 2018-05-29 | 2018-05-29 | Způsob výroby chemických sloučenin lithia metodou elektrodialýzy a zařízení k provádění tohoto způsobu |
PCT/CZ2019/050025 WO2019228577A2 (fr) | 2018-05-29 | 2019-05-24 | Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédé |
Publications (1)
Publication Number | Publication Date |
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EP3801842A2 true EP3801842A2 (fr) | 2021-04-14 |
Family
ID=67551037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19750051.5A Pending EP3801842A2 (fr) | 2018-05-29 | 2019-05-24 | Procédé de préparation de composés chimiques au lithium par un procédé d'électrodialyse et appareil pour la mise en oeuvre de ce procédé |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3801842A2 (fr) |
CN (1) | CN112218704B (fr) |
CZ (1) | CZ2018250A3 (fr) |
WO (1) | WO2019228577A2 (fr) |
Families Citing this family (9)
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CN113694733B (zh) * | 2020-05-20 | 2022-11-25 | 国家能源投资集团有限责任公司 | 一种基于双极膜电渗析装置的锂分离方法 |
CN112174172A (zh) * | 2020-11-03 | 2021-01-05 | 严永生 | 一种电渗析方法提纯浓缩氟化铍的制备方法 |
CN113023750A (zh) * | 2021-03-09 | 2021-06-25 | 河北工业大学 | 一种利用电渗析生产氢氧化钠的装置及方法 |
WO2022241518A1 (fr) * | 2021-05-19 | 2022-11-24 | Plastic Fabricators (WA) Pty Ltd t/a PFWA | Cellule d'électrodialyse |
US20230226494A1 (en) * | 2022-01-17 | 2023-07-20 | Ionic Solutions Ltd. | Process and apparatus for high recovery in electrodialysis and electrodeionization systems |
CN114634191A (zh) * | 2022-03-30 | 2022-06-17 | 温州大学新材料与产业技术研究院 | 一种高纯度硝酸锂的生产装置及方法 |
CN116239090A (zh) * | 2022-12-30 | 2023-06-09 | 杭州蓝然技术股份有限公司 | 一种磷酸锂制备磷酸和氢氧化锂的工艺 |
CN116251477B (zh) * | 2023-03-23 | 2023-10-10 | 河北云瑞化工设备有限公司 | 一种碳酸锂的提取装置及方法 |
CN116808832B (zh) * | 2023-08-29 | 2023-12-22 | 杭州匠容道环境科技有限公司 | 通过置换电渗析工艺生产氢氧化锂的方法和装置 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
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GB812377A (en) * | 1956-01-18 | 1959-04-22 | Exxon Research Engineering Co | A regenerative process for spent aqueous alkaline solutions |
NL86370C (fr) * | 1955-08-24 | |||
JP2001104743A (ja) * | 1999-10-07 | 2001-04-17 | Norihisa Miyamatsu | 空中の極性物質除去装置 |
US20060000713A1 (en) * | 2004-07-01 | 2006-01-05 | Carus Corporation | Methods and apparatus for electrodialysis salt splitting |
CN101056693B (zh) * | 2004-09-13 | 2012-04-18 | 南卡罗来纳大学 | 水脱盐工艺和装置 |
JP2011031232A (ja) * | 2009-08-04 | 2011-02-17 | Kee:Kk | 水酸化リチウムの製造方法 |
JP5769409B2 (ja) * | 2010-12-13 | 2015-08-26 | 株式会社アストム | 水酸化リチウムの製造方法 |
CA3013134C (fr) * | 2012-04-23 | 2021-05-18 | Nemaska Lithium Inc. | Procedes de preparation de sulfate de lithium |
RS61656B1 (sr) * | 2013-03-15 | 2021-04-29 | Nemaska Lithium Inc | Postupak za dobijanje litijum hidroksida |
CN103864249B (zh) * | 2014-03-28 | 2015-06-24 | 中国科学技术大学 | 一种由盐湖卤水提取氢氧化锂的方法 |
CN105983251A (zh) * | 2015-02-16 | 2016-10-05 | 秦才东 | 溶液中离子的交换和浓缩方法及装置 |
KR101700684B1 (ko) * | 2015-04-30 | 2017-01-31 | 재단법인 포항산업과학연구원 | 수산화리튬, 및 탄산리튬의 제조 방법 및 그 장치 |
WO2016175613A1 (fr) * | 2015-04-30 | 2016-11-03 | 재단법인 포항산업과학연구원 | Procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant |
CN107299361B (zh) * | 2016-08-31 | 2019-06-14 | 江苏力泰锂能科技有限公司 | 利用可溶性锂盐溶液制备氢氧化锂溶液的电渗析装置 |
KR101887173B1 (ko) * | 2016-10-10 | 2018-08-09 | 주식회사 포스코 | 리튬 화합물의 제조 방법 |
JP6864739B2 (ja) * | 2016-10-10 | 2021-04-28 | ポスコPosco | リチウム化合物の製造方法 |
CN107162023A (zh) * | 2017-05-25 | 2017-09-15 | 合肥工业大学 | 一种硝酸钾的制备系统及制备方法 |
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2018
- 2018-05-29 CZ CZ2018-250A patent/CZ2018250A3/cs unknown
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2019
- 2019-05-24 EP EP19750051.5A patent/EP3801842A2/fr active Pending
- 2019-05-24 WO PCT/CZ2019/050025 patent/WO2019228577A2/fr unknown
- 2019-05-24 CN CN201980035434.6A patent/CN112218704B/zh active Active
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Publication number | Publication date |
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CZ308122B6 (cs) | 2020-01-15 |
WO2019228577A3 (fr) | 2020-01-09 |
WO2019228577A2 (fr) | 2019-12-05 |
CN112218704B (zh) | 2023-03-28 |
CZ2018250A3 (cs) | 2020-01-15 |
CN112218704A (zh) | 2021-01-12 |
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