WO2023030655A1 - Procédé de préparation d'hydroxyde de lithium ou d'une solution aqueuse de celui-ci au moyen d'eau non traitée contenant du sel de lithium, produit ainsi produit et utilisation correspondante - Google Patents

Procédé de préparation d'hydroxyde de lithium ou d'une solution aqueuse de celui-ci au moyen d'eau non traitée contenant du sel de lithium, produit ainsi produit et utilisation correspondante Download PDF

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Publication number
WO2023030655A1
WO2023030655A1 PCT/EP2021/074416 EP2021074416W WO2023030655A1 WO 2023030655 A1 WO2023030655 A1 WO 2023030655A1 EP 2021074416 W EP2021074416 W EP 2021074416W WO 2023030655 A1 WO2023030655 A1 WO 2023030655A1
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mol
electrolyte
catholyte
electrodialysis
concentration
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PCT/EP2021/074416
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German (de)
English (en)
Inventor
Rene Wodrich
Ulrich Plantikow
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K-Utec Ag Salt Technologies
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Priority to PCT/EP2021/074416 priority Critical patent/WO2023030655A1/fr
Publication of WO2023030655A1 publication Critical patent/WO2023030655A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—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
    • B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
    • 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
    • C25B1/34—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
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms

Definitions

  • the invention relates to a method for producing lithium hydroxide (LiOH) or an aqueous solution thereof using a lithium salt-containing raw water according to claim 1, a product produced therewith according to claim 14 and a corresponding use according to claim 15.
  • LiOH lithium hydroxide
  • lithium can be found in large salt lakes with a content of around 0.5% by mass.
  • An object of the present invention is to recover lithium from these salt lakes.
  • the previous procedure is complex and not unproblematic from an environmental point of view.
  • LiOH lithium can be used as a starting material for the wet-chemical production of lithium iron phosphate, which is used as the cathode material in batteries.
  • LiOH is used for the production of high-temperature-resistant lubricating greases and as a carbon dioxide binder in space travel and in breathing apparatus.
  • Lithium hydroxide can be used advantageously for battery applications.
  • the object of the present invention is therefore to provide an improved method for producing lithium hydroxide from raw water containing lithium salts. Furthermore, it is an aspect of the present invention to provide a product produced therewith and a corresponding use.
  • an electrodialysis cell or an electrodialysis system is preferably used, which is known from the international patent application WO 2011/160 662 A1, compare, for example, FIG. 1 there and the associated parts of the description.
  • an electrodialysis cell and an electrodialysis system having this is provided, by means of which or whose an electrodialysis of a lithium salt-containing raw water can be carried out. If a high flow rate of the salt-containing liquid is set here, it is possible to prevent deposits from settling in the electrodialysis cell, in particular in its cathode compartment. In addition, the appropriate choice of different materials in the cell prevents any form of corrosion.
  • a method for producing lithium hydroxide or an aqueous solution thereof using raw water containing lithium salt having at least the following steps: a) providing a first electrolyte, the first electrolyte containing chloride ions; wherein the first electrolyte is produced from the raw water containing lithium salt or contains the raw water containing lithium salt; b) subjecting an electrodialysis to a cathodic reduction of the first electrolyte, resulting in a catholyte and producing a product in the form of lithium hydroxide or an aqueous solution thereof;
  • step (b) the concentration of chloride ions in the first electrolyte may decrease due to the electrodialysis reaction if not increased or stabilized in some other way.
  • step (b) in the first electrolyte, the concentration of hydroxide ions may increase due to the electrodialysis reaction unless otherwise decreased or stabilized.
  • the product produced with the method according to the invention can have completely dissolved lithium hydroxide (LiOH) or partially crystallized lithium hydroxide monohydrate (LiOH H 2 O).
  • the electrodialysis is carried out in an electrodialysis cell, the electrodialysis cell having three chambers, namely, a cathode compartment accommodating a cathode, a middle compartment, and an anode compartment accommodating an anode.
  • the electrodialysis cell known from the international patent application WO 2011/160 662 A1 or the electrodialysis system known therefrom can be used in all of the embodiments presented there.
  • the electrodialysis cell described in this application in particular in claim 15 and/or FIG. 1 and the associated parts of the description, can be used to carry out the method according to the invention.
  • step (b) the electrodialysis in step (b) is carried out under the following conditions:
  • concentration x is between greater than 0 and 19 mol/L or the following applies to the concentration x: 0 mol/L ⁇ x ⁇ 19 mol/L.
  • concentration y y ⁇ (5.5 mol/L - 0.846 • x) if the concentration x is between greater than 0 and 6 mol/L or if the following applies to the concentration x: 0 mol/L ⁇ x ⁇ 6 mol/L.
  • the conditions mean that the following applies to the concentration y: y ⁇ 0.5 mol/L if the concentration x is between greater than 6 and 19 mol/L or if the following applies to the concentration x: 6 mol/L ⁇ x ⁇ 19mol/L.
  • x is the concentration of the chloride ions (Cl- ) in the first electrolyte in the cathode compartment in mol/L; and y the concentration of the hydroxide ions (OH-) in the first electrolyte in the cathode compartment in mol/L.
  • x can be the concentration of lithium chloride (LiCl) in the first electrolyte in the cathode compartment in mol/L
  • y can be the concentration of lithium hydroxide (LiOH) in the first electrolyte in the cathode compartment in mol/L.
  • the electrodialysis according to step (b) in the method according to the invention can be carried out under the condition or conditions that the concentration of the lithium hydroxide dissolved in the first electrolyte is at least 50 % of the saturation concentration of lithium hydroxide (LiOH) in the first electrolyte, and/or that the concentration of lithium chloride (LiCl) in the first electrolyte is greater than 0 mol/L and less than or equal to 19 mol/L.
  • the saturation concentration is understood to be the greatest possible concentration of dissolved lithium hydroxide (LiOH) in the first electrolyte at the temperature under consideration.
  • the first electrolyte can be conducted through the cathode compartment of the electrodialysis cell at a flow rate of 0.05 to 0.5 m/s, preferably 0.1 to 0.3 m/s.
  • the above flow rate ranges can apply to the entire concentration range of x, namely 0 mol/L ⁇ x ⁇ 19 mol/L.
  • the aforementioned flow rate ranges can also preferably only apply to the concentration range 6 mol/L ⁇ x ⁇ 19 mol/L.
  • the inventors have found that the OH- is discharged too slowly from the cathode compartment and the OH- Concentration increases too quickly in the cathode compartment, which reduces the current yield and can lead to membrane-damaging precipitation. Furthermore, with such low flow rates of the first electrolyte, the temperature of the first electrolyte in the cathode space rises disadvantageously, since heat dissipation is no longer ensured. However, if the flow velocity is more than 0.3 m/s, in particular more than 0.5 m/s, the inventors have found that damage to the cathode membrane can occur.
  • the inventors have found in extensive test series that by complying with the conditions defined above with regard to the concentration of chloride ions or lithium chloride and hydroxide ions or lithium hydroxide in the first electrolyte in the cathode compartment when carrying out the electrodialysis according to the invention in the electrodialysis cell described a sufficient current yield of the electrodialysis can be achieved while avoiding membrane-damaging precipitations of lithium hydroxide. Consequently, by taking the concentration parameters into account, sufficient energy efficiency can be ensured in the production of lithium hydroxide by means of electrodialysis.
  • the use of a three-chamber electrodialysis cell is proposed for the first time to carry out electrodialysis to obtain lithium hydroxide.
  • This has the disadvantage that, in contrast to the conventionally used four-chamber electrodialysis cell, the chloride and hydroxide ions that are produced are not separated by an additional membrane.
  • the use of a three-chamber electrodialysis cell has the advantage that the use of an additional membrane can be dispensed with. This simplifies the design of the electrodialysis cell and makes it less expensive.
  • the electrodialysis method according to the invention can be carried out at a lower cell voltage, as a result of which the energy requirement is advantageously reduced.
  • an electrolyte is understood as meaning an ion-conducting fluid, in particular an aqueous salt solution.
  • a catholyte is understood to mean an electrolyte which has been electrochemically acted on by means of cathodic reduction.
  • An anolyte is understood to be an electrolyte that has been electrochemically acted on by means of anodic oxidation.
  • the method can also have at least one of the following steps: c) processing or preparing a portion of the catholyte, the concentration of alkaline earth metal ions in the catholyte being reduced by at least 98%, preferably at least 99%; whereby the concentration of chloride ions in the catholyte increases; which preferably results in the first electrolyte, using raw water containing lithium salt; and/or d) at least partially reusing the catholyte processed after step (c) as the first electrolyte in step (b).
  • step (c) the concentration of alkaline earth metal ions in the catholyte can be reduced by suitable measures known to those skilled in the art, such as precipitation or sorption
  • step (c) the concentration of hydroxide ions in the catholyte may decrease due to the electrodialysis reaction unless otherwise increased or stabilized.
  • At least a portion of the catholyte formed during the electrodialysis can be processed using a lithium salt-containing raw water.
  • the catholyte processed in this way can then be partially reused as the first electrolyte in step (b).
  • step (c) For further details on the processing step according to step (c), reference is made in full to the content of patent application WO 2011/160 663 A1 with the title: "Method for the treatment of saline raw water for the production of process water, process water produced with it and device for carrying out the procedure”.
  • the treatment methods disclosed therein can be used to process the catholyte according to step (c) of the method according to the invention.
  • step (b) can also be carried out under the following conditions (i) to (iii): (i) 0 mol/L ⁇ x ⁇ 19 mol/L; and
  • step (b) can preferably be carried out under the following conditions
  • the concentration y of the hydroxide ions (OH) (or alternatively of the lithium hydroxide) is accordingly adjusted to higher concentrations (between 70 and 100%, preferably between 80 and 100%, the maximum hydroxide ion concentration provided according to the invention (or the according to the invention maximum intended lithium hydroxide concentration) when the concentration x of the chloride ions (Cl-) (or alternatively of the lithium hydroxide) in the first electrolyte is between 0 and 6 mol/L, the inventors have found that a downstream separation of the lithium hydroxide produced (Outside the electrodialysis cell), for example by precipitation or concentration.
  • the process conditions (ii) listed above can also be used with the limitation described above to between 70 and 100%, preferably between 80 and 100%, of the maximum hydroxide ion concentration y provided according to the invention: 0.7 • (5.5 mol/L - 0.846 • x) ⁇ y ⁇ (5.5 mol/L - 0.846 • x), preferably 0.8 • (5.5 mol/L - 0.846 • x) ⁇ y ⁇ (5.5 mol/L - 0.846 • x), are combined.
  • the concentration x of the chloride ions (Cl ⁇ ) (or alternatively the lithium chloride) is adjusted to higher concentrations within the intended range, the inventors have found that the energy efficiency improves further. This is due to the power yield.
  • the method according to the invention can be limited to the following conditions, where x and y are as defined above:
  • the raw water containing lithium salt can be natural or artificially produced salt water, preferably sea water, water taken from surface water, preferably still water, sea water Brackish water, ground water, spring water, a natural or artificially produced brine, or mixtures or concentrates thereof.
  • the lithium salt-containing raw water can have a lithium salt content, in particular a content of lithium chloride, up to saturation, preferably in the range from 0.4 to 45% by weight, more preferably 6 to 40% by weight, in particular 10 up to 34% by weight.
  • the lithium salt-containing raw water can have a lithium salt content, in particular a lithium chloride content, in the range from 0.05 to 5% by weight, preferably 0.1 to 2% by weight, in particular 0.1 to 1% by weight .-%, exhibit.
  • step (c) The processing of the catholyte and/or the first electrolyte according to step (c) can be carried out batchwise or continuously.
  • a higher degree of elaboration of the first electrolyte and thus a higher system efficiency can be achieved by processing in batches. If, on the other hand, the catholyte is processed continuously, then advantageously smaller vessel sizes and/or a smaller number of containers are required to carry out the process.
  • first electrolyte and/or the catholyte can be circulated through the cathode compartment of the electrodialysis cell and via a storage vessel for the catholyte and/or the first electrolyte, at least during step (b).
  • the first electrolyte and/or the catholyte can be homogenized to compensate for different concentrations.
  • conditioning is understood to mean setting a predetermined pH value, a predetermined temperature and/or a predetermined concentration of, for example, chloride and/or hydroxide ions.
  • concentration can be set by selectively discharging used catholyte and selectively supplying fresh or, preferably, processed electrolyte.
  • first electrolyte and/or the catholyte can be tempered, in particular cooled, during one of steps (a) to (d).
  • a better conductivity of the electrolyte can be achieved by setting a higher temperature.
  • the electrolyte temperature to a maximum of 45° C., for example by cooling the electrolyte and/or the catholyte, the membranes arranged in the electrodialysis cell can be protected from thermal damage.
  • the first electrolyte and/or the catholyte can give off a gas, in particular hydrogen gas.
  • a gaseous reaction product such as hydrogen gas
  • the cell voltage may range from 3 to 10 volts, preferably from 3.5 to 8.5 volts (V).
  • the cell current density can be in a range from 500 to 3000, preferably from 1000 to 2500 amperes per square meter (A/m 2 ).
  • the method can have the step:
  • a non-oxidizable acid preferably nitric acid, phosphoric acid or sulfuric acid, in particular sulfuric acid, and /or their alkali metal salts, preferably sodium sulfate, sodium nitrate or sodium phosphate, or mixtures thereof.
  • the further, second electrolyte and/or the anolyte serve to advantageously increase the conductivity and thus to improve the electrodialysis reaction. If an acid is used as the second electrolyte and/or anolyte, this serves as a cost-effective source of protons. If a salt, such as sodium sulfate, is used as the second electrolyte and/or anolyte, this salt is converted to its corresponding acid after a short period of electrodialysis. In addition, an effect of the chlorine on the anode can thus be prevented.
  • a salt such as sodium sulfate
  • the method may include the step: f) during or after step (b) removing the lithium hydroxide product, preferably from the cathode compartment of the electrodialysis cell.
  • the method can have the step: g) conditioning of a saline water, in particular the lithium salt-containing raw water, by means of a hydrochloric acid produced as a by-product.
  • the conditioning of lithium salt-containing water using the generated hydrochloric acid for a desalination process advantageously prevents the formation of poorly soluble crusts that adhere firmly to the subsoil, so-called “scaling”, for example in seawater desalination plants.
  • scaling for example in seawater desalination plants.
  • the flow rate or through-flow rate or circulation rate of the first electrolyte in the cathode space can be 0.05 to 0.5 m/s, preferably 0.1 to 0.3 m/s. carry.
  • the electrodialysis cell (2) shown in FIG. 1 or the electrodialysis system (1) shown in FIG. 1, which are known from international patent application WO 2011/160 662 A1, are preferably used to carry out the method according to the invention.
  • the electrodialysis system has at least: the electrodialysis cell; wherein the electrodialysis cell comprises: an anion exchange membrane, a cation exchange membrane, a cathode, and an anode; the storage vessel for the catholyte and/or the first electrolyte; a reaction vessel for carrying out step (c) of the method according to the invention.
  • the electrodialysis cell has three chambers, namely a cathode space that accommodates the cathode, a middle chamber, and an anode space that accommodates the anode.
  • the anion exchange membrane is monopolar and anion-selective, but not cation-selective.
  • the cation exchange membrane is monopolar and cation-selective, but not anion selective. Consequently, neither the anion exchange membrane nor the cation exchange membrane is a bipolar membrane. This means that neither the anion exchange membrane nor the cation exchange membrane have a catalytic intermediate layer.
  • the electrodialysis cell used according to the invention and in particular the ion exchange membranes used therein are characterized by a simple construction and a high level of robustness and a low purchase price, especially compared to the use of bipolar membranes.
  • the central chamber through which an electrolyte can flow is always arranged between the anion exchanger membrane and the cation exchanger membrane.
  • the electrodialysis system can further comprise: a storage vessel for the product.
  • the storage vessel for the catholyte and/or the first electrolyte and/or the storage vessel for the anolyte and/or the second electrolyte can have at least one device for releasing gases, in particular hydrogen and/or oxygen gas.
  • the method according to the invention can also have the steps: h) during or after step (b), removing the lithium hydroxide-containing catholyte from the cathode compartment of the electrodialysis cell; j) Precipitation of lithium hydroxide monohydrate (LiOH ⁇ H 2 O) from the catholyte outside of the cathode compartment, preferably outside of the electrodialysis cell, the precipitation preferably taking place by cooling the catholyte or by removing water; and k) at least partial, preferably complete, separation of the precipitated lithium hydroxide monohydrate (LiOH•H 2 O) from the catholyte; l) increasing the concentration of lithium chloride (LiCl) in the catholyt
  • the object according to the invention is also achieved by the product according to the invention, preferably lithium hydroxide monohydrate, according to claim 14.
  • the product according to the invention has a lithium hydroxide (LiOH) content of at least 566 g LiOH/kg product (P) and is Process according to at least one of Claims 1 to 13.
  • LiOH lithium hydroxide
  • P LiOH/kg product
  • the object according to the invention is also achieved by the use according to claim 15.
  • the advantages and developments of the use according to the invention are analogous to those of the method according to the invention, as discussed above.
  • the electrodialysis cells or electrodialysis systems described above or in the following description of the figures, or modifications thereof can be used within the scope of the use according to the invention for producing lithium hydroxide or for carrying out the method according to the invention.
  • FIG. 1 shows a schematic overview of the electrodialysis system by means of which the production method according to the invention can be carried out.
  • FIG 3 shows an operating diagram for the production of lithium hydroxide according to the invention in the form of a concentration diagram (current yield as a function of the concentrations of lithium hydroxide (LiOH) and lithium chloride (LiCl)).
  • FIG. 4 shows an operating diagram based on the operating diagram according to FIG. 3, which indicates an operating range that is improved with regard to the current yield.
  • the electrodialysis system 1 shown in FIG. 1 has an electrodialysis cell 2, a storage vessel 4 for a first electrolyte E1 and/or a catholyte K Reaction vessel 6, a storage vessel 8 for a second electrolyte E2 and/or anolyte A and a storage vessel 10 for a by-product NP.
  • the electrodialysis cell 2 has a cathode space 12 , a middle chamber 14 and an anode space 16 .
  • the cathode space 12 is separated from the middle chamber 14 by an anion exchange membrane 18 .
  • the anode space 16 is separated from the central chamber 14 by a cation exchange membrane 20 .
  • a cathode 22 is arranged in the cathode chamber 12 and is surrounded by the first electrolyte E1 and/or by the catholyte K.
  • An anode 24 which is surrounded by the second electrolyte E2 and/or anolyte A, is arranged analogously in the anode chamber 16 .
  • the storage vessel 4 for the first electrolyte E1 and/or catholyte K has any shape, preferably cylindrical.
  • the reaction vessel 6 preferably has a cylindrical, preferably cylindroconical shape, but is not limited to this
  • the storage vessel 8 for the second electrolyte E2 and/or anolyte A and the storage vessel 10 for the by-product NP can have any shape.
  • the anolyte A loses H 2 O to water, while protons H + and gaseous oxygen O 2 are released at the anode 24 .
  • the anolyte A preferably contains sulfuric acid H 2 SO 4 , which serves to improve the conductivity but is not converted during the anode reaction.
  • Chloride ions Cl- migrate from the cathode compartment 12 through the anion exchanger membrane 18.
  • protons H + migrate from the anode compartment 16 through the cation exchanger membrane 20.
  • these two types of ions combine to form the by-product NP hydrogen chloride HCl or aqueous hydrochloric acid solution.
  • the first electrolyte E1 and/or catholyte K contained in the cathode compartment 12 of the electrodialysis cell 2 is constantly circulated via the storage vessel 4 by means of a pump P3. This makes it possible to degas the catholyte K by releasing hydrogen gas H 2 and at the same time to enrich it with chloride ions Cl ⁇ by supplying chloride ions CF from the outside into the storage vessel 4 .
  • the device for delivering the hydrogen gas H 2 is not shown in FIG. 1 for reasons of clarity.
  • the catholyte K can be adjusted to a chloride ion Cl- concentration which is optimal for the cathode reaction by circulating it into the storage vessel 4 .
  • the anolyte A in the anode chamber 16 constantly loses water, while gaseous oxygen O 2 is produced at the anode 24 .
  • the anolyte A can be effectively degassed by purging oxygen gas O 2 .
  • the device for delivering the oxygen gas O 2 is not shown in FIG. 1 for reasons of clarity.
  • the concentration of the anolyte A is diluted to the initial concentration before the reaction by supplying deionized water.
  • the by-product NP namely dilute hydrochloric acid HCl, is circulated via the middle chamber 14 of the electrodialysis cell 2 and the storage vessel 10 by means of a pump P5.
  • the by-product NP is delivered to the consumer, such as a seawater desalination plant, with a pump P6.
  • the volume of fully desalinated water corresponding to the delivery quantity is supplied in a level-controlled manner via a solenoid valve MV4.
  • This minimum concentration of chloride ions Cl- is in a range from 30 to 95%, preferably 33 to 90%, in particular 37 to 85% of the concentration of chloride ions Cl- in the first electrolyte E1 in step (a) at the start of the electrodialysis reaction .
  • the concentration of chloride ions Cl- is determined using a quantitative acid-base titration method with NaOH or HCl, if necessary with a color indicator.
  • the concentration of chloride ions Cl- can also be measured as AgCl by precipitation with AgNO 3 or via the conductivity of the catholyte K and/or the first electrolyte E1 and/or the by-product NP or via the electrical charge that has flowed during the electrodialysis reaction be calculated.
  • step (c) At least a subset of the catholyte K can be processed according to step (c) in such a way that the first electrolyte E1 results again.
  • the chloride ions Cl- required for processing are provided in the process water PW produced using the process there.
  • the method according to the invention has a number of advantages for the user. Essentially, the only starting materials required overall are raw water containing lithium salt, fully desalinated water and electricity.
  • the energy requirement of the electrodialysis reaction is, for example, 0.2 to 0.4 kWh per mole of lithium hydroxide LiOH produced.
  • the energy requirement can be further reduced by using higher concentrations of saline untreated water, as these have increased electrical conductivity.
  • the interfering alkaline earth metal ions are advantageously deposited essentially quantitatively and removed from the liquid.
  • the precipitation of poorly soluble alkaline earth metal salts in the electrodialysis cell 2 is effectively avoided. This advantageously brings about a long service life for the membranes of the electrodialysis system.
  • hydrogen H 2 and oxygen O 2 are produced separately from one another as exhaust gases, which can be released without problems or without risk or can be used for some other purpose.
  • the by-product NP produced with the method according to the invention can be metered into the anolyte A and/or the second electrolyte E2 in the anode space 16 .
  • the resulting oxygen, O 2 -chlorine, Cl 2 gas mixture is suitable for sterilizing water.
  • the electrodialysis system 1 can have other pipelines, pumps, valves and the like that are not described in detail, with which the individual vessels, such as the electrodialysis cell 2, the storage vessel 4, the reaction vessel 6, the storage vessel 8 and the storage vessel 10 are connected to each other. Raw materials, intermediate products and end products can thus be transported within the electrodialysis system 1 .
  • a product of the electrodialysis reaction the catholyte K, which has an increased concentration of hydroxide ions OH', is used for processing a lithium salt-containing raw water RW and thus as a starting material in the processing method according to step (d).
  • salt is understood as meaning all known salts, preferably alkali metal salts and/or alkaline earth metal salts, in particular lithium salts, more preferably salts with halide ions as anion, in particular LiCl, or mixtures thereof.
  • the invention permits further design approaches.
  • the storage vessel 4 for the catholyte K can also be used at the same time as a storage vessel for the process water PW of the processing method of step (c), which is not explained in detail.
  • one storage vessel can advantageously be saved.
  • the specific energy requirement is plotted as a function of the current yield. As can be seen from FIG. 2, the specific energy requirement shows an exponential curve with increasing current yield. A high current yield of more than 70%, for example, corresponds to a maximum specific energy requirement of around 0.30 kWh/mol.
  • FIG. 3 shows an operation diagram for the production of lithium hydroxide according to the invention in the form of a concentration diagram, which was developed by the inventors.
  • SA operating ranges with similar current efficiency
  • SA e.g., an operating range that has an SA of 65 to 75%) depending on the concentration of lithium hydroxide (LiOH) in the first electrolyte and the concentration of lithium chloride (LiCl) in the first electrolytes specified.
  • Adjacent operating regions are shown in Figure 3 separated by dotted lines.
  • the inventors determined an operating limit line (cf. solid line running from top left to bottom right in FIGS. 3 and 4). If this is exceeded, precipitation can occur in the cathode compartment and thus membrane damage.
  • the first electrolyte is conducted through the cell at a high flow rate or through-flow rate or circulation rate (for example 0.05 to 0.5 m/s, preferably 0.1 to 0.3 m/s), what a concentration of Cl- or LiCl up to 19 mol/L or even higher, precipitation only takes place outside the cathode space or the cell in the product container.
  • a high flow rate or through-flow rate or circulation rate for example 0.05 to 0.5 m/s, preferably 0.1 to 0.3 m/s
  • the optimal working range or operating range in the electrodialysis according to step (b) according to the invention can have the shape of a triangle in a concentration diagram such as FIG. 3 . From this, the inventors have derived the conditions (i) to (iii) reproduced in claim 1:
  • x is the concentration of Cl or LiCl in the first electrolyte in the cathode compartment in mol/L; and y is the concentration of OH or LiOH in the first electrolyte in the cathode compartment in mol/L.
  • the dotted curves in FIG. 3 delimit the operating ranges of similar current efficiencies which result at a particular concentration ratio of LiOH and LiCl. It can be seen here that at high concentrations of LiOH between 3.0 and 5.0 mol/L and at low concentrations of LiCl of up to 1.5 mol/L, a low current yield of between 5 and 15% in each case in the first electrolyte results. On the other hand, a high current yield of between 65 and 75% results with a LiOH concentration in the first electrolyte of up to 0.5 mol/L and a LiCl concentration of up to 6.0 mol/L. With high LiCl concentrations in the first electrolyte of more than 6.0 mol/L to 19 mol/L and low LiOH concentration in the first electrolyte, high current yields of up to 75% can also be achieved.
  • a working area with a high Cl or LiCl concentration and a low OH or LiOH concentration in the first electrolyte is preferred in order to use the method according to the present invention with a high current efficiency to obtain.
  • a particularly preferred operating range within this optimal working range is along the operating limit line (highest possible LiOH concentration, in each case based on a specific Cl or LiCl concentration) and at a high concentration of Cl or LiCl, since in this case a high conductivity of the first electrolyte is achieved with good downstream separability of the LiOH produced.
  • concentration parameters discussed above preferably apply in the event that the concentration of chloride ions in the middle chamber is 1.0 to 20.0 mol/L, in particular 1.5 to 6.0 mol/L , amounts to.

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Abstract

Selon l'invention, un procédé permet de préparer de l'hydroxyde de lithium ou une solution aqueuse de celui-ci au moyen d'eau non traitée contenant du sel de lithium, une électrolyse d'un premier électrolyte étant réalisée. L'électrodialyse est réalisée dans les conditions suivantes : y < 5,5 - 0,846 · x... (i); et 0 Mol/L < x ≤ 20 mol/L... (Ii). x est la concentration des ions chlorure (Cl-) dans le premier électrolyte dans la chambre de cathode; et y est la concentration des ions hydroxyde (OH-) dans le premier électrolyte dans la chambre de cathode. En variante, x peut être la concentration de chlorure de lithium (LiCl) dans le premier électrolyte dans la chambre de cathode; et y peut être la concentration d'hydroxyde de lithium (LiOH) dans le premier électrolyte dans la chambre de cathode.
PCT/EP2021/074416 2021-09-03 2021-09-03 Procédé de préparation d'hydroxyde de lithium ou d'une solution aqueuse de celui-ci au moyen d'eau non traitée contenant du sel de lithium, produit ainsi produit et utilisation correspondante WO2023030655A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036713A (en) * 1976-03-04 1977-07-19 Foote Mineral Company Process for the production of high purity lithium hydroxide
WO2009131628A1 (fr) * 2008-04-22 2009-10-29 Chemetall Foote Corporation Procédé de réalisation d'hydroxyde de lithium et d'acide chlorhydrique de haute pureté
WO2011160662A1 (fr) 2010-06-21 2011-12-29 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Procédé de production de chlorure d'hydrogène ou d'une solution aqueuse de chlorure d'hydrogène au moyen d'une eau non traitée salée, produit ainsi préparé, utilisation du produit et système d'électrodialyse
WO2011160663A1 (fr) 2010-06-21 2011-12-29 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Procédé de traitement d'une eau non traitée salée pour produire de l'eau traitée, eau traitée ainsi produite et dispositif pour la mise en oeuvre du procédé
WO2013153692A1 (fr) * 2012-04-13 2013-10-17 旭化成株式会社 Procédé de collecte de lithium
DE102015203395A1 (de) * 2015-02-25 2016-08-25 Technische Universität Bergakademie Freiberg Verfahren zur elektrodialytischen Herstellung von Lithiumhydroxid aus verunreinigten lithiumhaltigen wässrigen Diluaten
EP3326974A1 (fr) * 2015-05-13 2018-05-30 Research Institute of Industrial Science & Technology Procédé pour la production d'hydroxyde de lithium et du carbonate de lithium
DE102020107923A1 (de) * 2020-03-23 2021-09-23 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Verfahren zur Erzeugung von Lithiumhydroxid oder einer wässerigen Lösung desselben unter Verwendung eines Lithiumsalz-haltigen Rohwassers und entsprechende Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036713A (en) * 1976-03-04 1977-07-19 Foote Mineral Company Process for the production of high purity lithium hydroxide
WO2009131628A1 (fr) * 2008-04-22 2009-10-29 Chemetall Foote Corporation Procédé de réalisation d'hydroxyde de lithium et d'acide chlorhydrique de haute pureté
WO2011160662A1 (fr) 2010-06-21 2011-12-29 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Procédé de production de chlorure d'hydrogène ou d'une solution aqueuse de chlorure d'hydrogène au moyen d'une eau non traitée salée, produit ainsi préparé, utilisation du produit et système d'électrodialyse
WO2011160663A1 (fr) 2010-06-21 2011-12-29 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Procédé de traitement d'une eau non traitée salée pour produire de l'eau traitée, eau traitée ainsi produite et dispositif pour la mise en oeuvre du procédé
WO2013153692A1 (fr) * 2012-04-13 2013-10-17 旭化成株式会社 Procédé de collecte de lithium
DE102015203395A1 (de) * 2015-02-25 2016-08-25 Technische Universität Bergakademie Freiberg Verfahren zur elektrodialytischen Herstellung von Lithiumhydroxid aus verunreinigten lithiumhaltigen wässrigen Diluaten
EP3326974A1 (fr) * 2015-05-13 2018-05-30 Research Institute of Industrial Science & Technology Procédé pour la production d'hydroxyde de lithium et du carbonate de lithium
DE102020107923A1 (de) * 2020-03-23 2021-09-23 WME Gesellschaft für windkraftbetriebene Meerwasserentsalzung mbH Verfahren zur Erzeugung von Lithiumhydroxid oder einer wässerigen Lösung desselben unter Verwendung eines Lithiumsalz-haltigen Rohwassers und entsprechende Verwendung

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