CN116837419A - Method for extracting lithium from salt lake - Google Patents
Method for extracting lithium from salt lake Download PDFInfo
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- CN116837419A CN116837419A CN202311090192.5A CN202311090192A CN116837419A CN 116837419 A CN116837419 A CN 116837419A CN 202311090192 A CN202311090192 A CN 202311090192A CN 116837419 A CN116837419 A CN 116837419A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 169
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 129
- 239000000843 powder Substances 0.000 claims abstract description 71
- 239000012267 brine Substances 0.000 claims abstract description 65
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 238000002844 melting Methods 0.000 claims abstract description 42
- 230000008018 melting Effects 0.000 claims abstract description 42
- 238000005070 sampling Methods 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000011833 salt mixture Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000010025 steaming Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 35
- 230000008021 deposition Effects 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 159000000000 sodium salts Chemical class 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000004422 calculation algorithm Methods 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 238000010587 phase diagram Methods 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 150000003385 sodium Chemical class 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 8
- 235000002639 sodium chloride Nutrition 0.000 description 163
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 238000000605 extraction Methods 0.000 description 16
- 239000001103 potassium chloride Substances 0.000 description 16
- 235000011164 potassium chloride Nutrition 0.000 description 16
- 230000014509 gene expression Effects 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 235000011147 magnesium chloride Nutrition 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- -1 li + Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to a method for extracting lithium from a salt lake. The method comprises the following steps: pretreating the obtained salt lake brine to generate pretreated lithium-containing crystalline powder, wherein the pretreatment at least comprises steaming and sunning the salt lake brine; mixing a predetermined modulating salt in a predetermined proportion in the lithium-containing crystalline powder based on the sampling data about the lithium-containing crystalline powder and the target melting point of the mixture to produce a mixture of mixed predetermined modulating salts, the predetermined modulating salt being used to reduce the melting point of the mixture of mixed predetermined modulating salts; heating the mixed predetermined salt mixture to produce molten salt; and performing electrolytic separation for the molten salt using the electrode so as to deposit metallic lithium on the electrode. Therefore, the application can lower the melting point of the lithium salt mixture, further reduce the energy consumption of extracting lithium from the salt lake, and improve the recovery efficiency of lithium in the lithium extracting mode of extracting lithium from the salt lake.
Description
Technical Field
The present application relates generally to the field of lithium metal production and, in particular, to a method for salt lake lithium extraction.
Background
Lithium is an important component of batteries used in electric vehicles and electronic devices. With the rapid development of energy automobiles, electronic devices and energy storage technologies, the demand for lithium resources is increasing. Traditional lithium ore exploitation and expansion are limited by factors such as ore geography, and mass production of lithium resources is difficult. The salt lake is rich in lithium salt, so that the extraction of lithium from the salt lake is an important way for obtaining lithium resources.
Conventional methods for extracting lithium from salt lakes include, for example: adsorption coupled membrane process, leaching precipitation process, and electrodialysis precipitation process. For example, taking an adsorption coupling membrane method as an example, the scheme mainly includes: firstly, absorbing and extracting lithium ions in salt lake brine by utilizing the lithium ion selectivity of an adsorbent, and then realizing the concentration of the lithium ions and the separation of the lithium ions from other ions such as magnesium ions by eluting; then, the lithium solution is further concentrated and the brine is purified through a series of organic film gradient coupling, so that the lithium extraction of the salt lake is realized.
In the conventional method for extracting lithium from the salt lake, the content of lithium in the salt component of the salt lake brine is not high, and elements such as sodium, magnesium and the like in the salt component can influence the extraction of lithium. In addition, the ion exchange membrane required in the adsorption coupling membrane method depends on an inlet, and has the advantages of higher energy consumption, more byproducts and lower recovery efficiency of lithium.
In summary, the conventional method for extracting lithium from salt lakes has the following disadvantages: the energy consumption is higher, and the lithium recovery efficiency is lower.
Disclosure of Invention
Aiming at the problems, the application provides a method for extracting lithium from a salt lake, which can obviously reduce the melting point of a lithium salt mixture, further reduce the energy consumption of extracting lithium from the salt lake and improve the recovery efficiency of lithium in a lithium extraction mode of extracting lithium from the salt lake.
According to a first aspect of the present application there is provided a method for extracting lithium from a salt lake, the method comprising: pretreating the obtained salt lake brine to generate pretreated lithium-containing crystalline powder, wherein the pretreatment at least comprises steaming and sunning the obtained salt lake brine; mixing a predetermined modulating salt in a predetermined proportion in the lithium-containing crystalline powder based on the sampling data about the lithium-containing crystalline powder and the target melting point of the mixture to produce a mixture of mixed predetermined modulating salts, the predetermined modulating salt being used to reduce the melting point of the mixture of mixed predetermined modulating salts; heating the mixed predetermined salt mixture to produce molten salt; and performing electrolytic separation for the molten salt using the electrode so as to deposit metallic lithium on the electrode.
In some embodiments, the predetermined proportion of the predetermined modulating salt is determined via the steps of: optimizing stable phases existing under different components and temperatures in a multi-component system in the lithium-containing crystalline powder based on sampling data and a phase diagram calculation algorithm on the lithium-containing crystalline powder component so as to obtain a solid-liquid phase line; determining association data of melting points of the different components and the mixture based on the solidus and liquidus; and determining a predetermined modulating salt to be added corresponding to the target melting point and a predetermined proportion of the predetermined modulating salt to be added based on the target melting point of the mixture, and the association relationship data of the different components and the melting point of the mixture. Thus, the present application can not only significantly lower the melting point of the lithium salt mixture, but also precisely control the melting point of the lithium salt mixture.
In some embodiments, pre-treating the obtained salt lake brine to produce a pre-treated lithium-containing crystalline powder comprises: steaming and sun-drying the obtained salt lake brine to enable sodium salt to reach saturated solubility and separate out so as to generate residual brine after sodium removal by concentration and separated out sodium salt; and concentrating and crystallizing the generated residual brine so as to obtain crystallized salt mine.
In some embodiments, generating the remaining brine after removal of sodium via concentration comprises: at a control device, obtaining first sample data regarding a salt lake brine composition; calculating a predetermined precipitation concentration threshold before the magnesium salt or lithium salt solution in the salt lake brine reaches the precipitation concentration based on the solubility product algorithm and the first sampling data; and controlling the steaming and drying of the salt lake brine based on the calculated predetermined precipitation concentration threshold value, so that sodium salt in the salt lake brine is precipitated after reaching solubility, so as to generate residual brine after sodium removal by concentration and precipitated sodium salt, wherein the residual brine after sodium removal by concentration comprises: saturated sodium, magnesium, calcium, potassium, and lithium salt solutions having concentrations within a predetermined range from a predetermined precipitation concentration threshold.
In some embodiments, pre-treating the obtained salt lake brine to produce a pre-treated lithium-containing crystalline powder further comprises: crushing the obtained block of the crystallized salt mine so as to obtain salt mine powder; screening the salt mine powder to obtain screened target salt mine powder; and vacuum baking and dehydrating the target salt mine powder to generate the pretreated lithium-containing crystal powder.
In some embodiments, determining the proportioning of the predetermined modulating salt comprises: the predetermined proportion of the mixed predetermined modulation salt is determined based on the sampling data on the lithium-containing crystalline powder and the target melting point on the mixture of the mixed predetermined modulation salt and at least one of the target boiling point, the target saturated vapor pressure, the target viscosity, the target conductivity, and the target electrode potential on the molten salt.
In some embodiments, performing electrolytic separation with an electrode for molten salt to cause deposition of metallic lithium on the electrode comprises: sampling the molten salt to obtain third sampled data about the composition of the molten salt; calculating electrode potentials of the element lithium and other elements based on the Nernst equation and the third sampling data; providing molten salt into an electrorefining furnace; and applying the calculated electrode potentials on the electrodes of the electrorefining furnace so as to cause the metallic lithium and other elements to be sequentially deposited on the electrodes, the electrode potentials being respectively associated with deposition potentials of the metallic lithium and other elements.
In some embodiments, causing the sequential deposition of metallic lithium and other elements on the electrode comprises: applying a first electrode potential to the electrode such that magnesium metal precipitates for deposition on the electrode; and applying a second electrode potential to the electrode such that the metallic lithium precipitates for deposition on the electrode, the second electrode potential being lower than the first electrode potential.
In some embodiments, causing the sequential deposition of metallic lithium and other elements on the electrode comprises: continuously applying a predetermined electrolytic current such that the electrode potential varies with the predetermined electrolytic current so that metallic magnesium precipitates for deposition on the electrode; and causing metallic lithium to precipitate for deposition on the electrode.
In some embodiments, causing lithium metal to deposit on the electrode comprises: so that metallic magnesium, metallic sodium, metallic lithium, metallic potassium and calcium are sequentially deposited on the electrode.
In some embodiments, the predetermined modulating salt comprises: one or more of chloride, fluoride, nitrate and carbonate.
The summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the application, nor is it intended to be used to limit the scope of the application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present application, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 illustrates a flowchart of a method for extracting lithium from a salt lake according to an embodiment of the present application.
Fig. 2 illustrates a flow chart of a method for obtaining a lithium-containing crystalline powder according to an embodiment of the application.
Fig. 3 illustrates a flow chart of a method for causing metallic lithium to be deposited on an electrode according to an embodiment of the application.
Fig. 4 illustrates a schematic diagram of a plot of the extraction yield of lithium metal at different electrode potentials according to an embodiment of the application.
Fig. 5 illustrates a schematic of an initial deposition composition at different electrode potentials in accordance with an embodiment of the application.
Fig. 6 illustrates a schematic diagram of separation factors of different elements according to an embodiment of the application.
Fig. 7 illustrates a schematic diagram of a phase diagram of a mixture of lithium chloride and potassium chloride according to an embodiment of the present application.
Detailed Description
Preferred embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While the preferred embodiments of the present disclosure are illustrated in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The term "comprising" and variations thereof as used herein means open ended, i.e., "including but not limited to. The term "or" means "and/or" unless specifically stated otherwise. The term "based on" means "based at least in part on". The terms "one example embodiment" and "one embodiment" mean "at least one example embodiment. The term "another embodiment" means "at least one additional embodiment". The terms "first," "second," and the like, may refer to different or the same object.
As described above, in the above conventional method for extracting lithium from a salt lake, since the content of lithium in the salt component of the salt lake brine is not high, and elements such as sodium, magnesium, etc. present in the salt component may affect the extraction of lithium. In addition, the ion exchange membrane required in the adsorption coupling membrane method depends on an inlet, and has the advantages of higher energy consumption, more byproducts and lower recovery efficiency of lithium. Therefore, the conventional method for extracting lithium from a salt lake has disadvantages in that: the energy consumption is higher, and the lithium recovery efficiency is lower.
To at least partially address one or more of the above problems, as well as other potential problems, the present application proposes a method for extracting lithium from a salt lake. In the solution of the application, the lithium-containing crystalline powder is obtained by pre-treatment of the obtained salt lake brine (the pre-treatment at least comprises steaming and sun-drying the obtained salt lake brine); mixing a predetermined modulating salt in a predetermined proportion in the lithium-containing crystalline powder based on the sampling data about the lithium-containing crystalline powder to generate a mixed predetermined modulating salt mixture, and heating the mixed predetermined modulating salt mixture to generate molten salt; the application can obviously reduce the melting point of the mixture by mixing the predetermined modulation salt in the predetermined proportion, thereby obviously reducing the energy consumption required by generating the molten salt. In addition, the electrode is utilized to carry out electrolytic separation on molten salt so as to enable lithium metal to be deposited on the electrode, and the high-temperature electrochemical method is adopted to carry out electrolytic separation after the salt mixture is heated and melted, so that high-purity lithium metal, pure other byproduct metals and the like can be directly obtained. Therefore, the application can obviously reduce the energy consumption of extracting lithium from the salt lake and improve the recovery efficiency of lithium.
The technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, and they should not be construed as limiting the scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Fig. 1 illustrates a flow chart of a method 100 for salt lake lithium extraction according to an embodiment of the application. It should be understood that method 100 may also include additional steps not shown and/or that the illustrated steps may be omitted, as the scope of the application is not limited in this respect.
At step 102, the salt lake brine obtained is pre-treated to produce a pre-treated lithium-containing crystalline powder.
Regarding salt lake brine, the main components thereof are various chloride salts. For example, salt lake brine mainly includes: lithium chloride, sodium chloride, magnesium chloride, potassium chloride, calcium chloride, and the like. Wherein the higher content is sodium.
As to a method of producing a lithium-containing crystalline powder via pretreatment, it includes, for example: steaming and sun-drying the obtained salt lake brine to enable sodium salt to reach saturated solubility and separate out so as to generate residual brine after sodium removal by concentration and separated out sodium salt; concentrating and crystallizing the generated residual brine so as to obtain crystallized salt ores; crushing the obtained block of the crystallized salt mine so as to obtain salt mine powder; screening the salt mine powder to obtain screened target salt mine powder; and vacuum baking and dehydrating the target salt mine powder to generate the pretreated lithium-containing crystal powder. For example, the old brine of the Bohr sweat salt lake is obtained, and the old brine of the Bohr sweat salt lake is steamed and sun-dried to enable the sodium salt and the magnesium salt to reach saturated solubility in sequence to be separated out; all the old brine is evaporated and crystallized into crystallized salt mine; crushing and screening the crystallized salt mine, and drying the screened crystallized salt mine powder to obtain the pretreated lithium-containing crystallized powder.
The method 200 for generating lithium-containing crystals via pretreatment will be described in detail below in conjunction with fig. 2, and will not be described in detail herein.
In step 104, a predetermined modulating salt is mixed in the lithium-containing crystalline powder in a predetermined proportion based on the sampling data about the lithium-containing crystalline powder and the target melting point of the mixture to produce a mixture of mixed predetermined modulating salts for reducing the melting point of the mixture of mixed predetermined modulating salts.
For example, sampling the pre-processed lithium-containing crystalline powder generated at step 102 to obtain second sampled data regarding the composition of the lithium-containing crystalline powder; and determining a predetermined proportion of the mixed predetermined modulating salt based at least on the second sampled data and a target melting point for the mixture of mixed predetermined modulating salts. Then, a predetermined modulating salt is mixed in a predetermined ratio in the lithium-containing crystalline powder to produce a mixed predetermined modulating salt mixture.
For example, in some embodiments, after pretreatment of the obtained halfpiral brine, a lithium-containing crystalline powder is obtained. For example, 50g of the lithium-containing crystalline powder was sampled, and second sampling data concerning the composition of the lithium-containing crystalline powder was obtained by analyzing the sampled lithium-containing crystalline powder. For example, the second sample data indicates that the mass ratio of Li element, na element, K element, ca element, mg element in the lithium crystal powder is, for example, 0.0013:5.903:1.0:0.084:2.372. Correspondingly, liCl, naCl, KCl, caCl 2 、MgCl 2 The mass ratio of (3) is 0.0079:4.4024:1.9066:0.2326:5.1853. Then according to the lithium-containing crystalline powderAnd finally, calculating and determining association relation data of melting points of different components and the mixture by a phase diagram calculation algorithm of various components, wherein in some embodiments, corresponding components with lower melting points of the mixture under various components can be selected as a preset modulating salt so as to adjust adding of the preset modulating salt. For example, selecting to add 4.544g KCl, 21.048g MgCl 2 Make NaCl, KCl and MgCl 2 Is 19.87:13.42:45.70, thereby lowering the melting point to 383 ℃. If 4.544g of KCl and 21.048g of MgCl are not mixed 2 The lithium-containing crystalline powder is directly heated to a melting point of 700 ℃ or more.
In other embodiments, 4.550g KCl, 5.668g CaCl2, and 20.751g MgCl2 are added according to the second sample data of the above-described lithium-containing crystalline powder composition such that the mass ratio of NaCl to KCl to CaCl2 to MgCl2 is 18.70:12:67:6.66:42.84, thereby lowering the melting point to 380 ℃.
In some embodiments, mixing a predetermined proportion of a predetermined modulating salt in the lithium-containing crystalline powder comprises: based on sampling data about the lithium-containing crystalline powder, a predetermined proportion of a predetermined modulating salt is added to the lithium-containing crystalline powder so as to achieve the following: adjusting the weight percentage of lithium chloride to 42% -62%; adjusting the weight percentage of sodium chloride to 5% -10%; and adjusting the weight percentage of the potassium chloride to 30% -50%. By adopting the mode, the application can obviously reduce the melting point of the mixture, thereby reducing the energy consumption of extracting lithium from the salt lake.
In other embodiments, a method for determining a predetermined proportion of a predetermined modulation salt, for example, includes: optimizing stable phases present at different components and temperatures in a multi-component system in the lithium-containing crystalline powder based on sampling data (i.e., second sampling data mentioned later) and a phase diagram calculation algorithm (calpha) for the lithium-containing crystalline powder component to obtain a solidus and a liquidus; determining association data of melting points of the different components and the mixture based on the solidus and liquidus; and determining a predetermined modulating salt to be added and a predetermined proportion of the predetermined modulating salt to be added corresponding to the target melting point based on the target melting point of the mixture and the association relationship data of the different components and the melting point of the mixture. By adopting the means, the melting point of the mixed salt can be accurately reduced.
The phase diagram calculation algorithm (calpha) is described below in conjunction with expressions (1) and (2). The principle of the phase diagram calculation algorithm is to solve the coexistence line between the phases. To be used forAnd->For example, the coexistence of two phases, the following expression (1) illustrates that the chemical potentials of the same component in the two phases are equal.
（1）
In the above-mentioned expression (1),representing component i->Chemical potential in the phase. />Representing component i->Chemical potential in the phase. />Represents->Is a total gibbs free energy of (c). />Represents->Total gibbs free energy of the phase. />Representing component i->Amount of material in the phase. />Representing component i->Amount of material in the phase. />And->Respectively represent->And->And (3) phase (C). p represents pressure. T represents temperature. />Represents j is->The components in the phases are fixed and j is not equal to i, and the temperature and pressure are fixed.Represents j is->The components in the phases are fixed and j is not equal to i, and the temperature and pressure are fixed.
It will be appreciated that each phase is made up of a plurality of components mixed together. For example, the KCl phase is composed of components K and Cl. The following expression (2) illustrates a calculation algorithm of the molar gibbs free energy of each phase.
（2）
In the above-mentioned expression (2),representing the standard gibbs free energy of component i. />Representing the mole fraction of component i. />Representing the mole fraction of component j. />Representing the excess gibbs free energy. i represents a component. />Represents the molar Gibbs free energy. R represents a gas constant. T represents temperature.
To obtain an expression of the molar gibbs free energy of each phase at equilibrium, thermodynamic experiments or simulations may be required. For example, a phase diagram of the multi-component mixture is calculated based on the mixing enthalpy, heat capacity, vapor pressure, activity obtained via thermodynamic experiments or simulations.
Fig. 7 illustrates a schematic diagram of a phase diagram of a mixture of lithium chloride and potassium chloride according to an embodiment of the present application. Taking the phase diagram of the LiCl-KCl mixture as an example, as shown in FIG. 7, when the molar ratio of LiCl to KCl is 0:1, the melting point temperature of the mixture is 607 ℃. When the molar ratio of LiCl to KCl was 1:0, the melting point temperature of the mixture was 774 ℃. When a predetermined modulating salt (for example, KCl) is added to the lithium-containing crystalline powder in a predetermined ratio based on sampling data on the lithium-containing crystalline powder such that the molar ratio of LiCl to KCl is 0.58:0.42, the melting point of the mixture of the mixed predetermined modulating salt is the lowest, which is 352 ℃.
As another example, sampling is performed for the lithium-containing crystalline powder subjected to the pretreatment so as to obtain second sampling data on the composition of the lithium-containing crystalline powder; and determining a predetermined proportion of the mixed predetermined modulating salt based on the second sampled data and a target melting point for the mixture of the mixed predetermined modulating salt and at least one of a target boiling point, a target saturated vapor pressure, a target viscosity, a target conductivity, and a target electrode potential for the molten salt. And mixing a predetermined modulating salt in a predetermined ratio in the lithium-containing crystalline powder to produce a mixed predetermined modulating salt mixture. For example, adjusting the weight percent of lithium chloride to 42% -62%; adjusting the weight percentage of sodium chloride to 5% -10%; and adjusting the weight percentage of the potassium chloride to 30% -50%. By adopting the means, the application can obviously reduce the energy consumption. At step 106, the mixture of mixed predetermined modulation salts is heated to produce molten salt.
For example, in some embodiments, the molten salt density is, for example, 1.6g/cm and the temperature is 500 ℃ (773K).
In step 108, electrolytic separation is performed with respect to the molten salt using the electrode so that metallic lithium is deposited on the electrode.
As regards the electrodes, it is for example a parallel plate electrode. Experimental data show that the parallel plate electrode is adopted, a linear amplification rule is presented, and the method is suitable for scale expansion of lithium extraction in salt lakes.
As to a method of causing metallic lithium to be deposited on an electrode, it includes, for example: sampling the molten salt to obtain third sampled data about the composition of the molten salt; calculating electrode potentials of the element lithium and other elements based on the Nernst equation and the third sampling data; providing molten salt into an electrorefining furnace; and applying the calculated electrode potentials on the electrodes of the electrorefining furnace so as to cause the metallic lithium and other elements to be sequentially deposited on the electrodes, the electrode potentials being respectively associated with deposition potentials of the metallic lithium and other elements. The method 300 for depositing metallic lithium on the electrode will be described in detail below in conjunction with fig. 3, and will not be described again here.
In some embodiments, the electrode potential of lithium metal is-2.43 to-2.67V. Fig. 4 illustrates a schematic diagram of a plot of the extraction yield of lithium metal at different electrode potentials according to an embodiment of the application. According to the extraction rate of the metal lithium shown in fig. 4, the application can remarkably improve the extraction rate of the metal lithium.
In some embodiments, before the electrolytic separation begins, the electrode potential of each element is: the electrode potential of element Li is-2.57V, the electrode potential of element Na is-2.10V, the electrode potential of element K is-2.81V, the electrode potential of element Ca is-2.81V, and the electrode potential of element Mg is-1.88V; the initial deposition composition at its different potentials is then obtained based on the current relationship.
Fig. 5 illustrates a schematic of an initial deposition composition at different electrode potentials in accordance with an embodiment of the application. Specifically, the initial deposition composition of each element Li, na, K, ca, mg at different electrode potentials is schematically illustrated in fig. 5. The abscissa of fig. 5 indicates different electrode potentials. The ordinate of fig. 5 indicates the composition of the initial deposition element at different electrode potentials.
In some embodiments, the condition for co-deposition of elemental Mg and Na is c_na/c_mg=1.5656e+3 (where c_na represents the concentration of Na and c_mg represents the concentration of Mg). That is, na starts to deposit after the concentration of Mg is reduced to 2.8825 e-4.
At the beginning of Li deposition, the conditions for deposition were c_li/c_na= 0.8606 (where c_li represents the concentration of Li and c_na represents the concentration of Na). At this time, the concentration of each ion is, for example: the concentration of Li ions was 0.020mol/L, the concentration of Na ions was 0.0233 mol/L, the concentration of K ions was 2.733 mol/L, the concentration of Ca ions was 0.224 mol/L, and the concentration of Mg ions was almost absent, at which time the deposition potential was-2.43V.
When the elements Li and K are co-deposited, the deposition condition is c_li/c_k=2.7499e+11 (where c_li represents the concentration of Na and c_k represents the concentration of K). At this time, it is considered that all Li extraction is completed, and the deposition potential at this time is-2.67V. Since the amount of element K is large (about 100 times Li, na) at this time, the deposition process has less influence on the total salt amount, and thus the total ion number variation in the process can be ignored.
In the above scheme, the obtained salt lake brine is subjected to pretreatment (the pretreatment at least comprises steaming and sun-curing the salt lake brine) to obtain lithium-containing crystalline powder; mixing a predetermined modulating salt in a predetermined proportion in the lithium-containing crystalline powder based on the sampling data about the lithium-containing crystalline powder and the target melting point of the mixture to produce a mixed predetermined modulating salt mixture, and heating the mixed predetermined modulating salt mixture to produce a molten salt; the application can remarkably and accurately reduce the melting point of the lithium salt mixture by mixing the predetermined modulation salt in the predetermined proportion, thereby remarkably reducing the energy consumption required for generating the molten salt. In addition, the electrode is utilized to carry out electrolytic separation on molten salt so as to enable lithium metal to be deposited on the electrode, and the high-temperature electrochemical method is adopted to carry out electrolytic separation after the salt mixture is heated and melted, so that high-purity lithium metal, pure other byproduct metals and the like can be directly obtained. Therefore, the melting point of the lithium salt mixture can be obviously reduced, the energy consumption of extracting lithium from the salt lake is further reduced, and the recovery efficiency of lithium in the lithium extracting mode of extracting lithium from the salt lake is improved.
Further, the application can also obviously reduce the cost of extracting lithium from the salt lake. Experimental data shows that the cost of extracting lithium carbonate from the traditional salt lake is 3-4 ten thousand yuan/ton. The lithium yield of the electrolytic lithium extraction of the application under 100% efficiency is 0.2609 g/(Ah). The current efficiency is generally 94%, the electricity cost is about 40% of the total cost, and the pressure drop of the electrolytic cell is about 4.2V, so that the technology of the application for extracting lithium by electrolysis, such as converting the lithium into lithium carbonate, has the cost of 8134.68 DEG electricity/ton. Assuming that the industrial electricity cost is 2 yuan/degree, the cost of the electrolytic lithium extraction technology is about 1.6 ten thousand/ton, which is 1/2 to 1/3 of the cost of the traditional salt lake lithium carbonate extraction technology.
Fig. 2 illustrates a flow chart of a method 200 for obtaining a lithium-containing crystalline powder according to an embodiment of the application. It should be understood that method 200 may also include additional steps not shown and/or that the illustrated steps may be omitted, as the scope of the application is not limited in this respect.
In step 202, the salt lake brine obtained is steamed and sun-dried so that the sodium salt reaches a saturated solubility to precipitate out, so that the residual brine after removal of sodium via concentration and the precipitated sodium salt are generated.
For example, the obtained salt lake brine is steamed and sun-dried so that sodium chloride (for example, sodium chloride) in the salt lake brine is precipitated after reaching solubility, so that residual brine after removal of sodium via concentration and precipitated sodium salt are generated.
Specifically, regarding the method of producing the remaining brine and precipitated sodium salt, it includes, for example: at a control device, obtaining first sample data regarding a salt lake brine composition; calculating a predetermined precipitation concentration threshold before a magnesium salt (e.g., mgCl 2) or lithium salt (e.g., liCl) solution in the obtained salt lake brine reaches a precipitation concentration based on a solubility product algorithm and the first sampling data; based on a predetermined precipitation concentration threshold, the salt lake brine is steamed and sun-dried such that sodium salt (e.g., sodium chloride) in the salt lake brine is precipitated after reaching solubility, so as to generate residual brine after removal of sodium via concentration and precipitated sodium salt.
Regarding the remaining brine, it includes, for example: saturated sodium salts (e.g., sodium chloride) with magnesium salts (e.g., magnesium chloride) or lithium salts (e.g., lithium chloride) solutions. Wherein the difference between the concentration of magnesium salt and lithium salt in the residual brine and the preset precipitation concentration threshold value is within a preset range.
As regards the precipitated sodium salt, it may be a by-product crude salt.
As for the method of calculating the predetermined precipitation concentration threshold value, it is calculated based on a solubility product algorithm. It should be understood that in a saturated solution of sparingly soluble electrolyte, at a certain temperature, sparingly soluble electrolyte A in water m B n After dissolution and saturation, a dissolution equilibrium between the two phases is reached between the solid and the ions dissolved in the solution. The dissolution equilibrium expression and the algorithm for calculating the solubility product are described below in conjunction with expression (3).
（3）
In the above expression (3), A m B n A represents the composition of A ion and B ion m B n A type electrolyte. mB (mB) n- (aq) represents m B's dissolved in the solution n- 。nA m+ (aq) represents n A dissolved in the solution m+ 。K sp Representing the solubility product. Indicating the product of the powers of the ion concentrations as a constantCalled solubility product constant, abbreviated as solubility product. [ A ] m+ ] n Representing the power of the concentration of the A ions. [ B ] n- ] m Representing the power of the concentration of B ions.
In step 204, the resulting residual brine is concentrated and crystallized to obtain crystallized salt mine.
In step 206, the obtained bulk of crystalline salt mine is crushed to obtain salt mine powder.
At step 208, a screen is performed on the salt mine fines to obtain a screened target salt mine fines.
At step 210, vacuum baking dehydration is performed on the target salt mine fines to produce a pre-treated lithium-containing crystalline powder.
By adopting the means, the application can conveniently obtain the lithium-containing crystalline powder for generating molten salt for electrolytic separation
Fig. 3 illustrates a flow chart of a method 300 for depositing metallic lithium on an electrode according to an embodiment of the application. It should be understood that method 300 may also include additional steps not shown and/or may omit steps shown, as the scope of the present application is not limited in this respect.
At step 302, a sample is taken of the molten salt to obtain third sample data regarding the composition of the molten salt. For example, after heating the mixture of mixed predetermined modulation salts so as to generate molten salt, sampling is performed for the molten salt, and the obtained third sampling data on the composition of the molten salt is sent to the control apparatus for calculating the electrode potential of the electrode of the electric refining furnace.
In step 304, electrode potentials for the element lithium and other elements are calculated based on the Nernst equation and the third sampled data. In some embodiments, the control device calculates electrode potentials for elemental lithium and other elements based on the nernst equation, the third sampled data, the target purity and the separation rate of lithium metal. It should be appreciated that the target purity of lithium metal is related to the separation factor of the lithium element relative to other elements.
Expression (4) below exemplifies the algorithm of the nernst equation. The algorithm for calculating the electrode potential of elemental lithium and other elements is described below in conjunction with expression (4).
（4）
In the above-mentioned expression (4),E i representative elementiIs a potential of an electrode of (a).Representative elementiMolar fraction of the reduction of (2) on the electrode, is->Representative elementiActivity coefficient of the reduced substance on the electrode. In solid state electrode->Can be considered as 1.RRepresenting the gas constant, equal to 0.83144621 j/(k. Mol).TRepresenting kelvin temperature.FRepresenting the faraday constant, equal to 96485.33 library/mole. />Representative elementiMole fraction of oxides in the molten salt, +.>Representing the activity coefficient of the oxide of element i in the molten salt. />Representing elements in the electrolytic reactioniIs a number of transferred electrons. />Representative elementiIs a standard potential of (c). Representative elementiIs a potential apparent from the above. It should be understood that the electrode potential of an element is related to its environment, e.g., the proportion of the element, the composition of the materials of the system in which it is located, etc. The standard potential of an element is understood to be the potential of the electrode in the standard state and in the equilibrium state, which does not take into account fluctuations in concentration.
With respect to the standard potential of the element, the following table schematically shows the elements or metal ions Li included in the molten salt in some embodiments + Or Li, na + Or Na, K + Or K, ca 2+ Or Ca, mg 2+ Or standard potential of Mg.
In general, the activity of an element is related to its concentration by an activity coefficient, and thus the concentration and activity coefficient of an element can be used to characterize the activity of an element.
For solid state electrode systems, an activity coefficient at the electrode of 1 can be determined.
Regarding the surface concentrations of the element Li and other elements, when the overpotential is ignored, the surface concentrations of Li and other elements at the reaction equilibrium can be calculated by the following expressions (5) and (6).
（5）
（6）
In the above expressions (5) and (6),Mrepresentative ofLiOther elements than those described above.Representing the surface concentration of Li element on the electrode surface. />Representing the surface concentration of the other element M than Li at the electrode surface. The ratio of the surface concentrations in the expressions (5) and (6) represents the separation factor of Li element relative to other element M. It is understood that the larger the value of the separation factor, the higher the degree of separation of Li from other elements, the higher the purity of Li separated by electrolysis, and the better the separation effect. Should be treatedThe target purity of the electrolytically separated metallic lithium is related to the separation factor of the lithium element relative to the other elements. The separation factor is related to the apparent potential, which is related to the electrode potential, and thus the separation factor can be controlled by controlling the electrode potential.
Regarding activity coefficients of the element Li and other elements in the molten salt, the calculation method comprises the following steps: the apparent potential of Li and other metals in the molten salt is calculated based on the potentials of Li and other elements in the chloride salt system.
Taking the salt lake brine of the Naersham salt lake adopted in the example as an example, the salt lake brine contains ions SO 4 2- 、CO 3 2- The content of (2) is relatively low, so that the present application mainly contemplates the composition of the chloride salt. For example, in salt lake brine, li + 、Na + 、K + 、Ca 2+ 、Mg 2+ The mass ratio of (2) is 0.0013:5.903:1.0:0.084:2.372. Thus, li can be determined + 、Na + 、K + 、Ca 2+ 、Mg 2+ The molar ratio of (2) is 1:1371:136.6:11.19:521.1. the following Table II schematically shows Li + 、Na + 、K + 、Ca 2+ 、Mg 2+ Molar ratio and standard potential of (c).
The apparent potential (V, melt, vsNHE) and separation factor (Li, M) of element M (M is, for example, li and Na, K, ca, mg) in molten salt calculated in the examples of the present application are schematically shown in table three below. Fig. 6 illustrates a schematic diagram of separation factors of different elements according to an embodiment of the application.
At step 306, molten salt is provided to an electrorefining furnace.
At step 308, the calculated electrode potentials are applied to the electrodes of the electrorefining furnace so as to cause the sequential deposition of metallic lithium and other elements on the electrodes, the electrode potentials being associated with deposition potentials of metallic lithium and other elements, respectively.
In some embodiments, for example, the predetermined electrolytic current is continuously applied such that the electrode potential varies with the predetermined electrolytic current so that magnesium metal precipitates for deposition on the electrode; and causing the metallic lithium to precipitate for deposition on the electrode. By controlling the electrolysis current, magnesium is deposited on the electrode first, and then lithium is deposited on the electrode.
In some embodiments, a first electrode potential is applied to the electrode such that magnesium metal precipitates for deposition on the electrode; and applying a second electrode potential to the electrode such that the metallic lithium precipitates for deposition on the electrode. The second electrode potential is, for example, lower than the first electrode potential. The first electrode potential is, for example, -1.88V. The second electrode potential is, for example, a potential in the range of-2.43 to-2.67V.
The foregoing description of embodiments of the application has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (11)
1. A method for extracting lithium from a salt lake, the method comprising:
pretreating the obtained salt lake brine to generate pretreated lithium-containing crystalline powder, wherein the pretreatment at least comprises steaming and sunning the salt lake brine;
mixing a predetermined modulating salt in a predetermined proportion in the lithium-containing crystalline powder based on the sampling data about the lithium-containing crystalline powder and the target melting point of the mixture to produce a mixture of mixed predetermined modulating salts, the predetermined modulating salt being used to reduce the melting point of the mixture of mixed predetermined modulating salts;
heating the mixed predetermined salt mixture to produce molten salt; and
electrolytic separation is performed with respect to the molten salt using an electrode so that metallic lithium is deposited on the electrode.
2. The method of claim 1, wherein the predetermined proportion of the predetermined salt is determined via the steps of:
optimizing stable phases existing under different components and temperatures in a multi-component system in the lithium-containing crystalline powder based on sampling data and a phase diagram calculation algorithm on the lithium-containing crystalline powder component so as to obtain a solid-liquid phase line;
determining association data of melting points of the different components and the mixture based on the solidus and liquidus; and
and determining a predetermined modulation salt to be added and a predetermined proportion of the predetermined modulation salt to be added, which correspond to the target melting point, based on the target melting point of the mixture and the association relationship data of the different components and the melting point of the mixture.
3. The method of claim 1, wherein pre-treating the obtained salt lake brine to produce a pre-treated lithium-containing crystalline powder comprises:
steaming and sun-drying the obtained salt lake brine to enable sodium salt to reach saturated solubility and separate out so as to generate residual brine after sodium removal by concentration and separated out sodium salt; and
concentrating and crystallizing the generated residual brine to obtain crystallized salt mine.
4. The method of claim 3, wherein generating the residual brine after removal of sodium via concentration comprises:
at a control device, obtaining first sample data regarding a salt lake brine composition;
calculating a predetermined precipitation concentration threshold before the magnesium salt or lithium salt solution in the salt lake brine reaches the precipitation concentration based on the solubility product algorithm and the first sampling data; and
controlling steaming and drying of salt lake brine based on the calculated predetermined precipitation concentration threshold value so that sodium salt in the salt lake brine is precipitated after reaching solubility, so as to generate residual brine after sodium removal by concentration and precipitated sodium salt, wherein the residual brine after sodium removal by concentration comprises: saturated sodium, magnesium, calcium, potassium and lithium salt solutions having a concentration within a predetermined range from a predetermined precipitation concentration threshold.
5. The method of claim 3, wherein pre-treating the obtained salt lake brine to produce a pre-treated lithium-containing crystalline powder further comprises:
crushing the obtained block of the crystallized salt mine so as to obtain salt mine powder;
screening the salt mine powder to obtain screened target salt mine powder; and
vacuum baking and dewatering are carried out on the target salt mine powder to generate the lithium-containing crystal powder through pretreatment.
6. The method of claim 1, wherein the predetermined proportion of the predetermined modulating salt is determined via the steps of:
the predetermined proportion of the mixed predetermined modulation salt is determined based on the sampling data on the lithium-containing crystalline powder and the target melting point on the mixture of the mixed predetermined modulation salt and at least one of the target boiling point, the target saturated vapor pressure, the target viscosity, the target conductivity, and the target electrode potential on the molten salt.
7. The method of claim 1, wherein performing electrolytic separation of molten salt with an electrode to cause deposition of metallic lithium on the electrode comprises:
sampling the molten salt to obtain third sampled data about the composition of the molten salt;
calculating electrode potentials of the element lithium and other elements based on the Nernst equation and the third sampling data;
providing molten salt into an electrorefining furnace; and
the calculated electrode potential is applied to the electrodes of the electrorefining furnace so as to cause the sequential deposition of metallic lithium and other elements on the electrodes, said electrode potential being associated with the deposition potential of metallic lithium and other elements, respectively.
8. The method of claim 7, wherein causing metallic lithium and other elements to be sequentially deposited on the electrode comprises:
applying a first electrode potential to the electrode such that magnesium metal precipitates for deposition on the electrode; and
a second electrode potential is applied to the electrode such that metallic lithium precipitates for deposition on the electrode, the second electrode potential being lower than the first electrode potential.
9. The method of claim 7, wherein causing metallic lithium and other elements to be sequentially deposited on the electrode comprises:
continuously applying a predetermined electrolytic current such that the electrode potential varies with the predetermined electrolytic current so that metallic magnesium precipitates for deposition on the electrode; and
so that metallic lithium is precipitated to be deposited on the electrode.
10. The method of claim 1, wherein depositing lithium metal on the electrode comprises:
so that metallic magnesium, metallic sodium, metallic lithium, metallic potassium and calcium are sequentially deposited on the electrode.
11. The method of claim 1, wherein the predetermined modulating salt comprises: one or more of chloride, fluoride, nitrate and carbonate.
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