CN116964233A - Application of lithium ferricyanate, anolyte and salt lake brine water electrolysis lithium extraction method - Google Patents
Application of lithium ferricyanate, anolyte and salt lake brine water electrolysis lithium extraction method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 222
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 238000000605 extraction Methods 0.000 title claims abstract description 74
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 title claims description 22
- 239000012267 brine Substances 0.000 claims abstract description 84
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 84
- 238000009831 deintercalation Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000009830 intercalation Methods 0.000 claims abstract description 26
- 230000005611 electricity Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 25
- 239000003115 supporting electrolyte Substances 0.000 claims description 17
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 5
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 4
- 229910015207 Ni1/3Co1/3Mn1/3O Inorganic materials 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 claims 1
- 238000003809 water extraction Methods 0.000 claims 1
- 230000002687 intercalation Effects 0.000 abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 17
- -1 lithium iron cyanate Chemical compound 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 23
- 238000001179 sorption measurement Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000009296 electrodeionization Methods 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- MWCFXRVLEYZWBD-UHFFFAOYSA-N tetralithium;iron(2+);hexacyanide Chemical compound [Li+].[Li+].[Li+].[Li+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] MWCFXRVLEYZWBD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application belongs to the technical field of extracting lithium from brine, and particularly relates to application of lithium ferricyanate, an anolyte and a method for extracting lithium from salt lake brine by water and electricity, wherein the method comprises the steps of carrying out electric deintercalation and extraction on salt lake brine by adopting a salt lake brine water and electricity deintercalation and extraction device, wherein the salt lake brine water and electricity deintercalation and extraction device comprises an electrolytic tank, an anion exchange membrane, an anode and a cathode, the anion exchange membrane is arranged in the electrolytic tank to vertically divide the electrolytic tank into a cathode chamber and an anode chamber, the anode is arranged in the anode chamber, and the cathode is arranged in the cathode chamber; and applying voltage to the cathode and the anode to carry out electric deintercalation and extraction of lithium, and adding anode electrolyte into the anode chamber in the process of electric deintercalation and extraction of lithium. According to the lithium iron cyanate anode lithium ion sieve, lithium iron cyanate is used as an anode electrolyte to be added into an anode chamber, so that the intercalation amount of the cathode ion sieve can be ensured, the capacity of cathode and anode deintercalation lithium is more matched, and the lithium extraction efficiency is improved.
Description
Technical Field
The disclosure relates to the technical field of brine lithium extraction, in particular to application of lithium ferricyanate, an anolyte and a salt lake brine water electrolysis lithium extraction method.
Background
The extraction and recovery method of the lithium resource of the salt lake brine comprises an electrodialysis method, an evaporation crystallization method, a solvent extraction method, a precipitation method, an ion exchange method and an adsorption method. The adsorption method has lower cost and higher efficiency. However, in the exchange adsorption process, acid washing is required to produce secondary waste, and the permeability and solubility of the adsorbent are poor, which severely limits the industrial application thereof. The solvent extraction method has high yield, simple operation and easy industrial scale-up, but the method uses a large amount of organic solvent, which is easy to cause environmental pollution and equipment corrosion. The traditional lithium extraction method has the defects of high cost, high energy consumption, low separation efficiency and the like. The electric deintercalation is a new research direction for extracting lithium from the salt lake, and is a green and efficient technology for extracting lithium from the salt lake.
Electrochemical lithium extraction is developed according to the working principle of a lithium iron phosphate ion battery. The specific application thought is as follows: the reverse working principle of the lithium battery deintercalation with the aqueous solution is essentially that lithium ions in the solution are intercalated in a cathode material and then are subjected to subsequent treatment, the lithium ion-deintercalation battery anode material with a memory effect is adopted as an electrode material, salt lake brine is taken as a catholyte, and a supporting electrolyte without magnesium is taken as an anolyte, so that an electrochemical deintercalation system of 'lithium-rich adsorption material-supporting electrolyte-anion membrane-brine-lithium-deficient adsorption material' is formed. In the electrolysis process, electrons obtained from the cathode undergo a reduction reaction, so that lithium ions in salt lake brine are inserted into cathode materials, separation is further realized, and the effect of high-efficiency lithium extraction is finally realized through subsequent treatment and separation operation.
CN102382984B discloses a "rocking chair type" electrode system (LiFePO 4 /FePO 4 ) The method for extracting lithium by electric deintercalation comprises the following steps: the cell is divided by an anion selective exchange membrane into two compartments: liFePO is prepared 4 The electrode was placed in a recovery solution (0.5 mol/L NaCl), fePO 4 Placing in raw material liquid (lithium-containing brine). LiFePO under electric field 4 The anode performs oxidation (lithium removal) reaction, and the cathode performs reduction (lithium intercalation) reaction. Anions (Cl) in the raw material liquid in the process - ) Will migrate across the intermediate anion exchange membrane into the recovery liquid.
For ideal lithium extraction reaction, the anode extracts one lithium ion and the cathode also inserts one lithium ion, but in the actual reaction process, the cathode lithium intercalation process is influenced by the viscosity of brine and the concentration of lithium ions in the solution, so that the cathode lithium intercalation process is slower than the anode lithium intercalation process, the problems of cathode lithium removal and lithium intercalation capacity mismatch are caused, and especially when the operating voltage is increased, the speed difference of cathode lithium intercalation is increased. Using LiFePO 4 -FePO 4 The system is used for extracting lithium, and the polarities of the two electrodes are required to be continuously changed, so that the electrode materials coated on the cathode and the anode are required to be kept as consistent as possible, and the capacity matching design of the cathode and the anode cannot be carried out through the improvement of the electrodes. CN115818801A discloses the use of Pb-FePO 4 The system performs electrodeintercalation and extraction of lithium, and FePO is used 4 As a cathode, pb is used as an anode to absorb lithium in brine, and then the brine is replaced to remove lithium ions, so that the capacity of lithium removal and lithium intercalation of a cathode and an anode can be more matched, but the lithium extraction process is divided into two steps of lithium intercalation and lithium removal, so that the lithium extraction process is complicated, and the lithium extraction efficiency is affected.
In view of this, the present disclosure is specifically proposed.
Disclosure of Invention
The purpose of the disclosure comprises providing application of lithium ferricyanate in preparing anolyte for extracting lithium from brine water in salt lake.
Objects of the present disclosure include providing the use of lithium ferricyanate in the preparation of an anolyte for reducing lithium intercalation and deintercalation rate differences of cathodes and anodes in lithium intercalation and deintercalation of lake brine power.
The purpose of the disclosure also comprises providing an anolyte for extracting lithium by water electrolysis of salt lake brine.
The purpose of the disclosure also comprises providing a method for extracting lithium by water and electricity extraction of salt lake brine.
The purpose of the disclosure also includes providing a resource recovery method of salt lake brine.
In order to achieve at least one of the above objects of the present disclosure, the following technical solutions may be adopted:
in a first aspect, the present disclosure provides the use of lithium ferricyanate in the preparation of an anolyte for the extraction of lithium from salt lake brine electrolysis.
In a second aspect, the present disclosure provides the use of lithium ferricyanate in the preparation of an anolyte for reducing the lithium intercalation and deintercalation rate difference of a cathode and an anode in lithium extraction from a lake brine.
In some embodiments of the present disclosure, the lithium ferricyanate is added to the anode compartment of a salt lake brine hydropower deintercalation lithium extraction system.
In some embodiments of the present disclosure, the concentration of the lithium ferricyanate in the anolyte is 0.05-1mol/L.
In some embodiments of the present disclosure, the concentration of the lithium ferricyanate in the anolyte is 0.2-0.5mol/L.
In some embodiments of the present disclosure, the anolyte further comprises a supporting electrolyte.
In some embodiments of the present disclosure, the supporting electrolyte comprises lithium chloride.
In some embodiments of the present disclosure, the concentration of the lithium chloride in the anolyte is 40-60mmol/L.
In a third aspect, the present disclosure provides a salt lake brine hydropower deintercalation lithium-extracting anolyte, the components of which include lithium ferricyanate.
In some embodiments of the present disclosure, the concentration of the lithium ferricyanate in the anolyte is 0.05-1mol/L.
In some embodiments of the present disclosure, the composition further comprises a supporting electrolyte.
In some embodiments of the present disclosure, the supporting electrolyte comprises lithium chloride.
In some embodiments of the present disclosure, the concentration of the lithium chloride in the anolyte is 40-60mmol/L.
In a fourth aspect, the present disclosure provides a method for extracting lithium from brine, by water and electricity extraction in a salt lake, comprising:
the method comprises the steps that a salt lake brine water and electricity deintercalation lithium extraction device is adopted to carry out electric deintercalation lithium extraction on salt lake brine, the salt lake brine water and electricity deintercalation lithium extraction device comprises an electrolytic tank, an anion exchange membrane, an anode and a cathode, wherein the anion exchange membrane is arranged in the electrolytic tank to vertically divide the electrolytic tank into a cathode chamber and an anode chamber, the anode is arranged in the anode chamber, and the cathode is arranged in the cathode chamber;
and applying voltage to the cathode and the anode to carry out electric deintercalation and extraction of lithium, wherein in the electric deintercalation and extraction process of lithium, the anode chamber is internally added with the anolyte for the aqueous deintercalation and extraction of lithium of salt lake brine according to any one of the previous embodiments.
In some embodiments of the present disclosure, the lithium ferricyanate is added to the anode chamber before or during the initiation of the electrodeintercalation of lithium.
In some embodiments of the present disclosure, the voltage applied to the cathode and the anode is 0.4-0.8V.
In some embodiments of the present disclosure, the time for extracting lithium by electrodeionization is 2 to 6 hours.
In some embodiments of the present disclosure, after the end of the electrical deintercalation and extraction of lithium, the method further comprises changing the positions of the cathode and the anode, applying a voltage, and repeating the above steps until the enrichment of lithium from the cathode chamber to the anode chamber is completed, thereby forming a lithium-rich solution.
In some embodiments of the present disclosure, the concentration of lithium in the lithium-rich liquid is 3.5-4.1g/L.
In some embodiments of the present disclosure, the salt lake brine comprises lithium-containing brine.
In some embodiments of the present disclosure, the salt lake brine includes one or more of sulfate-type brine, chloride-type brine, and carbonate-type brine.
In some embodiments of the present disclosure, the cathode comprises FePO 4 、Li 1-x Mn 2 O 4 、Li 1-x Ni 1/3 Co 1/3 Mn 1/ 3 O 2 And Li (lithium) 7-x Ti 5 O 12 At least one of them.
In some embodiments of the present disclosure, the anode comprises LiFePO 4 、LiMn 2 O 4 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 And Li (lithium) 7 Ti 5 O 12 At least one of them.
In a fifth aspect, the present disclosure provides a method for recovering resources of salt lake brine, comprising a method for extracting lithium by hydro-power deintercalation of salt lake brine according to any one of the above embodiments.
Compared with the prior art, the beneficial effects of the present disclosure include:
as LiFePO is adopted in the rocking chair type electrochemical lithium extraction system 4 -FePO 4 The electrode system carries out lithium extraction reaction, liFePO 4 Is significantly faster than FePO 4 The larger the lithium intercalation rate difference between the cathode and anode, the more mismatched the lithium intercalation and deintercalation capacities will be, especially when treating low-concentration lithium-containing solutions. The present disclosure provides a novel use of lithium ferricyanate by combining lithium ferricyanate Li 4 Fe(CN) 6 As the anolyte is added into the anode chamber, the time of the electrodeionization increases, and Li in the anode chamber 4 Fe(CN) 6 Oxidation reaction occurs under the condition of electrification, fe (CN) 6 ) 4- →Fe(CN 6 ) 3- Resulting in reduced lithium ion extraction from the anode and ensuring FePO of the cathode 4 Can fully conduct lithium intercalation, fully ensure the adsorption capacity of the electrode, reduce the problem of capacity mismatch and improve the recovery rate of lithium.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
Fig. 1 is a working schematic diagram of a salt lake brine water electrolysis and intercalation lithium extraction method provided by the present disclosure.
Detailed Description
Embodiments of the present disclosure will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The endpoints of the ranges and any values disclosed in this disclosure are not limited to the precise range or value, and such range or value should be understood to encompass values approaching those range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present disclosure provides a new application of lithium ferricyanate, in particular, the present disclosure provides an application of lithium ferricyanate in preparing anolyte for salt lake brine electrolysis and lithium extraction.
In the disclosure, lithium ferricyanate is obtained by commercial purchase, and a manufacturer of the lithium ferricyanate is Hunan Han run material development limited company, and the research discovers that the lithium ferricyanate is added into an anode chamber as an anode electrolyte in the electric deintercalation and extraction of lithium from lake brine, so that oxidation reaction can occur in the electric deintercalation process to reduce the deintercalation amount of anode lithium ions, further the lithium deintercalation rate difference of a cathode and an anode is reduced, and simultaneously the lithium deintercalation capacity difference and the lithium intercalation capacity difference can also be reduced.
In the present disclosure, lithium ferricyanate is dissolved in the solution in the anode compartment to form a lithium ferricyanate solution. The concentration of lithium iron cyanate in the anolyte is 0.05-1mol/L, alternatively, the concentration of lithium iron cyanate in the anolyte is 0.2-0.5mol/L. In certain embodiments, the concentration of lithium ferrocyanide in the anolyte may be, for example, any one of 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or a range value therebetween.
In this regard, the present application also provides an anolyte for the water and electricity deintercalation of salt lake brine to extract lithium, the component of which comprises lithium ferrocyanide, the concentration of lithium ferrocyanide in the anolyte is 0.05-1mol/L, and in some embodiments, the concentration of lithium ferrocyanide in the anolyte may be, for example, any one of 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or a range value between any two thereof.
In certain embodiments, the composition further comprises a supporting electrolyte comprising lithium chloride, the concentration of lithium chloride in the anolyte being 40-60mmol/L.
The disclosure also provides a method for extracting lithium from brine by water and electricity extraction of salt lake brine, which comprises the following steps:
s1, forming an electrode system.
The anode and the cathode are selected to form an electrode system, and an anion exchange membrane is used for vertically dividing the electrolytic cell into a cathode chamber and an anode chamber.
The present disclosure may be applicable to a variety of electrode systems, including but not limited to LiFePO 4 /FePO 4 、LiMn 2 O 4 /Li 1-x Mn 2 O 4 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li 1-x Ni 1/3 Co 1/3 Mn 1/3 O 2 、Li 7 Ti 5 O 12 /Li 7-x Ti 5 O 12 Etc., in particular, the cathode comprises FePO 4 、Li 1-x Mn 2 O 4 、Li 1-x Ni 1/3 Co 1/3 Mn 1/3 O 2 And Li (lithium) 7-x Ti 5 O 12 Wherein x represents an under-lithium state. The anode comprises LiFePO 4 、LiMn 2 O 4 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 And Li (lithium) 7 Ti 5 O 12 At least one of them. In the present disclosure, the anion exchange membrane is a monovalent selective anion exchange membrane, which is commercially available from the manufacturer of sandisrael technologies, inc.
S2, adding the solution.
Salt lake brine of lithium to be extracted is added into the cathode chamber, supporting electrolyte and lithium ferricyanate are added into the anode chamber, and the adding time point of the lithium ferricyanate can be added into the anode chamber before or during the beginning of the electrodeintercalation lithium extraction.
The salt lake brine can be any lithium-containing salt lake brine, and mainly aims at brine with high magnesium-lithium ratio. Salt lake brines include, but are not limited to, one or more of sulfate brines, chloride brines, and carbonate brines. In some embodiments of the present disclosure, the composition of the salt lake brine comprises 0.21-0.47g/L Li + 、69.3g/L Na + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/L Ca 2+ 、8.24g/L SO 4 2- 。
The supporting electrolyte comprises lithium chloride with a concentration of 40-60mmol/L.
The concentration of the lithium ferricyanate solution is in the range of 0.05-1mol/L, and in certain embodiments, the concentration of the lithium ferricyanate solution may be, for example, any one of 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or a range value between any two.
S3, extracting lithium by electric stripping.
And applying voltage to the cathode and the anode to perform electrical deintercalation and extraction of lithium. The applied voltage is 0.4-0.8V, and the time for extracting lithium by electrical deintercalation is 2-6h.
In certain embodiments, the applied voltage may be, for example, any one or a range of values between any two of 0.4V, 0.5V, 0.6V, 0.7V, 0.8V. The time of extracting lithium by electric deintercalation is any one or any range value between any two of 2h, 3h, 4h, 5h and 6h.
S4, exchanging electrode positions.
After the electrodeintercalation and lithium extraction are finished, the positions of the cathode and the anode are exchanged, voltage is applied, and the steps are repeated until the enrichment of lithium from the cathode chamber to the anode chamber is completed, so that lithium-rich liquid is formed, and the concentration of lithium in the lithium-rich liquid is 3.5-4.1g/L.
Referring to fig. 1, the lithium extraction process according to the present disclosure mainly includes: liFePO under the action of electric field 4 The anode releases lithium ions into the anolyte (lithium ferricyanate + supporting electrolyte) to form FePO 4 At the same time FePO 4 Cathode absorbs lithium ions in lithium-containing brine to form LiFePO 4 The method comprises the steps of carrying out a first treatment on the surface of the Exchanging the cathode and anode, repeating the above process, enriching the lithium cathode chamber in the salt lake brine into the anode chamber, in the present disclosure, by adding lithium ferricyanate into the anode chamber, along with the increase of the electrodeintercalation time, the Li in the anode chamber at this time 4 Fe(CN) 6 Oxidation reaction occurs under the condition of electrification, fe (CN) 6 ) 4- →Fe(CN 6 ) 3- Resulting in reduced lithium ion extraction from the anode and ensuring FePO of the cathode 4 Can fully conduct lithium intercalation, fully ensure the adsorption capacity of the electrode, reduce the problem of capacity mismatch and improve the recovery rate of lithium.
The disclosure provides a resource recovery method of salt lake brine, which comprises the method for extracting lithium by water and electricity deintercalation of salt lake brine.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
Example 1
The embodiment provides a salt lake brine water electrolysis and lithium extraction method, which comprises the following steps:
(1) Using LiFePO 4 Is anode, liFePO 4 FePO after delithiation 4 As cathode with monovalent selective anionsThe exchange membrane divides the cathode and anode into a cathode chamber and an anode chamber.
(2) Injecting salt lake brine to be extracted with lithium into a cathode chamber, and adding Li into an anode chamber 4 Fe(CN) 6 And a supporting electrolyte (lithium chloride), li 4 Fe(CN) 6 The solution and lithium chloride together act as an anolyte.
The brine comprises the following components: 0.47g/L Li + 、69.3g/L Na + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/LCa 2+ 、8.24g/L SO 4 2- 。
Li in the anolyte 4 Fe(CN) 6 The concentration of (C) was 0.3mol/L, and the concentration of lithium chloride was 50mmol/L.
(3) A voltage of 0.6V was applied across the cathode and anode for a period of 4h.
(4) After the two electrodes respectively complete the corresponding inserting/extracting process, the positions of the two electrodes are exchanged, the process is repeated once, the reaction is stopped when the current is reduced to 0.3mA, and the enrichment of lithium from the cathode chamber to the anode chamber can be realized, so that lithium-rich liquid is formed.
Example 2
The embodiment provides a salt lake brine water electrolysis and lithium extraction method, which comprises the following steps:
(1) Using LiFePO 4 Is anode, liFePO 4 FePO after delithiation 4 As the cathode, a monovalent selective anion exchange membrane is used to divide the cathode and anode into a cathode chamber and an anode chamber.
(2) Injecting salt lake brine to be extracted with lithium into a cathode chamber, and adding Li into an anode chamber 4 Fe(CN) 6 And a supporting electrolyte (lithium chloride), li 4 Fe(CN) 6 The solution and lithium chloride together act as an anolyte.
The brine comprises the following components: 0.47g/L Li + 、69.3g/L Na + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/LCa 2+ 、8.24g/L SO 4 2- 。
Li in the anolyte 4 Fe(CN) 6 The concentration of (C) was 0.5mol/L, and the concentration of lithium chloride was 50mmol/L.
(3) A voltage of 0.4V was applied across the cathode and anode for a period of 6h.
(4) After the two electrodes respectively complete the corresponding inserting/extracting process, the positions of the two electrodes are exchanged, the process is repeated once, the reaction is stopped when the current is reduced to 0.3mA, and the enrichment of lithium from the cathode chamber to the anode chamber can be realized, so that lithium-rich liquid is formed.
Example 3:
the embodiment provides a salt lake brine water electrolysis and lithium extraction method, which comprises the following steps:
(1) Using LiFePO 4 Is anode, liFePO 4 FePO after delithiation 4 As the cathode, a monovalent selective anion exchange membrane is used to divide the cathode and anode into a cathode chamber and an anode chamber.
(2) Injecting salt lake brine to be extracted with lithium into a cathode chamber, and adding Li into an anode chamber 4 Fe(CN) 6 And a supporting electrolyte (lithium chloride), li 4 Fe(CN) 6 The solution and lithium chloride together act as an anolyte.
The brine comprises the following components: 0.47g/L Li + 、69.3g/L Na + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/LCa 2+ 、8.24g/L SO 4 2- 。
Li in the anolyte 4 Fe(CN) 6 The concentration of (C) was 0.05mol/L, and the concentration of lithium chloride was 50mmol/L.
(3) A voltage of 0.8V was applied across the cathode and anode for 2h.
(4) After the two electrodes respectively complete the corresponding inserting/extracting process, the positions of the two electrodes are exchanged, the process is repeated once, the reaction is stopped when the current is reduced to 0.3mA, and the enrichment of lithium from the cathode chamber to the anode chamber can be realized, so that lithium-rich liquid is formed.
Example 4:
the embodiment provides a salt lake brine water electrolysis and lithium extraction method, which comprises the following steps:
(1) Using LiFePO 4 Is anode, liFePO 4 FePO after delithiation 4 As the cathode, a monovalent selective anion exchange membrane is used to divide the cathode and anode into a cathode chamber and an anode chamber.
(2) And injecting salt lake brine of lithium to be extracted into the cathode chamber, and adding lithium chloride solution into the anode chamber as anode electrolyte.
The brine comprises the following components: 0.47g/L Li + 、69.3g/L Na + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/LCa 2+ 、8.24g/L SO 4 2- 。
The concentration of lithium chloride in the anolyte was 50mmol/L.
(3) Applying a voltage of 0.8V to both ends of the cathode and anode, adding Li into the anode chamber solution after the electric deintercalation reaction is carried out for 3 hours 4 Fe(CN) 6 Li in the anolyte 4 Fe(CN) 6 The concentration of (C) was 0.35mol/L, and electrolysis was continued for 1 hour.
(4) After the two electrodes respectively complete the corresponding inserting/extracting process, the positions of the two electrodes are exchanged, the process is repeated once, the reaction is stopped when the current is reduced to 0.3mA, and the enrichment of lithium from the cathode chamber to the anode chamber can be realized, so that lithium-rich liquid is formed.
Example 5
The difference between this example and example 1 is that the voltage applied by the electrical detachment in step (3) is 0.4V, and the other steps are the same as in example 1.
Example 6
The difference between this example and example 1 is that the voltage applied by the electrical detachment in step (3) is 0.8V, and the other steps are the same as in example 1.
Example 7
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 0.1mol/L, and the other steps were the same as in example 1.
Example 8
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 0.2mol/L, and the other steps were the same as in example 1.
Example 9
This embodimentThe difference from example 1 is Li in the step (3) 4 Fe(CN) 6 The concentration of (C) was 0.4mol/L, and the other steps were the same as in example 1.
Example 10
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 0.5mol/L, and the other steps were the same as in example 1.
Example 11
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 0.6mol/L, and the other steps were the same as in example 1.
Example 12
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 0.8mol/L, and the other steps were the same as in example 1.
Example 13
The difference between this example and example 1 is Li in step (3) 4 Fe(CN) 6 The concentration of (C) was 1mol/L, and the other steps were the same as in example 1.
Example 14
The difference between this example and example 1 is that the concentration of lithium chloride in step (3) is 40mol/L, and the other steps are the same as in example 1.
Example 15
The difference between this example and example 1 is that the concentration of lithium chloride in step (3) is 60mol/L, and the other steps are the same as in example 1.
Example 16
The difference between this example and example 1 is LiMn in step (1) 2 O 4 Is anode, li 1-x Mn 2 O 4 The other steps were the same as in example 1 except that the cathode was used.
Example 17
The difference between this example and example 1 is that the brine in step (2) has the following composition: 0.47g/L Li + 、69.3g/LNa + 、111.20g/L Mg 2+ 、6.43g/L K + 、2.99g/L Ca 2+ 、8.24g/L SO 4 2- 。
Comparative example 1
This comparative example is substantially the same as example 1 except that in step (3) of this comparative example, li is not added in the anode chamber 4 Fe(CN) 6 Only a lithium chloride solution (lithium chloride concentration: 50 mmol/L) was added, and the other steps were the same as in example 1.
Comparative example 2
This comparative example is substantially the same as example 1 except that in step (3) of this comparative example, only Li was added in the anode chamber 4 Fe(CN) 6 Wherein Li is 4 Fe(CN) 6 The concentration of (C) was 0.3mol/L, and the procedure was the same as in example 1 except that a lithium chloride solution was not added.
Comparative example 3
This comparative example is substantially the same as example 1 except that in step (3) of this comparative example, li is added in the anode chamber 4 Fe(CN) 6 The concentration of (C) was 0.01mol/L.
Comparative example 4
This comparative example is substantially the same as example 1 except that in step (3) of this comparative example, li is added in the anode chamber 4 Fe(CN) 6 The concentration of (C) was 1.5mol/L.
Comparative example 5
The difference between this example and example 1 is that the voltage applied by the electrical detachment in step (3) is 0.2V, and the other steps are the same as in example 1.
Comparative example 6
The difference between this example and example 1 is that the voltage applied by the electrodeionization in step (3) was 1.0V, and the other steps were the same as in example 1.
Comparative example 7
This comparative example is substantially the same as example 1 except that Li is added to the anode chamber in step (3) of this comparative example 4 Fe(CN) 6 Instead of potassium sulfate.
And (3) performance detection:
the main indexes of the extracted lithium obtained after the lithium extraction experiments on the electrodes obtained in the examples and comparative examples are shown in the following table.
Wherein, the calculation method of the lithium recovery rate is (C 0 -C e )/C 0 ×100％。C 0 The measurement unit is g/L for the initial brine lithium ion concentration; c (C) e The measurement unit is g/L for the concentration of lithium ions in brine after electrolysis.
The calculation method of the concentration of the obtained lithium-rich liquid is direct detection.
The electrode adsorption capacity was calculated as adsorption capacity q=v (C 0 -C e ) And/m. V is brine volume, and the unit volume is 1L; c (C) 0 The measurement unit is g/L for the initial brine lithium ion concentration; c (C) e The measurement unit is g/L for the concentration of lithium ions in brine after electrolysis; m is the mass of the electrode material, and the unit weight is 1g.
From examples 1, examples 5 to 6 and comparative examples 5 and 6, it was found that the adsorption capacity of the electrode was reduced when the voltage was too large or too small, because the electrode lithium extraction efficiency was too low and the voltage was too large to cause Fe (CN 6) 3- Oxidation has too strong inhibition effect on lithium removal.
It can be seen from example 1, examples 7 to 13 and comparative examples 3 to 4 that when Li 4 Fe(CN) 6 The concentration of (C) is controlled to be 0.2-0.5mol/L, which is more favorable for the increase of the adsorption capacity of the electrode.
It can be seen from examples 1 and examples 14-15 that the lithium extraction index does not differ much when the concentration of lithium chloride is within the scope of the present disclosure.
As can be seen from examples 1 and examples 16-17, the methods provided by the present disclosure are applicable to a variety of electrode systems, as well as to a variety of brines.
As can be seen from example 1 and comparative example 1, li was added to the recovered liquid 4 Fe(CN) 6 Can obviously increase the adsorption capacity of the electrode, thereby improving the concentration of lithium in the recovery liquid and the recovery rate of lithium,description of Li addition in anode 4 Fe(CN) 6 The intercalation amount of the cathode ion sieve can be ensured, so that the capacity of cathode and anode deintercalation lithium is more matched, and the lithium extraction efficiency is improved.
As can be seen from example 1 and comparative example 2, only Li was used 4 Fe(CN) 6 As an anolyte, li alone 4 Fe(CN) 6 The ionization equilibrium constant of (2) is not high, resulting in a significantly lower lithium extraction index than in example 1, where Li is used 4 Fe(CN) 6 The supporting electrolyte is used as the anode electrolyte together, so that the conductivity of the solution can be improved, and the lithium extraction efficiency is improved.
As can be seen from example 1 and comparative example 7, other reagents were selected instead of Li 4 Fe(CN) 6 When this is the case, the effect is significantly worse than in example 1.
In summary, as LiFePO is adopted in the rocking chair type electrochemical lithium extraction system 4 -FePO 4 The electrode system carries out lithium extraction reaction, liFePO 4 Is significantly faster than FePO 4 The larger the lithium intercalation rate difference between the cathode and anode, the more mismatched the lithium intercalation and deintercalation capacities will be, especially when treating low-concentration lithium-containing solutions. The present disclosure provides a novel use of lithium ferricyanate by combining lithium ferricyanate Li 4 Fe(CN) 6 As the anolyte is added into the anode chamber, the time of the electrodeionization increases, and Li in the anode chamber 4 Fe(CN) 6 Oxidation reaction occurs under the condition of electrification, fe (CN) 6 ) 4- →Fe(CN 6 ) 3- Resulting in reduced lithium ion extraction from the anode and ensuring FePO of the cathode 4 Can fully conduct lithium intercalation, fully ensure the adsorption capacity of the electrode, reduce the problem of capacity mismatch and improve the recovery rate of lithium.
The above describes in detail the optional embodiments of the present disclosure, but the present disclosure is not limited thereto. Within the scope of the technical idea of the present disclosure, various simple modifications may be made to the technical solution of the present disclosure, including that each technical feature is combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosure of the present disclosure, which falls within the protection scope of the present disclosure.
Industrial applicability
As LiFePO is adopted in the rocking chair type electrochemical lithium extraction system 4 -FePO 4 The electrode system carries out lithium extraction reaction, liFePO 4 Is significantly faster than FePO 4 The larger the lithium intercalation rate difference between the cathode and anode, the more mismatched the lithium intercalation and deintercalation capacities will be, especially when treating low-concentration lithium-containing solutions. The present disclosure provides a novel use of lithium ferricyanate by combining lithium ferricyanate Li 4 Fe(CN) 6 As the anolyte is added into the anode chamber, the time of the electrodeionization increases, and Li in the anode chamber 4 Fe(CN) 6 Oxidation reaction occurs under the condition of electrification, fe (CN) 6 ) 4- →Fe(CN 6 ) 3- Resulting in reduced lithium ion extraction from the anode and ensuring FePO of the cathode 4 Can fully conduct lithium intercalation, fully ensure the adsorption capacity of the electrode, reduce the problem of capacity mismatch and improve the recovery rate of lithium.
Claims (24)
1. Application of lithium ferricyanate in preparing anolyte for extracting lithium from brine in salt lake by water and electricity desorption.
2. The application of lithium ferricyanate in preparing the anode electrolyte for reducing the lithium intercalation-deintercalation rate difference of cathode and anode in extracting lithium from lake brine.
3. The use according to claim 1 or 2, wherein the lithium ferricyanate is added into the anode compartment of a salt lake brine hydropower deintercalation lithium extraction system.
4. The use according to claim 1 or 2, characterized in that the concentration of lithium ferricyanate in the anolyte is 0.05-1mol/L.
5. The use according to claim 1 or 2, characterized in that the concentration of lithium ferricyanate in the anolyte is 0.2-0.5mol/L.
6. The use according to claim 1 or 2, wherein the anolyte further comprises a supporting electrolyte.
7. The use of claim 6, wherein the supporting electrolyte comprises lithium chloride.
8. The use according to claim 7, characterized in that the concentration of lithium chloride in the anolyte is 40-60mmol/L.
9. The anolyte for extracting lithium by water and electricity extraction of salt lake brine is characterized by comprising the following components of lithium ferrocyanate.
10. The anolyte of claim 9 wherein the concentration of lithium ferricyanate in the anolyte is from 0.05 to 1mol/L.
11. The anolyte of salt lake brine hydropower deintercalation of lithium of any one of claims 9-10 wherein the composition further comprises a supporting electrolyte.
12. The anolyte of salt lake brine hydropower deintercalation of lithium of claim 11 wherein the supporting electrolyte comprises lithium chloride.
13. The anolyte of salt lake brine hydropower deintercalation and extraction of lithium of claim 12, wherein the concentration of lithium chloride in the anolyte is 40-60mmol/L.
14. The method for extracting lithium by water and electricity extraction of salt lake brine is characterized by comprising the following steps of:
the method comprises the steps that a salt lake brine water and electricity deintercalation lithium extraction device is adopted to carry out electric deintercalation lithium extraction on salt lake brine, the salt lake brine water and electricity deintercalation lithium extraction device comprises an electrolytic tank, an anion exchange membrane, an anode and a cathode, wherein the anion exchange membrane is arranged in the electrolytic tank to vertically divide the electrolytic tank into a cathode chamber and an anode chamber, the anode is arranged in the anode chamber, and the cathode is arranged in the cathode chamber;
applying voltage to the cathode and the anode to carry out electric deintercalation and extraction of lithium, wherein the anode chamber is internally added with the anolyte for the salt lake brine electrolysis and deintercalation and extraction of lithium in the electric deintercalation and extraction of lithium.
15. The method for extracting lithium from salt lake brine by water electrolysis according to claim 14, wherein the lithium ferricyanate is added into the anode chamber before or during the beginning of the extraction of lithium from the brine electrolysis.
16. A salt lake brine hydropower deintercalation lithium extraction method according to any one of claims 14-15, wherein the voltage applied to the cathode and the anode is 0.4-0.8V.
17. The method for extracting lithium from salt lake brine by water electrolysis according to any one of claims 14 to 16, wherein the time for extracting lithium by water electrolysis is 2 to 6 hours.
18. The method of any one of claims 14-17, further comprising changing the positions of the cathode and the anode after the electrointercalation lithium extraction is completed, applying a voltage, and repeating the above steps until the enrichment of lithium from the cathode chamber to the anode chamber is completed, thereby forming a lithium-rich solution.
19. The method for extracting lithium from salt lake brine by water electrolysis and de-intercalation according to claim 18, wherein the concentration of lithium in the lithium-rich solution is 3.5-4.1g/L.
20. The method for the aqueous dehydrointercalation of lithium from a salt lake brine according to any one of claims 14-19 wherein the salt lake brine comprises lithium-containing brine.
21. The method of claim 14-20, wherein the salt lake brine comprises one or more of sulfate-type brine, chloride-type brine, and carbonate-type brine.
22. A salt lake brine hydropower deintercalation lithium extraction method according to any one of claims 14-21, wherein the cathode comprises FePO 4 、Li 1-x Mn 2 O 4 、Li 1-x Ni 1/3 Co 1/3 Mn 1/3 O 2 And Li (lithium) 7-x Ti 5 O 12 At least one of them.
23. A salt lake brine hydropower deintercalation lithium extraction method according to any one of claims 14-22, wherein the anode comprises LiFePO 4 、LiMn 2 O 4 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 And Li (lithium) 7 Ti 5 O 12 At least one of them.
24. A method for recovering lithium from salt lake brine, which comprises the method for extracting lithium from salt lake brine by water electrolysis and water extraction according to any one of claims 14 to 23.
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