CN116497232A - Continuous cation exchange membrane/solvent extraction/FCDI synergistic coupling lithium extraction method - Google Patents
Continuous cation exchange membrane/solvent extraction/FCDI synergistic coupling lithium extraction method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 99
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 238000005341 cation exchange Methods 0.000 title claims abstract description 66
- 238000000605 extraction Methods 0.000 title claims abstract description 27
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 16
- 238000000409 membrane extraction Methods 0.000 title claims abstract description 11
- 238000010168 coupling process Methods 0.000 title claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 9
- 230000008878 coupling Effects 0.000 title claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 title description 5
- 239000012267 brine Substances 0.000 claims abstract description 103
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- 230000005684 electric field Effects 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 209
- 239000002002 slurry Substances 0.000 claims description 200
- 239000000243 solution Substances 0.000 claims description 109
- 239000007788 liquid Substances 0.000 claims description 100
- 238000003795 desorption Methods 0.000 claims description 70
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 52
- 239000003011 anion exchange membrane Substances 0.000 claims description 52
- 238000005086 pumping Methods 0.000 claims description 50
- 150000001450 anions Chemical class 0.000 claims description 30
- 239000011780 sodium chloride Substances 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 16
- 230000008929 regeneration Effects 0.000 claims description 16
- 238000011069 regeneration method Methods 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 13
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 13
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 9
- -1 azo ion Chemical class 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 239000002482 conductive additive Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000002003 electrode paste Substances 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 32
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000011267 electrode slurry Substances 0.000 abstract description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- 238000002242 deionisation method Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000010354 integration Effects 0.000 abstract 1
- 230000002572 peristaltic effect Effects 0.000 description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 238000013508 migration Methods 0.000 description 13
- 230000005012 migration Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/302—Ethers or epoxides
- C22B3/304—Crown ethers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a continuous lithium extraction method by cooperative coupling of a cation exchange membrane/solvent extraction/flow capacitance deionization technology (FCDI), which utilizes the advantages of high efficiency and high concentration multiplying power of the FCDI technology in the field of salt concentration and the high selectivity characteristics of the cation exchange membrane and the solvent extraction technology in the field of salt lake lithium resource extraction, and realizes the selective separation and enrichment of lithium ions in salt lake brine through the system integration of a cation exchange membrane/solvent extraction/FCDI process unit under the driving action of an electric field. The organic reagent is used in small amount and can be recycled. The continuous operation of adsorption-desorption of the carbon particle flowing electrode slurry for recycling can be completed, and the content of magnesium in lithium-containing brine is well reduced, so that the purposes of separating magnesium and lithium and extracting lithium are achieved. The method has the advantages of high selectivity, high energy utilization efficiency, environmental friendliness, realization of high-efficiency separation and high-power concentration of lithium ions, and the like, and has remarkable technical advantages and application prospects in the application of recovering lithium from high-Mg/Li brine.
Description
Technical Field
The invention belongs to the technical field of salt lake lithium extraction, and particularly relates to a continuous cation exchange membrane/solvent extraction/FCDI synergistic coupling lithium extraction method which is suitable for extracting lithium salt from salt water with high magnesium-lithium ratio such as salt lake.
Background
In recent years, with the rapid development of the lithium battery industry, the yields of lithium and its compounds as lithium ion battery raw materials have been significantly increased, and most of lithium is extracted from minerals and brine. Compared with minerals, the lithium reserves of the salt lake in China are rich, and the salt lake is a more ideal lithium resource. However, due to the practical problems of low grade, high magnesium-lithium ratio, high sodium-lithium ratio and the like of the salt lake lithium resources in China, the difficulty in extracting the salt lake lithium resources is high, the technical threshold is high, and the development and the utilization of the salt lake lithium resources are severely limited. Therefore, the research and development of the advanced salt lake lithium resource extraction technology has important significance.
At present, methods for extracting lithium from lithium-containing brine mainly comprise a precipitation method, a calcination leaching method, an ion exchange adsorption method, a solvent extraction method and the like. The precipitation method is only suitable for extracting lithium from salt lake brine with low magnesium-lithium ratio, and has high process energy consumption, large reagent consumption and high cost; the hydrogen chloride generated in the process of the calcination leaching method has serious corrosion to equipment; the ion sieve metal oxide adsorption method in the adsorption method is used for extracting lithium and has the problems of large dissolution loss rate, short service life, difficult forming granulation and the like; the application of the solvent extraction method for extracting lithium has the problems of dissolution loss of the extractant and environmental pollution, and needs to be further optimized.
Disclosure of Invention
Aiming at the defects of unfriendly environment, large amount of organic solvent and extractant loss and the like in the field of extracting lithium from salt lakes in the prior solution extraction technology,
the invention mainly aims to provide a novel continuous cation exchange membrane/solvent extraction/FCDI synergistic coupling lithium extraction method which has a high selective extraction effect on lithium ions in salt lake brine, can be recycled for multiple times, has low pollution, and has good application prospect and technical advantage.
In order to achieve the above task, the present invention adopts the following technical solutions:
the continuous cation exchange membrane/solvent extraction/FCDI collaborative coupling lithium extraction method is characterized in that equipment used by the method comprises an external direct current power supply, an electrode connected with the external direct current power supply, an adsorption chamber directly contacted with the electrode, a flowing electrode circulation slurry tank connected with the adsorption chamber, a lithium-containing brine channel connected with the adsorption chamber, conductive adsorption slurry directly contacted with the electrode and circulated in the adsorption chamber, an anion exchange membrane directly contacted with the conductive adsorption slurry at an anode side, a cation exchange membrane directly contacted with the conductive adsorption slurry at a cathode side, a lithium ion selective liquid film separation layer packaged by two layers of cation exchange membranes and contacted with the conductive adsorption slurry at the cathode side, and a desorption FCDI device for desorbing anions and cations.
Under the action of an external electric field, lithium ions in a lithium-containing solution in the lithium-containing brine channel migrate to the cathode side through an organic phase in the lithium ion selective liquid film layer and the two layers of cation exchange membranes and are adsorbed in cathode side conductive adsorption slurry, and anions migrate through the anion exchange membrane and are adsorbed in anode conductive adsorption slurry;
after adsorption slurry in the cathode side carbon slurry tank is saturated, respectively pumping the conductive slurry in the cathode side carbon slurry tank and the anode side carbon slurry tank into a desorption FCDI device, and carrying out desorption operation on anions and cations adsorbed in the carbon slurry by the desorption FCDI device under the action of an electric field, wherein at the moment, lithium ions and anions on the surfaces of cathode side and anode side conductive adsorption slurry particles respectively pass through a cation exchange membrane and an anion exchange membrane to enter a qualified liquid chamber, so that lithium-rich qualified liquid is formed.
The specific operation process is as follows:
(1) The lithium extraction process comprises the following steps:
the conductive adsorption slurry flowing electrode in the circulating slurry tank is pumped into the electrode adsorption chambers at the two sides of the cathode and the anode, and the lithium-containing brine is pumped into the lithium-containing brine channel; the current collectors of the anode side and the cathode side adsorption chambers are respectively connected with the anode and the cathode of a power supply, constant current or constant voltage is applied, lithium ions in lithium-containing brine sequentially migrate through a cation exchange membrane, a lithium ion selective liquid membrane layer and a cation exchange membrane to a cathode conductive adsorption slurry chamber under the action of an electric field and are adsorbed on the surfaces of conductive adsorption slurry particles, anions in brine migrate through the anion exchange membrane under the action of the electric field and are adsorbed on the surfaces of the particles in the anode side conductive adsorption slurry, the conductive adsorption slurry on the anode side and lithium-containing brine continuously circulate in the adsorption chamber and the brine chamber respectively, the lithium-containing brine becomes lithium-removing brine after passing through an adsorption unit, and the lithium-removing brine is stored and reused or discharged in a waste way;
(2) And (3) a lithium removal process:
and after lithium adsorption saturation of cathode side circulating conductive adsorption slurry, respectively pumping the conductive adsorption slurry in the cathode and anode circulating tanks into a carbon slurry regeneration system, wherein anode side circulating conductive adsorption slurry is pumped into the cathode side circulating slurry tank, cathode side circulating conductive adsorption slurry is pumped into the anode side circulating slurry tank, and then carrying out desorption operation under constant current or constant voltage through a desorption FCDI device. At this time, lithium ions on the surface of the conductive adsorption slurry particles on the cathode side are desorbed and pass through the cation exchange membrane to enter the qualified liquid channel under the action of an electric field. Anions on the surfaces of the conductive adsorption slurry particles on the anode side pass through the anion exchange membrane and enter the qualified liquid channel to form lithium-rich qualified liquid.
The lithium-rich qualification solution is either subjected to a mechanical operation or directly passed to the next process unit (depending on the desired target lithium concentration). After the ions adsorbed by the conductive paste on the cathode and anode sides are thoroughly desorbed, the ions are respectively pumped into an anode-side electrode paste storage tank and a cathode-side electrode paste storage tank in the adsorption unit to continue the adsorption operation.
(3) Cyclic enrichment:
and (3) performing the cyclic reciprocating operation of the step (1) and the step (2) until the concentration of lithium ions in the original brine is reduced to a target value, and then replacing fresh brine to continue the operation of the step (1) and the step (2).
Specifically, the lithium-containing brine comprises raw brine of a salt lake, old brine of the salt lake and high-magnesium-lithium ratio lithium-containing brine subjected to evaporation pretreatment, wherein the pH value is 2-10; the concentration of lithium ions in the lithium-containing brine is 0.5 g/L-15 g/L; the concentration of lithium ions transferred to the cathode side conductive adsorption slurry is 2 g/L-10 g/L; the pH value of the cathode side slurry liquid is 1-6; the initial Mg/Li in the high-magnesium-lithium ratio lithium-containing brine is 1000:1 to 0.
Further, the conductive adsorption slurry is prepared from active materials and conductive additives according to the mass ratio of 7:3 to 9:1 is added into salt water with the concentration of 0-5g/L to prepare solution; the solid content of the flowing conductive adsorption slurry is 10-40%; wherein:
the active material component comprises one or more of active carbon, honeycomb carbon, coconut shell carbon and coal granular carbon;
the conductive additive comprises the following components: one or more of acetylene black, graphite, carbon black and carbon nanotubes;
the saline is NaCl solution or KCl solution.
The width of the liquid film separating layer is 1-50mm, and the liquid film separating layer comprises an extractant and an ionic liquid;
the extractant comprises n-tributyl phosphate (TBP), isobutyl phosphate (TIBP), one of crown ethers and azo ion chelating-associating extraction systems, and the volume ratio of the extractant to the total organic phase is 70-90%;
The ionic liquid comprises 1-butyl-3-methylimidazole tetraferrate ([ C) 4 mim][FeCl 4 ]) 1-butyl-3-methylimidazole hexafluorophosphate ([ C) 4 mim][PF 6 ]) 1-butyl-3-methylimidazole phosphotungstates ([ Bmim)] 3 PW 12 O 40 ) 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 2 mim][NTf 2 ]) And 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 4 mim][NTf 2 ]) One or more of the above organic phases accounts for 10 to 30 percent of the total organic phase by volume.
The cation exchange membrane comprises a commercial cation exchange membrane, or a cation exchange membrane reported in the literature, or a commercial single-divalent cation selective separation membrane.
The anion exchange membrane is selected from self-made anion exchange membranes or commercial anion exchange membranes.
The voltage of the external power supply acting between the electrodes is 0-5.0V.
The continuous cation exchange membrane/solvent extraction/FCDI collaborative coupling lithium extraction method of the invention develops a novel salt lake lithium extraction method suitable for an electric drive environment by utilizing the advantages of high efficiency and high concentration multiplying power of the FCDI technology in the salt concentration field and the high selectivity characteristics of the cation exchange membrane and solvent extraction technology in the salt lake lithium resource extraction field, and realizes FCDI, solvent extraction and membrane method Li + And the synergistic lithium extraction is coupled with the sieving technology. Not only avoids the problem of solvent loss of extractant caused by direct contact between lithium brine extracted by the traditional extraction method and organic extractant, but also effectively utilizes solvent extraction and membrane method Li + The screening technology has the advantage of high lithium selection, and simultaneously couples the characteristic of high-power concentration of the FCDI technology on the salt solution, so that the efficient separation and enrichment of the salt lake lithium resource are realized. Therefore, the method has remarkable technical advantages and application prospects in the field of salt lake lithium resource extraction.
Compared with the prior art, the technical innovation brought is that:
1. the ion exchange membrane is combined with the action of the flowing electrode capacitance adsorption, so that the separation and extraction efficiency of lithium can be effectively improved, and the adopted ion exchange membrane is multiple in variety, low in cost and capable of being circularly operated.
2. Overcomes the defects of unfriendly environment, large use of organic solvents, loss of extractant and the like in the field of extracting lithium from salt lakes in the prior solution extraction technology, and has the advantages of small consumption of the adopted organic reagents and recycling.
3. The continuous operation of adsorption-desorption of the carbon particle flowing electrode slurry for recycling can be completed, and the content of magnesium in lithium-containing brine is well reduced, so that the purposes of separating magnesium and lithium and extracting lithium are achieved.
Drawings
Fig. 1 is a schematic diagram of a lithium extraction method based on flow electrode capacitive desalination according to an embodiment.
Fig. 2 is a schematic diagram of a structure according to the principle of fig. 1.
The marks in the figures represent: 1. the device comprises an external power supply, a circulating slurry tank, an adsorption chamber, a metal titanium current collector, a cation exchange membrane, an anion exchange membrane, a liquid membrane separation layer, a conductive adsorption slurry and a lithium-containing brine chamber, wherein the external power supply, the circulating slurry tank, the adsorption chamber and the conductive adsorption slurry are respectively arranged in the adsorption chamber, the metal titanium current collector, the anion exchange membrane and the anion exchange membrane are respectively arranged in the adsorption chamber, and the conductive adsorption slurry is respectively arranged in the adsorption chamber.
The invention is described in further detail below with reference to the drawings and examples.
Detailed Description
Referring to fig. 1 and 2, the present embodiment provides a continuous method for extracting lithium by co-coupling of cation exchange membrane/solvent extraction/FCDI, which comprises: an external power supply 1, a circulating slurry tank 2, an adsorption chamber 3, two electrodes 4, two cation exchange membranes 5, an anion exchange membrane 6, a lithium ion selective liquid membrane separation layer 7 and conductive adsorption slurry 8. The two electrodes 4 are respectively connected with the positive electrode and the negative electrode of the external power supply 1 and are in direct contact with the conductive adsorption slurry 8. When salt lake brine enters the lithium-containing brine chamber 9, a current loop is formed, lithium ions in the salt lake brine migrate to a cathode chamber through an organic phase in the organic phase chamber under the action of an external voltage, and anions migrate to an anode chamber through an anion exchange membrane 6. The liquid film separation layer 7 having selectivity to lithium ions can separate lithium ions from impurities such as magnesium ions, calcium ions, potassium ions, and the like, thereby enriching lithium ions in the anode-side conductive adsorption slurry 8. When the equipment runs for a certain time, the cathode and anode conductive adsorption slurries 8 are close to the saturated adsorption capacity, at the moment, after the cathode side conductive adsorption slurries 8 are adsorbed and saturated, the conductive adsorption slurries 8 are pumped into a flowing electrode desorption channel in a desorption FCDI device, lithium ions and anions on the particle surfaces of the cathode side conductive adsorption slurries 8 and the anode side conductive adsorption slurries respectively pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter a qualified liquid channel, and the qualified liquid is used for collecting the lithium ions and the corresponding anions which are moved in from two sides to form a lithium-rich qualified liquid.
The specific operation process is as follows:
(1) The lithium extraction process comprises the following steps:
the conductive adsorption slurry 8 in the circulating slurry tank 2 is pumped into the electrode adsorption chambers 3 at the two sides of the cathode and the anode by the flowing electrode, and the lithium-containing brine is pumped into the lithium-containing brine channel; the current collectors of the anode side and the cathode side adsorption chamber 3 are respectively connected with the anode and the cathode of a power supply, constant current or constant voltage is applied, lithium ions in lithium-containing brine sequentially migrate through the cation exchange membrane 5, the lithium ion selective liquid membrane layer and the cation exchange membrane 5 to the cathode conductive adsorption slurry chamber under the action of an electric field and are adsorbed to the particle surfaces of the conductive adsorption slurry 8, anions in the brine migrate through the anion exchange membrane 6 under the action of the electric field and are adsorbed to the particle surfaces in the anode side conductive adsorption slurry 8, the conductive adsorption slurry 8 on the anode side and lithium-containing brine continuously circulate in the adsorption chamber 3 and the brine chamber respectively, the lithium-containing brine becomes lithium-removed brine after passing through the adsorption unit, and the lithium-removed brine is stored and reused or discarded for discharging;
(2) And (3) a lithium removal process:
after lithium adsorption saturation of the cathode side circulating conductive adsorption slurry 8, simultaneously pumping the conductive adsorption slurry 8 in the cathode and anode circulating tanks into a carbon slurry regeneration system respectively, wherein the anode side circulating conductive adsorption slurry 8 is pumped into the cathode side circulating slurry tank 2 (desorption), the cathode side circulating conductive adsorption slurry 8 is pumped into the anode side circulating slurry tank 2 (desorption), and then the desorption operation is carried out through a desorption FCDI device under constant current or constant voltage conditions (shown in fig. 2). At this time, lithium ions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side are desorbed and pass through the cation exchange membrane 5 to enter the qualified liquid channel under the action of an electric field. Anions on the particle surfaces of the anode side conductive adsorption slurry 8 pass through the anion exchange membrane 6 and enter a qualified liquid channel to form lithium-rich qualified liquid.
The lithium-rich qualification solution is either subjected to a mechanical operation or directly passed to the next process unit (depending on the desired target lithium concentration). After the ions adsorbed by the conductive paste on the cathode and anode sides are thoroughly desorbed, the ions are respectively pumped into an anode-side electrode paste storage tank and a cathode-side electrode paste storage tank in the adsorption unit to continue the adsorption operation.
(3) Cyclic enrichment:
and (3) performing the cyclic reciprocating operation of the step (1) and the step (2) until the concentration of lithium ions in the original brine is reduced to a target value, and then replacing fresh brine to continue the operation of the step (1) and the step (2).
In this example, the cation exchange membrane 5 is selected to have high ion conductivity, good organic barrier capability and good lithium ion permselectivity, and mainly comprises a commercial cation exchange membrane, a commercial mono-divalent cation selective separation membrane, preferably a Shan Duojia cation selective separation membrane. The anion exchange membrane 6 selected should have high ion conductivity and mainly include anion exchange membranes commercially available and those reported in the literature, and the like.
Further, the extractant layer selected should have both good ion conductivity and high lithium ion selectivity. Mainly comprises two parts of lithium ion extractant and organic ionic liquid. Wherein the extractant mainly comprises n-tributyl phosphate (TBP), isobutyl phosphate (TIBP), one of crown ethers and azo ion chelate-association extraction systems, preferably TBP or TIBP. The organic ionic liquid mainly comprises 1-butyl-3-methylimidazole ferrate ([ C) 4 mim][FeCl 4 ]) 1-butyl-3-methylimidazole hexafluorophosphate ([ C) 4 mim][PF 6 ]) 1-butyl-3-methylimidazole phosphotungstates ([ Bmim)] 3 PW 12 O 40 ) 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 2 mim][NTf 2 ]) And 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 4 mim][NTf 2 ]) One or more of them, preferably [ C ] 2 mim][NTf 2 ]Or [ C ] 4 mim][NTf 2 ]。
Specifically, the slurry selected should have good adsorption performance, conductivity and cycle stability for anions and cations. Mainly comprises active materials, conductive additives and brine. The ratio of the active material to the conductive additive is 7:3 to 9:1, preferably 8:2. wherein the active material mainly comprises one or more of active carbon, graphite, acetylene black and carbon black, and the active carbon is preferred. The conductive additive mainly comprises graphite, acetylene black, carbon black and carbon nanotubes, preferably carbon black. The brine mainly comprises NaCl solution and KCl solution, preferably NaCl solution, and the concentration is 0-5g/L, preferably 1g/L.
Specifically, the electrode material mainly comprises a graphite current collector, a metallic titanium current collector, a carbon cloth electrode and a titanium ruthenium-coated electrode, and the graphite current collector is preferred.
The following are specific examples given by the inventors.
Example 1:
80g of activated carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate and 8ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide were mixed in a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + The organic phase of (2) is pumped into the liquid film chamber, the thickness of the liquid film chamber is controlled to be 3mm, and the peristaltic pump is stopped after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L; 5L of configured brine is circulated in the brine chamber and brought into full contact with the anion exchange membrane 6 and the cation exchange membrane 5 on both sides.
Applying 3.0V voltage to the metal titanium current collectors 4 at two sides by using an external power supply 1, maintaining the temperature at 25 ℃ for 8 hours, after the maintenance is finished, pumping the conductive adsorption slurry 8 which is adsorbed in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 which is circulated at the anode side into the cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 which is circulated at the cathode side into the anode-side circulation slurry tank 2, respectively connecting the current collectors of the anode-side desorption chamber and the cathode-side desorption chamber with the anode and the cathode of the power supply, adjusting the voltage to 4.0V, performing desorption operation by a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively allowing lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 at the cathode side and the anode side to pass through the cation exchange membrane 5 and the anion exchange membrane 6 to enter the qualified liquid channel, wherein the process lasts for 30 minutes. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution channel is as follows: li (Li) + ：7.2g/L，Mg 2+ :4.68g/L. Migration rate of lithium ionsThe rate is 75g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 0.65 in the receiving solution: 1.
example 2:
80g of honeycomb carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate was mixed with 8ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide at a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + :1g/L，Mg 2+ :50g/L，Na + 10g/L, 5L of configured brine is circulated in the brine chamber and fully contacted with the anion exchange membrane 6 and the cation exchange membrane 5 at the two sides.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：5.38g/L，Mg 2+ :6.45g/L. The migration rate of lithium ions was 56g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 drop into the receiving solution1.2：1。
Example 3:
80g of coconut shell carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate was mixed with 8ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide at a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + :1g/L，Mg 2+ :50g/L，Na + 10g/L, 5L of configured brine is circulated in the brine chamber and fully contacted with the anion exchange membrane 6 and the cation exchange membrane 5 at the two sides.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the anode-side circulation conductive adsorption slurry 8 into a cathode-side circulation slurry tank 2, pumping the cathode-side circulation conductive adsorption slurry 8 into the anode-side circulation slurry tank 2, respectively connecting current collectors of an anode-side desorption chamber and a cathode-side desorption chamber with a positive electrode and a negative electrode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively allowing lithium ions and anions on the particle surfaces of the cathode-side and anode-side conductive adsorption slurry 8 to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel, wherein the process lasts for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：4.89g/L，Mg 2+ :6.85g/L. The migration rate of lithium ions was 51g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 down to 1.4:1 in the receiving solution.
Example 4:
90g of activated carbon and 10g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate was reacted with 4ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide at 8:2, and adding an equal amount (40 ml) of a 1mol/L LiCl solution, shaking the mixed liquid for 1 hour, standing for 30 minutes, and separating out Li-containing solution using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L,Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：6.53g/L，Mg 2+ :4.90g/L. The migration rate of lithium ions was 68g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 down to 0.75:1 in the receiving solution.
Example 5:
120g of activated carbon and 30g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate was mixed with 4ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide at a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：7.01g/L，Mg 2+ :6.17g/L. The migration rate of lithium ions was 73g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 0.88 in the receiving solution: 1.
example 6:
80g of activated carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate and 8ml of 1-butyl-3-methylimidazole hexafluorophosphate were mixed in a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：4.90g/L，Mg 2+ :8.81mg/L. The migration rate of lithium ions was 51g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 1.8 in the receiving solution: 1.
example 7:
80g of activated carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate and 8ml of 1-butyl-3-methylimidazole tetrachloroFerrite was mixed at a volume ratio of 8:2, and an equivalent (40 ml) of 1mol/L LiCl solution was added thereto, the mixed liquid was shaken well for 1 hour, and after standing for 30 minutes, li-containing was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively allowing lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：7.49g/L，Mg 2+ :6.51g/L. The migration rate of lithium ions was 78g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 0.87 in the receiving solution: 1.
example 8:
conductive adsorption paste 8 was prepared as in example 5. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump. 36ml of tributyl phosphate was reacted with 4ml of 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide at 9:1, and adding an equal amount (40 ml) of a 1mol/L LiCl solution, shaking the mixed liquid for 1 hour, standing for 30 minutes, and separating out Li-containing solution using a separating funnel + Is poured into a liquid film chamberThe thickness of the liquid film chamber is controlled to be 3mm, and the peristaltic pump is stopped after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：7.87g/L，Mg 2+ :4.33mg/L. The migration rate of lithium ions was 82g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 0.55 in the receiving solution: 1.
example 9:
conductive adsorption paste 8 was prepared as in example 1. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump. A liquid film separation layer 7 was prepared in the same manner as in example 1, the thickness of the liquid film chamber was controlled to 3mm, and the peristaltic pump was stopped after the liquid film chamber was filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：100g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
Applying 3.0V voltage to the two-side metal titanium current collector 4 by using an external power supply 1, and thenMaintained at 25℃for 8h. After 8h, pumping the conductive adsorption slurry 8 which is adsorbed in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 which circulates on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 which circulates on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel, wherein the process lasts for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：6.34g/L，Mg 2+ :15.84mg/L. The migration rate of lithium ions was 66g/m 2 H, mg/Li in the solution is calculated from 100 in the initial water inlet solution: 1 to 2.5 in the receiving solution: 1.
example 10:
80g of activated carbon and 20g of carbon black were uniformly mixed, and the mixed powder was added to 1L of 0.1mol/L NaCl solution to form electroconductive adsorption paste 8. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump.
32ml of tributyl phosphate and 8ml of 1-butyl-3-methylimidazole hexafluorophosphate were mixed in a volume ratio of 8:2, an equivalent (40 ml) of 1mol/L LiCl solution was added, the mixed solution was shaken well for 1 hour, and after standing for 30 minutes, li-containing solution was separated out using a separating funnel + Pouring the organic phase into the liquid film chamber, controlling the thickness of the liquid film chamber to be 3mm, and stopping the peristaltic pump after the liquid film chamber is filled.
The components of the prepared brine are as follows: li (Li) + ：0.5g/L，Mg 2+ ：100g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8 hours, the conductive adsorption slurry 8 which is adsorbed in the cathode and anode circulating tank is pumped into In the carbon slurry regeneration system, conductive adsorption slurry 8 circulated on the anode side is pumped into a cathode side circulation slurry tank 2, conductive adsorption slurry 8 circulated on the cathode side is pumped into the anode side circulation slurry tank 2, current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side are respectively connected with the anode and the cathode of a power supply, the voltage is adjusted to be 4.0V, desorption operation is carried out through a desorption FCDI device, 500ml of 0.1g/L NaCl solution is pumped into a qualified liquid channel, and lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side respectively pass through a cation exchange membrane 5 and an anion exchange membrane 6 and enter the qualified liquid channel, and the process lasts for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：4.41g/L,Mg 2+ :14.55mg/L. The migration rate of lithium ions was 46g/m 2 H, mg/Li in solution is formed by 200 in initial water inlet solution: 1 to 3.3 in the receiving solution: 1.
example 11:
conductive adsorption paste 8 was prepared as in example 5. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump. A liquid film separation layer 7 was prepared in the same manner as in example 5, the thickness of the liquid film chamber was controlled to 3mm, and the peristaltic pump was stopped after the liquid film chamber was filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
An external power supply 1 was used to apply 8.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8 hours, the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank is pumped into a carbon slurry regeneration system respectively, the conductive adsorption slurry 8 circulated on the anode side is pumped into the cathode-side circulation slurry tank 2, the conductive adsorption slurry 8 circulated on the cathode side is pumped into the anode-side circulation slurry tank 2, current collectors of the anode-side desorption chamber and the cathode-side desorption chamber are respectively connected with the anode and the cathode of a power supply, the voltage is adjusted to be 4.0V, desorption operation is carried out through a desorption FCDI device, 500ml of 0.1g/L NaCl solution is pumped into a qualified liquid channel, and lithium ions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side are pumped into a cathode-side circulation slurry tank 2Anions pass through the cation exchange membrane 5 and the anion exchange membrane 6 respectively to enter the qualified liquid channel, and the process lasts for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：8.16g/L，Mg 2+ :40.8mg/L. The migration rate of lithium ions was 85g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 into the receiving solution 5:1.
Example 12:
conductive adsorption paste 8 was prepared as in example 1. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump. A liquid film separation layer 7 was prepared in the same manner as in example 1, the thickness of the liquid film chamber was controlled to 6mm, and the peristaltic pump was stopped after the liquid film chamber was filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 8 hours. After 8h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：4.42g/L，Mg 2+ :6.84mg/L. The migration rate of lithium ions was 46g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 1.55 in the receiving solution: 1.
example 13:
conductive adsorption paste 8 was prepared as in example 6. The conductive adsorption slurry 8 is circulated in the bipolar mixing chamber and the adsorption chamber 3 by a peristaltic pump. A liquid film separation layer 7 was prepared in the same manner as in example 6, the thickness of the liquid film chamber was controlled to 3mm, and the peristaltic pump was stopped after the liquid film chamber was filled.
The components of the prepared brine are as follows: li (Li) + ：1g/L，Mg 2+ ：50g/L，Na + :10g/L, 5L of configured brine was circulated in the brine chamber and brought into full contact with both the anion exchange membrane 6 and the cation exchange membrane 5.
The external power supply 1 was used to apply a voltage of 3.0V to the two-sided metallic titanium current collector 4, which was maintained at 25 ℃ for 20 hours. After 20h, pumping the conductive adsorption slurry 8 after adsorption in the cathode-anode circulation tank into a carbon slurry regeneration system respectively, pumping the conductive adsorption slurry 8 circulated on the anode side into a cathode-side circulation slurry tank 2, pumping the conductive adsorption slurry 8 circulated on the cathode side into the anode-side circulation slurry tank 2, respectively connecting current collectors of a desorption chamber on the anode side and a desorption chamber on the cathode side with the anode and the cathode side, respectively connecting the anode and the cathode of a power supply, adjusting the voltage to be 4.0V, carrying out desorption operation through a desorption FCDI device, pumping 500ml of 0.1g/L NaCl solution into a qualified liquid channel, and respectively enabling lithium ions and anions on the particle surfaces of the conductive adsorption slurry 8 on the cathode side and the anode side to pass through a cation exchange membrane 5 and an anion exchange membrane 6 to enter the qualified liquid channel for 30min. After the power-on is finished, the ion concentration of the concentrated solution in the qualified solution chamber is as follows: li (Li) + ：9.84g/L，Mg 2+ :34.44mg/L. The migration rate of lithium ions was 41g/m 2 H, mg/Li in solution is determined by 50% in the initial aqueous solution: 1 to 3.5 in the receiving solution: 1.
although the foregoing embodiments have been described in detail for the purpose of illustration, it should be understood that the foregoing embodiments are preferred examples of the invention, and that the invention is not limited to these embodiments. Various additions, substitutions and simple modifications to the technical solutions without departing from the technical solutions of the present invention will be apparent to those skilled in the art, and they are intended to fall within the scope of the present invention as defined in the appended claims.
Claims (9)
1. The continuous cation exchange membrane/solvent extraction/FCDI collaborative coupling lithium extraction method is characterized in that the method adopts equipment comprising an external direct current power supply, an electrode connected with the external direct current power supply, an adsorption chamber directly contacted with the electrode, a conductive adsorption electrode circulating slurry tank connected with the adsorption chamber, a lithium-containing brine channel connected with the adsorption chamber, conductive adsorption slurry directly contacted with the electrode and circulated in the adsorption chamber, an anion exchange membrane directly contacted with the conductive adsorption slurry at the anode side, a cation exchange membrane directly contacted with the conductive adsorption slurry at the cathode side, a lithium ion selective liquid film separation layer packaged by two layers of cation exchange membranes and contacted with the conductive adsorption slurry at the cathode side, and a desorption FCDI device for desorbing anions and cations;
Under the action of an external electric field, lithium ions in a lithium-containing solution in the lithium-containing brine channel migrate to the cathode side through an organic phase in the lithium ion selective liquid film layer and the two layers of cation exchange membranes and are adsorbed in cathode side conductive adsorption slurry, and anions migrate through the anion exchange membrane and are adsorbed in anode conductive adsorption slurry;
after adsorption slurry in the cathode side carbon slurry tank is saturated, respectively pumping the conductive slurry in the cathode side carbon slurry tank and the anode side carbon slurry tank into a desorption FCDI device, and carrying out desorption operation on anions and cations adsorbed in the carbon slurry by the desorption FCDI device under the action of an electric field, wherein at the moment, lithium ions and anions on the surfaces of cathode side and anode side conductive adsorption slurry particles respectively pass through a cation exchange membrane and an anion exchange membrane to enter a qualified liquid chamber, so that lithium-rich qualified liquid is formed.
2. The method of claim 1, wherein the specific operation is:
(1) The lithium extraction process comprises the following steps:
the conductive adsorption slurry flowing electrode in the circulating slurry tank is pumped into the electrode adsorption chambers at the two sides of the cathode and the anode, and the lithium-containing brine is pumped into the lithium-containing brine channel; the current collectors of the anode side and the cathode side adsorption chambers are respectively connected with the anode and the cathode of a power supply, constant current or constant voltage is applied, lithium ions in lithium-containing brine sequentially migrate through a cation exchange membrane, a lithium ion selective liquid membrane layer and a cation exchange membrane to a cathode conductive adsorption slurry chamber under the action of an electric field and are adsorbed on the surfaces of conductive adsorption slurry particles, anions in brine migrate through the anion exchange membrane under the action of the electric field and are adsorbed on the surfaces of the particles in the anode side conductive adsorption slurry, the conductive adsorption slurry on the anode side and lithium-containing brine continuously circulate in the adsorption chamber and the brine chamber respectively, the lithium-containing brine becomes lithium-removing brine after passing through an adsorption unit, and the lithium-removing brine is stored and reused or discharged in a waste way;
(2) And (3) a lithium removal process:
after lithium adsorption saturation of cathode side circulating conductive adsorption slurry, respectively pumping the conductive adsorption slurry in a cathode-anode circulating tank into a carbon slurry regeneration system, wherein anode side circulating conductive adsorption slurry is pumped into a cathode side circulating slurry tank, cathode side circulating conductive adsorption slurry is pumped into an anode side circulating slurry tank, and then desorption operation is carried out through a desorption FCDI device under constant current or constant voltage conditions; at the moment, lithium ions on the surfaces of the conductive adsorption slurry particles on the cathode side are desorbed and pass through the cation exchange membrane to enter a qualified liquid channel under the action of an electric field; anions on the surfaces of the conductive adsorption slurry particles on the anode side pass through the anion exchange membrane and enter a qualified liquid channel to form lithium-rich qualified liquid;
performing mechanically-applied operation on the lithium-rich qualified liquid or directly entering the next process unit; after the ions adsorbed by the conductive paste at the cathode and anode sides are thoroughly desorbed, respectively pumping the ions into an anode-side electrode paste storage tank and a cathode-side electrode paste storage tank in an adsorption unit to continue the adsorption operation;
(3) Cyclic enrichment:
and (3) performing the cyclic reciprocating operation of the step (1) and the step (2) until the concentration of lithium ions in the original brine is reduced to a target value, and then replacing fresh brine to continue the operation of the step (1) and the step (2).
3. The method of claim 1, wherein the lithium-containing brine comprises a salt lake raw brine, a salt lake aged brine, and an evaporation-pretreated high magnesium-to-lithium ratio lithium-containing brine, having a pH of 2-10; the concentration of lithium ions in the lithium-containing brine is 0.5 g/L-15 g/L; the concentration of lithium ions transferred to the cathode side conductive adsorption slurry is 2 g/L-10 g/L; the pH value of the cathode side slurry liquid is 1-6; the initial Mg/Li in the high-magnesium-lithium ratio lithium-containing brine is 1000:1 to 0.
4. The method of claim 1, wherein the electrode comprises a graphite current collector, a metallic titanium current collector, a carbon cloth electrode, or a titanium ruthenium coated electrode.
5. The method of claim 1, wherein the conductive adsorption paste comprises active materials and conductive additives according to a mass ratio of 7:3 to 9:1 is added into salt water with the concentration of 0-5g/L to prepare solution; the solid content of the flowing conductive adsorption slurry is 10-40%; wherein:
the active material component comprises one or more of active carbon, honeycomb carbon, coconut shell carbon and coal granular carbon;
the conductive additive comprises the following components: one or more of acetylene black, graphite, carbon black and carbon nanotubes;
The saline is NaCl solution or KCl solution.
6. The method of claim 1, wherein the liquid film separation layer has a width of 1 to 50mm and comprises an extractant and an ionic liquid;
the extractant comprises n-tributyl phosphate (TBP), isobutyl phosphate (TIBP), one of crown ethers and azo ion chelating-associating extraction systems, and the volume ratio of the extractant to the total organic phase is 70-90%;
the ionic liquid comprises 1-butyl-3-methylimidazole tetraferrate ([ C) 4 mim][FeCl 4 ]) 1-butyl-3-methylimidazole hexafluorophosphate ([ C) 4 mim][PF 6 ]) 1-butyl-3-methylimidazole phosphotungstates ([ Bmim)] 3 PW 12 O 40 ) 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 2 mim][NTf 2 ]) And 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide ([ C) 4 mim][NTf 2 ]) One or more of the above organic phases accounts for 10 to 30 percent of the total organic phase by volume.
7. The method of claim 1, wherein the cation exchange membrane is selected from a commercial cation exchange membrane, or a reported cation exchange membrane, or a commercial single-divalent cation selective separation membrane.
8. The method of claim 1, wherein the anion exchange membrane is selected from a homemade anion exchange membrane or a commercial anion exchange membrane.
9. The method of claim 1, wherein the voltage applied between the electrodes by the external power source is 0-5.0V.
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| CN117305584B (en) * | 2023-11-29 | 2024-02-09 | 中国科学院过程工程研究所 | System and method for extracting lithium by mobile slurry electrodelapsing |
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