CN108060308B - Method and device for separating lithium from lithium-containing solution - Google Patents
Method and device for separating lithium from lithium-containing solution Download PDFInfo
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- CN108060308B CN108060308B CN201711320030.0A CN201711320030A CN108060308B CN 108060308 B CN108060308 B CN 108060308B CN 201711320030 A CN201711320030 A CN 201711320030A CN 108060308 B CN108060308 B CN 108060308B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 173
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 72
- 239000012074 organic phase Substances 0.000 claims abstract description 72
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 62
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 116
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 20
- 239000012267 brine Substances 0.000 claims description 19
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 19
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 17
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001962 electrophoresis Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000010416 ion conductor Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 10
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000010439 graphite Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000003115 supporting electrolyte Substances 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
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- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 230000003204 osmotic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
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- 238000005370 electroosmosis Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 229910001234 light alloy Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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Images
Classifications
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- 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
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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)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method and a device for separating lithium from a lithium-containing solution, wherein the method comprises the following steps: an ion exchange membrane is adopted to divide an electrolytic cell into an anode chamber, an organic phase chamber and a cathode chamber, lithium ions in a lithium-containing solution in the anode chamber are transferred to a lithium-enriched liquid in the cathode chamber through an organic phase in the organic phase chamber under the action of an external voltage, wherein the organic phase is an organic reagent which can selectively and chemically react with the lithium ions in the lithium-containing solution; the device comprises an electrolytic cell, and an ion exchange membrane is adopted to divide the electrolytic cell into an anode chamber, an organic phase chamber and a cathode chamber, wherein the organic phase chamber is positioned between the anode chamber and the cathode chamber. Compared with the problem of low separation efficiency of lithium ions and other metal ions in the lithium-containing solution in the prior art, the method and the device for separating lithium from the lithium-containing solution provided by the invention can be used for treating the lithium-containing solution with higher magnesium-lithium ratio.
Description
Technical Field
The invention relates to metallurgy technology, in particular to a method and a device for separating lithium from a lithium-containing solution.
Background
Lithium is the least dense metal and is widely used in atomic reactors, as well as in the production of light alloys and lithium batteries. Around 70% of lithium resources are allocated in salt lakes globally, and more than 80% of lithium products are obtained by extraction of lithium from salt lakes. The Chinese salt lake has a large quantity, rich lithium storage capacity and high grade.
However, most of the salt lake brine has the magnesium-lithium ratio of more than 40, and the highest magnesium-lithium ratio reaches 1837. Mg-Li-due to its diagonal position in the periodic Table of the elements2+With Li+The chemical properties of the magnesium and the lithium are very similar, and the separation of magnesium and lithium is very difficult, so that the extraction and the application of lithium are severely restricted.
At present, the recovery process of lithium in salt lake brine mainly adopts a precipitation method, a carbonization method, a calcination leaching method, an ion exchange adsorption method or a solvent extraction method and the like. The lithium-magnesium separation by the precipitation method and the carbonization method is suitable for extracting lithium from salt lake brine with low magnesium-lithium ratio, and most of the problems of high energy consumption, large reagent consumption, high cost and the like exist; the calcination leaching method has high process energy consumption, and the hydrogen chloride generated in the process has serious corrosion to equipment; the problems of high dissolution loss rate, short service life, difficult molding and granulation and the like exist in the lithium extraction by the ion sieve metal oxide adsorption method in the adsorption method; the application of the solvent extraction method for extracting lithium still has the problems of equipment corrosion, solvent loss of an extracting agent, high cost and the like, and needs to be further optimized.
At present, most of the existing lithium extraction processes in salt lakes are established on the basis of high-quality brine with low magnesium-lithium ratio (magnesium-lithium ratio is less than or equal to 6: 1). For example, chinese patent application publication No. CN1626443A, which discloses a method for separating magnesium and concentrating lithium from salt lake brine. The method adopts a circulation process to concentrate lithium by leading salt lake brine to pass through a one-stage or multi-stage electrodialyzer and utilizing a monovalent selective ion exchange membrane to obtain lithium-rich low-magnesium brine.
The method can well reduce the content of magnesium in the obtained product, and achieve the purposes of separating magnesium and lithium and extracting lithium, but is suitable for salt lake brine with low magnesium and lithium content, and the cost of the adopted monovalent ion exchange membrane is high; in the separation process, other univalent metal ions are difficult to be effectively separated from lithium, and the content of other metal ions in the obtained product is still high.
Disclosure of Invention
The invention provides a method and a device for separating lithium from a lithium-containing solution, which overcome the problems or at least partially solve the problems, so as to solve the technical problems of low efficiency, high impurity content and high cost when lithium is separated from salt lake brine or the lithium-containing solution.
According to one aspect of the present invention, there is provided a method for separating lithium from a lithium-containing solution, comprising dividing an electrolytic cell into an anode chamber, an organic phase chamber and a cathode chamber by an ion exchange membrane, wherein lithium ions in the lithium-containing solution in the anode chamber migrate into a lithium-rich solution in the cathode chamber through an organic phase in the organic phase chamber under the action of an applied voltage; wherein the organic phase is an organic reagent capable of selectively chemically reacting with lithium ions in the lithium-containing solution.
Specifically, the electrolytic cell is divided into three parts, namely an anode chamber, an organic phase chamber and a cathode chamber, by two ion exchange membranes, and the organic phase chamber is positioned between the anode chamber and the cathode chamber. And filling different solutions or reagents into the anode chamber, the organic phase chamber and the cathode chamber respectively, and reacting under the action of an applied voltage.
Specifically, prior to treatment, the anode chamber contains a lithium-containing solution to be treated, the organic phase chamber contains an organic reagent, and the cathode chamber contains a supporting electrolyte, which is an initial solution of a lithium-rich solution. Because the anode chamber, the organic phase chamber or the cathode chamber are separated by the ion exchange membrane, when the anode chamber, the organic phase chamber and the cathode chamber are filled with corresponding reagents, the organic phase chamber is positioned between the anode chamber and the cathode chamber, and the organic phase in the organic phase chamber, the lithium-containing solution in the anode chamber and the supporting electrolyte in the cathode chamber cannot freely flow mutually, so that the preparation is carried out for further separating lithium from the lithium-containing solution.
Specifically, an anode is arranged in the lithium-containing solution in the anode chamber, a cathode is arranged in the supporting electrolyte in the cathode chamber, and a direct current power supply is externally connected between the anode and the cathode for applying an external voltage between the reagents in the anode chamber and the cathode chamber. Under the action of the applied voltage, ions in the reagent in the electrolytic cell can be uniformly transferred under the action of the applied voltage.
However, the organic reagent composing the organic phase can selectively react with lithium ions, and under the action of an applied voltage, lithium ions in a complex obtained by the reaction of the organic phase and lithium can migrate to the cathode chamber, so that the lithium ions in the lithium-containing solution which penetrate through the ion exchange membrane and enter the organic phase are brought into the supporting electrolyte in the cathode chamber through the organic phase to form a lithium-enriched solution. The complex obtained by the reaction is electrolyzed at the boundary of the organic phase chamber and the cathode chamber under the action of an external voltage to obtain free lithium ions, and the lithium ions penetrate through the ion exchange membrane to enter into the lithium enrichment solution, so that the aims of extracting and enriching lithium are fulfilled.
Meanwhile, other metal ions or impurities in the lithium-containing solution and the organic reagent cannot react, so that other metal ions or impurities entering the organic phase chamber through the ion exchange membrane cannot continuously migrate to the cathode chamber through the organic phase, and still mainly stay in the anode chamber. The chemical reaction of lithium ions with the organic reagent at the boundary of the organic phase chamber and the anode chamber, and the electrolysis of the reaction products at the boundary of the organic phase chamber and the cathode chamber, form a dynamic equilibrium process. Under the action of the applied voltage, the lithium ions in the lithium-containing solution continuously migrate to the lithium-enriched solution in the cathode chamber, so that the lithium ions in the lithium-containing solution are separated from other impurities.
On the basis of the above embodiments, the organic reagents used are specifically: mixed reagent containing dibenzoyltoluene (HDBM) and trioctylphosphine oxide (TOPO), mixed reagent containing fluoro beta-diketone and trioctylphosphine oxide, mixed reagent containing tributyl phosphate (TBP) and diisobutyl ketone (DIBK), mixed reagent containing tributyl phosphate and FeCl3A mixed reagent containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide, a mixed reagent containing tributyl phosphate and
one or more of the mixed reagent, N-di (1-methylheptyl) hexanamide and N263.
Preferably, the organic reagent can be tributyl phosphate and FeCl3A mixed reagent containing tributyl phosphate (TBP) and diisobutyl ketone (DIBK), a mixed reagent containing tributyl phosphate and
and one or more of a mixed reagent containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide.
Specifically, the reagent can selectively and chemically react with lithium ions in the lithium-containing solution, so that the lithium ions in the lithium-containing solution enter the lithium-enriched liquid in the cathode chamber through the organic phase. The organic reagent which can selectively react with the lithium ions is adopted to separate the lithium ions from other metal ions or impurities in the lithium-containing solution, so that not only monovalent lithium ions can be effectively separated from metal ions in other valence states, but also the lithium ions and other monovalent metal ions can be effectively separatedSeparation of (3), e.g. Na+、K+And the purity and enrichment rate of the extracted and enriched lithium are higher by the aid of the plasma. Therefore, the method can play a good role in separating lithium in a solution with a high magnesium-lithium ratio, so as to effectively separate lithium from other impurities and achieve the purposes of enriching and purifying lithium.
On the basis of the above embodiment, the concentration of lithium ions in the lithium-containing solution is 0.05-20 g/L; preferably 0.5g/L to 15 g/L; more preferably 0.5g/L to 5 g/L. The lithium ion concentration in the lithium-containing solution is in a certain range, so that the current efficiency and the production efficiency can be improved, and when the lithium ion concentration in the lithium-containing solution is too low, the recovery cost is high, and the recovery benefit is poor.
Specifically, during the actual recovery process, the concentration of lithium ions in the lithium-containing solution in the anode chamber is continuously reduced as the lithium ions in the lithium-containing solution are continuously migrated to and enriched in the cathode chamber. When the lithium ion concentration in the anode chamber is reduced to a certain concentration, new lithium-containing solution to be treated is added into the anode chamber, so that the lithium ion concentration in the lithium-containing solution in the anode chamber is maintained in a proper range.
It is understood that the lithium-containing solution to be treated may be periodically and quantitatively replenished into the anode chamber under the application of the applied voltage, or the lithium-containing solution to be treated may be continuously replenished into the anode chamber at a certain rate, depending on the efficiency of lithium ion transfer from the anode chamber to the cathode chamber.
On the basis of the above embodiment, the method of the present invention is particularly suitable for salt lake brine, old brine produced in the evaporation process of salt lake brine, gas field brine, old lithium battery recycling liquid or lithium-containing wastewater in the lithium carbonate production process.
In particular, the waste liquid, seawater or salt lake brine contains lithium ions with higher concentration, and has more resources or wastes which easily have adverse effects on the environment, and the lithium recovery from the waste liquid, seawater or salt lake brine can generate higher economic benefits.
Based on the above-described embodiment, the concentration of lithium ions transferred to the lithium-rich liquid in the cathode compartment is maintained at 1 to 30g/L, preferably 2 to 10 g/L. Specifically, when lithium ions are continuously enriched in the lithium-enriched liquid in the cathode chamber, the concentration of the lithium ions contained in the lithium-enriched liquid is continuously increased. When the concentration of lithium ions contained in the lithium-enriched liquid is increased to a certain concentration, the osmotic pressure due to the concentration difference decreases the efficiency of lithium ion transfer to the cathode chamber. When lithium ions migrate from the lithium-containing solution to the lithium-enriched solution in the cathode chamber, the applied pressure needs to be increased, which reduces the utilization efficiency of the current generated by the applied voltage.
Specifically, when the lithium ions enriched in the lithium enrichment solution reach a certain concentration, a precipitation method or an extraction method can be adopted to prepare lithium in the lithium enrichment solution into a lithium salt product so as to further enrich and utilize the lithium. Meanwhile, the concentration of the lithium ions enriched in the cathode chamber can be reduced, and the concentration of the lithium ions in the cathode chamber relative to the concentration of the lithium ions in the anode chamber is reduced, so that the lithium ions can migrate into the cathode chamber to be enriched. The solution obtained after the precipitation method or the extraction method is adopted to extract lithium can be recycled and used for the lithium enrichment solution in the cathode chamber. It will be appreciated that where precipitation or extraction is used to further extract lithium, the cathode compartment may also be supplemented with a supporting electrolyte accordingly.
Based on the above examples, the concentration ratio of lithium ions in the lithium-containing solution to lithium ions transferred to the lithium-enriched solution is 5:1 to 0.1:1, preferably 3:1 to 0.25: 1. Specifically, by maintaining the ratio of the concentration of lithium ions in the anode chamber to the concentration of lithium ions enriched in the cathode chamber within a suitable range, it is possible to reduce the adverse effect of osmotic pressure caused by an excessively high concentration of lithium ions in the cathode chamber and to improve the current efficiency of the applied voltage. At the same time, the efficiency and rate of lithium ion transport into the cathode compartment can also be increased.
On the basis of the above embodiment, the ion exchange membrane is one or more of a microporous polytetrafluoroethylene membrane, a porous polypropylene membrane, a proton exchange membrane, a cation exchange membrane, an electrophoretic cathode membrane and a fast ion conductor membrane.
Specifically, the ion exchange membrane for separating the anode chamber from the organic phase chamber may be the same as or different from the ion exchange membrane for separating the cathode chamber from the organic phase chamber. For example, when the ion exchange membrane for separating the anode chamber from the organic phase chamber is a microporous polytetrafluoroethylene membrane, the ion exchange membrane for separating the cathode chamber from the organic phase chamber may be a microporous polytetrafluoroethylene membrane, or other types of ion exchange membranes may be used.
In particular, when the ion exchange membrane employs an exchange membrane having selective permeation, the separation efficiency of lithium ions from other metal ions or impurities can be further improved.
On the basis of the above examples, the width of the organic phase chamber is 1 to 50 mm; preferably 5-10 mm. The width of the organic phase chamber is kept in a proper range, so that lithium ions can be smoothly transferred to the cathode chamber through the organic phase chamber, and the problem that the transfer efficiency of the lithium ions is influenced by the chelation of a complex obtained by the reaction of the lithium ions and an organic reagent can be avoided. It will be appreciated that, depending on the scale of the electrolytic cell, the width of the organic phase chamber may be suitably adjusted to enrich the target ions in the anode chamber into the cathode chamber.
Based on the above embodiment, the applied voltage generates a current density between the anode chamber and the cathode chamber of 5-100A/m2Preferably 20 to 50A/m2(ii) a The temperature of the lithium-containing solution, the organic phase and the lithium-enriched solution in the electrolytic cell is 0-80 degrees, preferably 10-40 degrees.
Specifically, to increase the efficiency of lithium ion transport into the cathode compartment, the applied voltage is maintained in a suitable range to produce a current density between the two electrodes. In addition, the organic phase chamber is maintained in an appropriate width range, and the current density is maintained in an appropriate range, so that the separation effect on lithium ions can be further enhanced. The current density is too high, so that a large amount of side reactions are easily caused, and the current efficiency is reduced; too small results in a reduced rate of electromigration, resulting in lower production extraction efficiency.
In the electrolytic cell, because the anode chamber, the organic phase chamber and the cathode chamber are separated by only adopting the ion exchange membrane, the temperatures of the lithium-containing solution in the anode chamber, the organic phase in the organic phase chamber and the lithium-enriched solution in the cathode chamber are consistent. The low temperature can affect the migration rate of ions in the reagent in the electrolytic bath; the temperature is too high, some organic phase components are volatile and cause loss, the solution temperature needs additional energy for heating, and the production cost is increased due to the high temperature.
Based on the above embodiment, the initial solution of the lithium-enriched solution, i.e. the supporting electrolyte, is a non-toxic, cheap and readily available inorganic salt solution, specifically NaCl, KCl, HCl, NH4Cl、Na2SO4、K2SO4、NaNO3And KNO3One or more of NaCl, HCl and K may be more preferable2SO4And NaNO3One or more of them.
On the basis of the embodiment, the anode material adopts any one of conductive carbon felt, carbon fiber felt, sponge graphite, high-purity graphite plate, platinum group metal and alloy foil thereof, carbon fiber cloth and graphite paper; the cathode material can be any one of conductive carbon felt, carbon fiber felt, sponge graphite, high-purity graphite plate, platinum group metal and alloy foil thereof, carbon fiber cloth, graphite paper, stainless steel and titanium material.
On the basis of the above examples, the pH of the lithium-containing solution was maintained at 1 to 9, and the pH of the lithium-rich solution was maintained at 1 to 8. The pH values of the lithium-containing solution and the lithium enrichment solution are kept in a proper range, so that the effect of lithium separation can be prevented from being influenced by precipitation or complexation of metal ions in the solution.
On the basis of the embodiment, an ion exchange membrane is adopted to divide an electrolytic cell into an anode chamber, an organic phase chamber and a cathode chamber, and lithium ions in a lithium-containing solution in the anode chamber are transferred to a lithium-enriched solution in the cathode chamber through an organic phase in the organic phase chamber under the action of an external voltage;
wherein the organic reagent in the organic phase is a mixed reagent containing dibenzoyl toluene (HDBM) and trioctyl phosphine oxide (TOPO), a mixed reagent containing fluorine beta-diketone and trioctyl phosphine oxide, a mixed reagent containing tributyl phosphate (TBP) and diisobutyl ketone (DIBK), a mixed reagent containing tributyl phosphate and FeCl3A mixed reagent containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide, a mixed reagent containing tributyl phosphate andone or more of the mixed reagent, N-di (1-methylheptyl) hexanamide and N263;
the concentration of lithium ions in the lithium-containing solution is 0.1-20 g/L;
the concentration of lithium ions transferred to the lithium enrichment solution is 0.05-20 g/L;
the pH of the lithium-containing solution is 1 to 9, preferably 2 to 5;
the pH of the lithium-rich solution is 1 to 8, preferably 1 to 5.
Specifically, the pH in the lithium-containing solution and/or the lithium-rich liquid is maintained in a suitable range, and precipitation of lithium ions present therein or formation of complexes, which are disadvantageous for separation, can be avoided.
It will be appreciated that the method is also applicable to separation between other different ion species.
Referring to fig. 1, there is also provided an apparatus for separating lithium from a lithium-containing solution according to another aspect of the present invention, including: an electrolytic cell for separating and extracting lithium, which is partitioned into an anode chamber, an organic phase chamber and a cathode chamber by an ion exchange membrane 1, wherein the organic phase chamber is positioned between the anode chamber and the cathode chamber; an anode 2 connected with a direct current power supply is arranged in the anode chamber, and a cathode 3 connected with the direct current power supply is arranged in the cathode chamber; and the anode chamber, the organic phase chamber and the cathode chamber are respectively connected with a circulating pump for conveying a reagent.
The beneficial effects of the invention are mainly as follows:
(1) an ion exchange membrane is adopted to separate a lithium-containing solution, an organic phase and a lithium enrichment solution in an electrolytic tank, under the action of an external voltage, lithium in the lithium-containing solution enters the lithium enrichment solution through the organic phase which can selectively perform chemical reaction with lithium ions, and the lithium ions in the lithium-containing solution can be effectively separated from other metal ions or impurities to achieve the purpose of extracting the lithium; by adopting the method, the lithium-containing solution with high magnesium-lithium ratio can be well separated, and the content of sodium ions is effectively reduced;
(2) the ion exchange membrane is combined with the electroosmosis effect, so that the separation and extraction efficiency of lithium can be effectively improved, and the adopted ion exchange membranes are various and low in cost;
(3) the adopted organic reagent and supporting electrolyte have low cost and small dosage and can be recycled;
(4) the lithium ion concentration in the lithium-containing solution has a wide variation range and strong applicability.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for separating lithium from a lithium-containing waste liquid according to an embodiment of the present invention.
Description of reference numerals:
1-an ion exchange membrane; 2-an anode; 3-cathode.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The organic phase chambers in the following examples all have the same width.
Example 1
By adopting the electrolytic cell, the anode and the cathode are made of carbon fiber cloth, the two ion exchange membranes are microporous polytetrafluoroethylene membranes, 300ml of lithium-containing solution is contained in the anode chamber, and the anode chamber comprises the following positive ions: mg (magnesium)2+100g/L、Li+2g/L、Na+3.5g/L、K+3g/L and Ca2+2 g/L; the organic phase chamber is filled with tributyl phosphate and FeCl3The cathode chamber is filled with 300ml of supporting electrolyte with the concentration of 1mol/L NaCl. The reagents in the three chambers are respectively circulated by a pump, and the current density is controlled to be 25A/m at 30 DEG C2The pH value of the lithium-containing solution in the anode chamber is kept to be about 5, and the pH value of the solution in the cathode chamber is kept to be 2-3. The metal ion concentration in the cathode chamber after 10 hours of electrolysis is shown in the following table.
Example 2:
by adopting the electrolytic cell, the anode and the cathode are made of materialsHigh-purity graphite, two ion exchange membranes are porous polypropylene membranes, 300ml lithium-containing solution is filled in the anode chamber, and the positive ions of the high-purity graphite comprise: mg (magnesium)2+15g/L、Li+20g/L、Na+6g/L、K+4g/L and Ca2+2g/L, the organic phase chamber is filled with a mixed reagent of tributyl phosphate and dibenzoyl toluene, and the cathode chamber is filled with 300ml of 2mol/L K2SO4The supporting electrolyte of (1). The solutions in the three chambers are respectively circulated by pumps, and the current density is controlled to be 40A/m at 40 DEG C2The pH value of the lithium-containing solution in the anode chamber is kept to be 3.5, and the pH value of the solution in the cathode chamber is controlled to be in a range of 4-5. The metal ion concentration in the cathode compartment after electrolysis for 14 hours is shown in the following table.
Example 3:
by adopting the electrolytic cell, the anode material is high-purity graphite, the cathode material is stainless steel, the two ion exchange membranes are proton exchange membranes, 300mL of lithium-containing solution is filled in the anode chamber, 2700mL of lithium-containing solution is prepared outside for circulating supplement, and the anode composition is as follows: mg (magnesium)2+95g/L、Li+0.5g/L、Na+5.4g/L、K+3.2g/L and Ca2+3g/L organic phase chamber is filled with tributyl phosphate and ClO- 4300ml of a supporting electrolyte with a HCl concentration of 0.1mol/L are filled in the cathode chamber. The solutions in the three chambers are respectively circulated by pumps, and the current density is controlled to be 15A/m at 20 DEG C2The pH value of the lithium-containing solution in the anode chamber is kept at about 5, and the pH value of the solution in the cathode chamber is kept at about 4. The metal ion concentration in the cathode compartment after 30 hours of electrolysis is shown in the following table.
Example 4:
by adopting the electrolytic cell, the anode material is conductive carbon felt, the cathode material is foamed nickel, the two ion exchange membranes are electrophoresis cathode membranes, and 300ml of waste lithium ions are filled in the anode chamberThe cation composition of the recovered waste liquid of the sub-battery is as follows: li+3g/L、Cu2+2g/L、Na+1g/L、Ca2+0.5g/L、Co3+3.5g/L、Al3+2.5g/L、Ni2+2.5g/L and Mn4+3g/L, the organic phase chamber is filled with a mixed reagent of phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide, and the cathode chamber is filled with 300ml of NaNO with the concentration of 3mol/L3The three-chamber solutions are respectively circulated by a pump, and the current density is controlled to be 30A/m at 10 DEG C2The pH value of the lithium-containing solution in the anode chamber is kept between 2 and 3, and the pH value of the solution in the cathode chamber is controlled between 1.5 and 2.5. The metal ion concentration in the cathode compartment after 8 hours of electrolysis is shown in the following table.
Example 5:
by adopting the electrolytic cell, the anode material is sponge graphite, the cathode material is ruthenium-coated titanium mesh, the two ion exchange membranes are cation exchange membranes, 300mL of lithium-containing solution is filled in the anode chamber, 2700mL of lithium-containing solution is prepared outside for supplementing the reduction of lithium concentration, and the cation composition of the electrolytic cell is as follows: li+0.1g/L、Na+200g/L、Ca2+0.5g/L、Fe3+1.2g/L and Zn2+0.5g/L, N-di (1-methylheptyl) hexanamide in the organic phase chamber, and 300ml KNO with concentration of 1mol/L in the cathode chamber3The three-chamber solutions are respectively circulated by a pump, and the current density is controlled to be 50A/m at 30 DEG C2The pH value of the lithium-containing solution in the anode chamber is kept to be about 2, and the pH value of the solution in the cathode chamber is kept to be 1-3. The metal ion concentration in the cathode compartment after 50 hours of electrolysis is shown in the following table.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method of separating lithium from a lithium-containing solution, characterized by: an ion exchange membrane is adopted to divide an electrolytic cell into an anode chamber, an organic phase chamber and a cathode chamber, and lithium ions in a lithium-containing solution in the anode chamber are transferred to a lithium enrichment solution in the cathode chamber through an organic phase in the organic phase chamber under the action of an external voltage; wherein the organic phase is an organic reagent capable of selectively chemically reacting with lithium ions in the lithium-containing solution;
the concentration of lithium ions in the lithium-containing solution is 0.5-15 g/L;
the concentration of lithium ions transferred to the lithium enrichment solution is 2-10 g/L;
the pH of the lithium-containing solution is 2-5, and the pH of the lithium-enriched solution is 1-5;
the concentration ratio of the lithium ions in the lithium-containing solution to the lithium ions transferred to the lithium-enriched solution is 3:1-0.25: 1;
the organic reagent is:
mixed reagent containing dibenzoyltoluene and trioctylphosphine oxide, mixed reagent containing fluoro beta-diketone and trioctylphosphine oxide, mixed reagent containing tributyl phosphate and diisobutyl ketone, mixed reagent containing tributyl phosphate and FeCl3A mixed reagent containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide, a mixed reagent containing tributyl phosphate and
one or more of the mixed reagent, N-bis (1-methylheptyl) hexanamide and N263.
2. The method of claim 1, wherein the organic reagent is:
containing tributyl phosphate and FeCl3A mixed reagent containing tributyl phosphate (TBP) and diisobutyl ketone (DIBK), a mixed reagent containing tributyl phosphate and
and one or more of mixed reagents containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide.
3. The method of claim 1, wherein the step of separating lithium from the lithium-containing solution comprises:
the lithium-containing solution is preferably salt lake brine, old brine generated in the evaporation process of the salt lake brine, gas field brine, waste lithium battery recovery liquid or lithium-containing wastewater in the lithium carbonate production process.
4. The method of claim 1, wherein the ion exchange membrane is:
one or more of a microporous polytetrafluoroethylene membrane, a porous polypropylene membrane, a proton exchange membrane, a cation exchange membrane, an electrophoresis cathode membrane and a fast ion conductor membrane.
5. The method of claim 1, wherein the step of separating lithium from the lithium-containing solution comprises:
the applied voltage generates a current density between the anode and cathode compartments of 5-100A/m2；
The width of the organic chamber is 1-50 mm;
the temperature of the lithium-containing solution, the organic phase and the lithium enrichment solution in the electrolytic cell is 0-80 ℃.
6. The method of claim 5, wherein the step of separating lithium from the lithium-containing solution comprises:
the applied voltage generates a current density between the anode and cathode chambers of 20-50A/m2；
The width of the organic chamber is 5-10 mm;
the temperature of the lithium-containing solution, the organic phase and the lithium enrichment solution in the electrolytic cell is 10-40 ℃.
7. As claimed in any one of claims 1 to 6The method for separating lithium from a lithium-containing solution is characterized in that the initial solution of the lithium-rich solution is as follows: a soluble inorganic salt solution; the soluble inorganic salt solution comprises NaCl, KCl, HCl and NH4Cl、Na2SO4、K2SO4、NaNO3And KNO3One or more of them.
8. The apparatus of any one of claims 1 to 7, comprising:
an electrolytic cell for separating and extracting lithium, the electrolytic cell employing an ion exchange membrane to separate an anode compartment, an organic phase compartment and a cathode compartment, the organic phase compartment being located between the anode compartment and the cathode compartment;
the anode connected with a direct current power supply is arranged in the anode chamber, and the cathode connected with the direct current power supply is arranged in the cathode chamber;
the lithium ion battery comprises an anode chamber, an organic phase chamber and a cathode chamber, wherein the anode chamber contains a lithium-containing solution, the organic phase chamber contains an organic phase, the cathode chamber contains a lithium-containing enriched solution, the organic phase is an organic reagent which can selectively and chemically react with lithium ions in the lithium-containing solution, and the lithium ions in the lithium-containing solution in the anode chamber are transferred to the lithium-containing enriched solution in the cathode chamber through the organic phase in the organic phase chamber under the action of an external voltage;
the organic reagent is:
mixed reagent containing dibenzoyltoluene and trioctylphosphine oxide, mixed reagent containing fluoro beta-diketone and trioctylphosphine oxide, mixed reagent containing tributyl phosphate and diisobutyl ketone, mixed reagent containing tributyl phosphate and FeCl3A mixed reagent containing phenyl (azo-1) -2-hydroxynaphthalene and trioctylphosphine oxide, a mixed reagent containing tributyl phosphate and
one or more of the mixed reagent, N-bis (1-methylheptyl) hexanamide and N263.
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| CN115386740A (en) * | 2022-08-30 | 2022-11-25 | 中南大学 | Method and device for extracting lithium from brine or seawater based on electrodialysis principle |
| CN115369264B (en) * | 2022-09-05 | 2023-09-22 | 山西大学 | Method for separating lithium ions from lithium-containing waste residue acid system |
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