CN115744992B - Separation method of lithium and transition metal - Google Patents
Separation method of lithium and transition metal Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 43
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 36
- 238000000926 separation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 60
- 239000002893 slag Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052748 manganese Inorganic materials 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- -1 transition metal salt Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910000299 transition metal carbonate Inorganic materials 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- RKGLUDFWIKNKMX-UHFFFAOYSA-L dilithium;sulfate;hydrate Chemical compound [Li+].[Li+].O.[O-]S([O-])(=O)=O RKGLUDFWIKNKMX-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating lithium from transition metal, and belongs to the field of separation and recovery of valuable metals. The method comprises the following steps: preparing a saturated alkali solution and a saturated carbonate solution; slowly dripping saturated alkali solution into the mixed salt solution, monitoring the pH of the solution, stopping dripping the saturated alkali solution after the pH of the solution reaches about neutrality, starting dripping saturated carbonate solution until the pH of the solution reaches 8-10, and stirring for reaction; and (3) carrying out solid-liquid separation on the reaction product to obtain precipitation slag and filtrate, washing the precipitation slag, collecting washing liquid after washing into the filtrate, and finally drying the filtrate and the precipitation slag to obtain lithium-rich liquid and carbonate rich in transition metal. The method is environment-friendly, simple to operate and good in precipitation separation effect, and realizes accurate retention and enrichment of lithium elements while effectively separating valuable components in the mixed metal solution.
Description
Technical Field
The invention relates to the technical field of valuable metal recovery, in particular to a separation method of lithium and transition metal.
Background
With the rapid development of new energy automobiles, lithium ion power batteries with high energy density and low self-discharge rate are widely applied to the new energy automobiles, however, a great number of scrapped retired lithium batteries also cause certain challenges for environmental protection and metal recovery and regeneration. At present, the fire method and the wet method recovery regeneration are main methods for recovering lithium ion batteries, and the two methods can finally obtain a mixed solution of lithium and other metal ions, and Li, ni, co, mn, cu, al, fe plasma is leached in the recovery solution in a leaching mode, and the mixed ion solution is pretreated and then impurities such as Al, fe and the like are removed to obtain the mixed solution of lithium and transition metal.
The separation and recovery of the metal mixed solution mainly comprises the modes of chemical precipitation, solid-liquid separation, solvent extraction, back extraction, ion exchange, electrochemical deposition and the like, wherein the solvent extraction adopts a large amount of ion special-effect extractants, such as N902 to Cu extraction and TBP to Li extraction, the ion exchange adopts the mode of resin selective adsorption to recover metal elements, the solvent extraction and the ion exchange are high in price, and the industrial large-scale application is not facilitated. The chemical precipitation separation recovery cost is low, the application is wide, the technology is mature, the product purity is high, but the defect that the lithium is recovered finally and the inclusion loss is more is easily caused when the lithium and transition metal mixed solution is recovered. In CN115074551A, solvent extraction separation of lithium and other transition metals is realized by preparing an organic phase of a hydrophobic eutectic solvent and tributyl phosphate and mixing and vibrating the organic phase with a water phase containing lithium, nickel and cobalt, and the method has better separation effect, but the extraction process is complicated in process and relatively high in cost, so that the method is unfavorable for large-scale industrial application; in CN110257631B, an acidic leaching solution containing lithium, nickel, cobalt and manganese is used as an electrolyte and is electrolyzed, and deposits of a lithium-containing solution and transition metal are left after the reaction. The invention aims to seek a metal separation method of lithium and transition metal, which is simple and convenient to operate, relatively low in cost and relatively outstanding in separation effect.
Disclosure of Invention
The invention provides a method for separating and recovering lithium and other transition metals from a mixed solution of lithium and transition metals, which aims to solve the problems of difficult separation process of lithium and transition metals and low recovery rate of lithium.
In order to achieve the technical effects, the invention provides the following technical scheme:
A method for separating lithium from a transition metal, comprising the steps of: (1) Mixing lithium salt and transition metal salt, adding deionized water, and stirring until the lithium salt and the transition metal salt are completely dissolved to obtain a mixed salt solution; (2) preparing a saturated strong base solution and a saturated carbonate solution; (3) Slowly dripping saturated alkali solution into the mixed salt solution, monitoring the pH of the solution, stopping dripping the saturated alkali solution after the pH of the solution reaches neutrality, starting dripping saturated carbonate solution until the pH of the solution reaches 8-10, and stirring for reaction; (4) And (3) carrying out solid-liquid separation on the reaction product of the step (3) to obtain precipitation slag and filtrate, washing the precipitation slag with washing water, collecting the washing water after washing into the filtrate, and finally drying the filtrate and the precipitation slag to obtain lithium-rich liquid and carbonate rich in transition metals.
The further technical scheme is that the concentration of lithium ions in the mixed salt solution in the step (1) is 0.5-10 g/L, the concentration of transition metal ions is 2-80 g/L, the transition metal salt is sulfate or nitrate of transition metal, and the transition metal is one or more selected from nickel, cobalt, manganese and copper.
The further technical scheme is that in the step (2), the strong base is sodium hydroxide or potassium hydroxide, and the carbonate is potassium carbonate or sodium carbonate.
The action of the strong base in step (2) is mainly to adjust the pH, while the action of the carbonate is mainly to precipitate the transition metal ions, so that the precipitated phase formed is mainly carbonate precipitation of the transition metal such as MnCO 3、NiCO3, etc.
The further technical proposal is that after the strong alkali solution is added in the step (3), the solution pH reaches 6-7, and then the saturated alkali solution is stopped to be added dropwise, and the pH is regulated before the carbonate is added, thereby being beneficial to reducing the carbonate loss caused by directly adding the carbonate.
The further technical proposal is that the amount of carbonate substances added in the step (3) is 1 to 1.5 times of the theoretical dosage so as to ensure the full conversion of transition metal to carbonate precipitation, and the adding speed of saturated carbonate is 5 to 50mL/min.
The theoretical amount is the amount of carbonate consumed when all transition metals are just fully reacted with carbonate.
The further technical proposal is that the saturated carbonate solution in the step (3) is continuously reacted after being added, the reaction temperature is 25-75 ℃, the stirring intensity is 100-500 rpm/min, and the reaction time is 3-9 h. The reaction chemical formula is as follows:
(m+n)X2++2mOH-+nCO3 2-→mX(OH)2·nXCO3
X(OH)2+CO3 2-→XCO3+2OH-
The pH value regulated in the first stage in the step (3) is 6-7, and the acidity of the solution is regulated to the pH value, so that the loss of carbonate radical caused by the acid production of sodium carbonate can be reduced. And then the adding amount of sodium carbonate is 1-1.5 of the theoretical dosage (the theoretical dosage is calculated according to the condition that the transition metal carbonate is just completely generated), the liquid adding speed is 5-50 mL/min, the proper liquid adding speed is favorable for forming precipitated slag with good filtering performance, if the liquid adding speed is too fast, the local supersaturation degree is easily high, the particle growth is inhibited, and finally fine crystal grains are formed, so that the filtering performance is poor, the lithium loss is increased, and therefore, the liquid adding speed needs to be controlled to be not too fast.
In the step (3), alkali liquor is continuously added after the addition of sodium carbonate is finished and the pH is monitored until the end point pH is 8-10, in order to verify the feasibility of separating and recovering the lithium and transition metal mixed solution through carbonate precipitation, a Li +-Mn2+-CO3 2--SO4 2--H2 O system is established, the relation between the ion concentration and the pH change of the solution and the occurrence state change of transition metal ions in the solution (Mn is used for replacing a plurality of transition metal elements), when the pH of the solution reaches about 10, the Mn 2+ in the solution is about 10 -5 mol/L, the solution can be regarded as complete precipitation, and when the pH is less than 11, no lithium carbonate precipitate is formed in the solution all the time, so that the separation of lithium and transition metal can be proved by theoretical calculation.
The further technical proposal is that the solid-liquid separation process in the step (4) is carried out by suction filtration, the total amount of washing water is 2mL/g slag to 5mL/g slag, the washing water temperature is 50 to 80 ℃ and the washing times are 3 to 5 times.
Compared with the prior art, the invention has the following beneficial effects: by adopting the separation method, the mixed solution of lithium and transition metal can be treated to obtain higher element separation efficiency and selective recovery rate of lithium element, and more than 99% of lithium can be completely separated and recovered theoretically. The method has the advantages of very remarkable beneficial effects, simple operation, low cost and mature process, can realize high-selectivity and high-purity recovery of lithium resources, and has important significance for the current increasing precious lithium resources.
Drawings
FIG. 1 is a schematic flow chart of metal separation in a solution of lithium and transition metals;
FIG. 2 is a graph showing the total concentration of each ion in the Li +-Mn2+-CO3 2--SO4 2--H2 O system as a function of pH.
Detailed Description
Technical applications and effects in the present concept will be clearly and completely explained in the following examples. And experiments were performed with manganese instead of numerous transition metals. The following examples are only some of the examples related to the present invention, and all other related cases not subjected to innovative concepts are within the scope of the invention.
Example 1
(1) Preparation of mixed metal ion solution: 100g of manganese sulfate monohydrate and 10g of lithium sulfate monohydrate powder are mixed, and deionized water is added to the mixed solid to prepare 1000mL of solution for later use.
(2) Preparation of saturated NaOH and Na2CO3 solutions: taking 100g of sodium hydroxide solid, adding deionized water into the sodium hydroxide solid in batches, continuously stirring until the solution becomes clear and only a small amount of NaOH solid remains, and filtering to obtain a saturated NaOH solution for later use; 500mL of deionized water is taken, na2CO3 powder is added into the solution, stirring is continuously carried out in the adding process until the solution can not be dissolved any more, and the adding amount of sodium carbonate is recorded, so that a saturated Na2CO3 solution is formed for standby.
(3) Precipitation of transition metals: 100mL of the mixed metal salt solution in the step (1) was taken, placed in a heating and stirring tank, and stirring was started after the temperature of the solution was set to 25 ℃. Gradually dropwise adding the saturated sodium hydroxide solution in the step (2) into the solution, monitoring the pH at the same time, adjusting the pH to 6.5, then starting to dropwise add the saturated sodium carbonate solution with the theoretical dosage at the liquid inlet speed of 10mL/min, continuously adjusting the pH to 10 after the addition is finished, continuously reacting for about 3 hours after the pH is stable, and keeping the pH, the temperature and the stirring strength stable in the process.
(4) After solid-liquid separation, lithium-rich liquid and transition metal carbonate are obtained: and (3) carrying out suction filtration on the reaction solution obtained in the step (3), preparing deionized water at 50 ℃ to wash precipitation slag obtained by suction filtration, washing the slag for three times in total with the total amount of washing water of 5mL/g slag, collecting the washing liquid into filtrate, collecting the filtrate and the precipitation slag, and drying to obtain lithium-rich liquid and carbonate rich in transition metals. The content of lithium, manganese and sodium in the filtrate and the precipitation slag are detected and combined, and the result shows that the enrichment rate of lithium in the lithium-rich liquid is 98.05 percent, the residual concentration of manganese is 5.1mg/L and a certain amount of sodium element is contained; drying the manganese-containing precipitate, weighing, dissolving and detecting the ion content in the solution, and finding that the main impurity elements in the manganese precipitate are lithium and sodium elements, wherein the lithium accounts for 0.39% of the mass of the manganese slag, the sodium accounts for 0.55% of the total mass, the total mass is not more than 1%, and the enrichment rate of manganese is 99.95%.
Example 2
The embodiment provides a method for separating and recovering lithium and transition metal, wherein the reaction temperature in the third step in the embodiment 1 is changed to 75 ℃, and the other steps and technological parameters are unchanged. The content of lithium, manganese and sodium in the filtrate and the precipitation slag are detected and combined, and the result shows that the enrichment rate of lithium in the lithium-rich liquid is 99.13 percent, the residual concentration of manganese is 3.2mg/L and the lithium-rich liquid contains a certain amount of sodium element; drying the manganese-containing precipitate, weighing, dissolving and detecting the ion content in the solution, and finding that the main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.25% of the mass of the manganese slag, sodium accounts for 0.25% of the total mass, the total mass accounts for about 0.5%, and the enrichment rate of manganese is 99.95%. By observing the result after temperature rise, the lithium inclusion loss is not difficult to be found to be reduced, because the high temperature promotes the growth of manganese carbonate crystal nucleus, further optimizes the filtering performance of slag phase and improves the enrichment recovery rate of lithium.
Example 3
The embodiment provides a method for separating and recovering lithium and transition metal, wherein the pH of the reaction end point in the step three in the embodiment 1 is changed to 8, and the rest steps and process parameters are unchanged. The content of lithium, manganese and sodium in the filtrate and the precipitation slag are detected and combined, and the result shows that the enrichment rate of lithium in the lithium-rich liquid is 99.24%, the residual concentration of manganese is 67.2mg/L and a certain amount of sodium element is contained; drying the manganese-containing precipitate, weighing, dissolving and detecting the ion content in the solution, and finding that the main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.35% of the mass of the manganese slag, sodium accounts for 0.43% of the total mass, the total mass is not more than 1%, and the enrichment rate of manganese is 98.13%. By lowering the endpoint pH, it is not difficult to find a decrease in the enrichment of manganese, as lower endpoint pH results in failure of the manganese to achieve a complete precipitation effect.
Example 4
The embodiment provides a method for separating and recovering lithium and transition metal, wherein the reaction time in the third step in the embodiment 1 is changed to 9 hours, and the rest steps and process parameters are unchanged. The content of lithium, manganese and sodium in the filtrate and the precipitation slag are detected and combined, and the result shows that the enrichment rate of lithium in the lithium-rich liquid is 99.64 percent, the residual concentration of manganese is 8.2mg/L and the lithium-rich liquid contains a certain amount of sodium element; drying the manganese-containing precipitate, weighing, dissolving and detecting the ion content in the solution, and finding that the main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.16% of the mass of the manganese slag, sodium accounts for 0.27% of the total mass, the total mass is not more than 0.5%, and the enrichment rate of manganese is 99.63%. By extending the reaction time, it is not difficult to find that the enrichment rate of manganese is reduced and the inclusion loss of lithium is reduced, because the sufficient stirring time allows the crystal nuclei to be gradually formed so that the filtration performance of the slag phase is sufficiently optimized.
Although the application has been described herein with reference to the above-described illustrative embodiments thereof, the foregoing embodiments are merely preferred embodiments of the present application, and it should be understood that the embodiments of the present application are not limited to the above-described embodiments, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.
Claims (3)
1. A method for separating lithium from a transition metal, comprising the steps of: (1) Mixing lithium salt and transition metal salt, adding deionized water, and stirring until the lithium salt and the transition metal salt are completely dissolved to obtain a mixed salt solution; the concentration of lithium ions in the mixed salt solution is 0.5-10 g/L, the concentration of transition metal ions is 2-80 g/L, the transition metal salt is sulfate or nitrate of transition metal, and the transition metal contains one or more of nickel, cobalt, manganese and copper valuable transition metals; (2) preparing a saturated strong base solution and a saturated carbonate solution; (3) Slowly dripping saturated alkali solution into the mixed salt solution, monitoring the pH of the solution, stopping dripping the saturated alkali solution after the pH of the solution reaches neutrality, starting dripping the saturated carbonate solution until the pH of the solution reaches 8-10, stopping stirring and reacting; the amount of carbonate substances added in the step (3) is 1-1.5 times of the theoretical dosage, and the adding speed of the saturated carbonate solution is 5-50 mL/min; continuing the reaction after the saturated carbonate solution is added in the step (3), keeping the reaction temperature at 25-75 ℃ in the whole process, and stirring at 100-500 rpm for 3-9 hours; (4) And (3) carrying out solid-liquid separation on the reaction product of the step (3) to obtain precipitation slag and filtrate, washing the precipitation slag with washing water, collecting the washing water after washing into the filtrate, and finally drying the filtrate and the precipitation slag to obtain lithium-rich liquid and carbonate rich in transition metals.
2. The method of claim 1, wherein the strong base in step (2) is selected from one or a mixture of sodium hydroxide and potassium hydroxide, and the carbonate is one or a mixture of potassium carbonate and sodium carbonate.
3. The method for separating lithium from transition metal according to claim 1, wherein the solid-liquid separation process in the step (4) is performed by suction filtration, the total amount of washing water is 2-5 mL/g slag, the washing water temperature is 50-80 ℃, and the washing times are 3-5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211662934.2A CN115744992B (en) | 2022-12-23 | 2022-12-23 | Separation method of lithium and transition metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2001092152A1 (en) * | 2000-05-31 | 2001-12-06 | Carboxyque Francaise | Method for recuperating a metal in carbonate or hydrogenocarbonate form |
| CN106848474A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method of high efficiente callback positive electrode material precursor and lithium carbonate from lithium ion cell anode waste |
| CN109338105A (en) * | 2018-10-16 | 2019-02-15 | 长沙矿冶研究院有限责任公司 | A method of valuable metal is efficiently separated from the mixed solution of nickel and cobalt containing manganese lithium |
| CN110994063A (en) * | 2019-11-28 | 2020-04-10 | 怀德创建有限公司 | Recovery method for selectively extracting lithium and transition metal from lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092152A1 (en) * | 2000-05-31 | 2001-12-06 | Carboxyque Francaise | Method for recuperating a metal in carbonate or hydrogenocarbonate form |
| CN106848474A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method of high efficiente callback positive electrode material precursor and lithium carbonate from lithium ion cell anode waste |
| CN109338105A (en) * | 2018-10-16 | 2019-02-15 | 长沙矿冶研究院有限责任公司 | A method of valuable metal is efficiently separated from the mixed solution of nickel and cobalt containing manganese lithium |
| CN110994063A (en) * | 2019-11-28 | 2020-04-10 | 怀德创建有限公司 | Recovery method for selectively extracting lithium and transition metal from lithium ion battery anode material |
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