CN115744992A - Method for separating lithium and transition metal - Google Patents
Method for separating lithium and transition metal Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 44
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000002893 slag Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 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 19
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052748 manganese Inorganic materials 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 5
- 229910001416 lithium ion 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
- 230000035484 reaction time Effects 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 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
- 239000000463 material Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 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
- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 2
- 230000014759 maintenance of location Effects 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
- 230000008569 process Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 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
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 238000005868 electrolysis reaction 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
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
Classifications
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- 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 and transition metal, and belongs to the field of valuable metal separation and recovery. The method comprises the following steps: preparing a saturated strong alkali solution and a saturated carbonate solution; slowly dropping a saturated strong base solution into the mixed salt solution, monitoring the pH of the solution, stopping dropping the saturated strong base solution when the pH of the solution reaches about neutral, starting dropping a saturated carbonate solution until the pH of the solution reaches 8-10, and then stirring for reaction; and (3) carrying out solid-liquid separation on the reaction product to obtain precipitation slag and filtrate, washing the precipitation slag, merging the washed washing liquid into the filtrate, and finally drying the filtrate and the precipitation slag to obtain a lithium-rich liquid and transition metal-rich carbonate. The method is environment-friendly, simple to operate and good in precipitation separation effect, and realizes accurate retention and enrichment of lithium element while effectively separating various 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 method for separating lithium and transition metal.
Background
With the rapid development of new energy vehicles, lithium ion power batteries with high energy density and low self-discharge rate are beginning to be applied in new energy vehicles in large quantities, however, a large quantity of scrapped retired lithium batteries also pose certain challenges for environmental protection and metal recycling. At present, the pyrogenic process and the wet process recovery regeneration are the mainstream methods for lithium ion battery recovery, and both the pyrogenic process and the wet process recovery regeneration can finally obtain a mixed solution of lithium and other metal ions, li, ni, co, mn, cu, al, fe and other ions are dissolved and soaked in a recovery solution by adopting a leaching mode and the like, and the mixed ion solution is pretreated to remove impurities such as Al, fe and the like to obtain a lithium and transition metal mixed solution.
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-specific extractants, such as N902 for Cu extraction, TBP for Li extraction, the ion exchange adopts resin for selective adsorption and recovery of metal elements, and the modes of solvent extraction, ion exchange and the like are expensive and are not beneficial to large-scale industrial application. The chemical precipitation separation and recovery has low cost, wide application, mature technology and high product purity, but easily causes the defect of final recovery of lithium and more inclusion loss when the mixed solution of lithium and transition metal is recovered. In CN115074551A, a hydrophobic eutectic solvent and an organic phase of tributyl phosphate are prepared and mixed with a water phase containing lithium nickel cobalt to vibrate so as to realize solvent extraction and separation of lithium and other transition metals, the method has a good separation effect, but the extraction process is complicated in process and relatively high in cost, and is not beneficial to large-scale industrial application; CN110257631B uses acidic leaching solution containing lithium, nickel, cobalt and manganese as electrolyte and carries out electrolysis, and deposits containing lithium solution and transition metal are left after reaction. The invention aims to provide a metal separation method of lithium and transition metal, which is simple and convenient to operate, relatively low in cost and outstanding in separation effect.
Disclosure of Invention
The invention aims to solve the problems of difficult separation process of lithium and transition metal and low lithium recovery rate, and provides a method for separating and recovering lithium and other transition metals from a mixed solution of lithium and transition metals.
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 alkali solution and a saturated carbonate solution; (3) Slowly dropping a saturated strong base solution into the mixed salt solution, monitoring the pH of the solution, stopping dropping the saturated strong base solution when the pH of the solution is neutral, starting dropping a saturated carbonate solution until the pH of the solution reaches 8-10, and then stirring for reaction; (4) And (3) carrying out solid-liquid separation on the reaction product obtained in the step (3) to obtain precipitation slag and filtrate, washing the precipitation slag with washing water, merging the washing liquid after washing into the filtrate, and finally drying the filtrate and the precipitation slag to obtain a lithium-rich liquid and carbonate rich in transition metal.
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 selected from one or more of 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 strong base in step (2) mainly acts to adjust the pH, and the carbonate mainly acts to precipitate the transition metal ion, so that the phase of the precipitate formed is mainly a carbonate precipitate of the transition metal such as MnCO 3 、NiCO 3 And so on.
The further technical scheme is that after the strong alkali solution is added in the step (3), the dropwise addition of the saturated strong alkali solution is stopped after the pH value of the solution reaches 6-7, and the pH value is adjusted before the carbonate is added, so that the loss of the carbonate caused by directly adding the carbonate is reduced.
The further technical proposal is that the amount of the carbonate substance added in the step (3) is 1 to 1.5 times of the theoretical dosage to ensure the full conversion of the transition metal to the carbonate precipitate thereof, and the adding speed of the saturated carbonate is 5 to 50mL/min.
The theoretical amount of carbonate used is the amount of carbonate consumed when all the transition metal has just completely reacted with the carbonate.
The further technical proposal is that the saturated carbonate solution in the step (3) is continuously reacted after the addition is finished, 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:
(m+n)X 2+ +2mOH - +nCO 3 2- →mX(OH) 2 ·nXCO 3
X(OH) 2 +CO 3 2- →XCO 3 +2OH -
the pH value regulated in the first stage in the step (3) is 6-7, and the carbonate loss caused by gas generation when sodium carbonate meets acid can be reduced by regulating the acidity of the solution to the pH value. Then the adding amount of sodium carbonate is 1-1.5 of the theoretical amount (the theoretical amount is calculated according to the fact that 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 precipitation slag with good filtering performance, if the liquid adding speed is too fast, the local supersaturation degree is too high, the particle growth is inhibited, finally, fine grains are formed, the filtering performance is poor, the lithium loss is increased, and therefore the liquid adding speed is not suitable for being too fast.
In the step (3), after the sodium carbonate is added, continuously adding the alkaliMonitoring the pH of the solution until the final pH is 8-10, and establishing Li for verifying the feasibility of the separation and recovery of the lithium and transition metal mixed solution through carbonate precipitation + -Mn 2+ -CO 3 2- -SO 4 2- -H 2 Calculating 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 replaces a plurality of transition metal elements), and obtaining Mn in the solution when the pH of the solution reaches about 10 2+ Is 10 -5 Around mol/L, can be regarded as complete precipitation, and when the pH is equal to<At 11, no lithium carbonate precipitate is formed in the solution at all times, so theoretical calculations prove that lithium can be separated from the transition metal by this method.
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-5 mL/g slag, the washing water temperature is 50-80 ℃, and the washing times are 3-5 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 obvious 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 increasingly precious lithium resources.
Drawings
FIG. 1 is a schematic flow diagram of the separation of metals from a solution of lithium and transition metals;
FIG. 2 is Li + -Mn 2+ -CO 3 2- -SO 4 2- -H 2 The relationship between the total concentration of each ion in the O system and the pH.
Detailed Description
The technical application and effects of the present concept will be clearly and completely explained in the following with reference to the embodiments. And manganese was used instead of a number of transition metals. The following examples are only some of the examples related to the present invention, and the other related cases without innovative concept are all within the scope of the present 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 into the mixed solid to prepare 1000mL of solution for later use.
(2) Preparation of saturated NaOH and Na2CO3 solution: 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; and (3) adding Na2CO3 powder into 500mL of deionized water, continuously stirring in the adding process until the solution can not be dissolved any more, recording the adding amount of the sodium carbonate, and forming a saturated Na2CO3 solution for later use.
(3) Precipitation of transition metals: taking 100mL of the mixed metal salt solution in the step (1), putting the solution into a heating stirring tank, setting the temperature of the solution to be 25 ℃, and then starting stirring. And (3) gradually dropwise adding the saturated sodium hydroxide solution obtained in the step (2) into the solution, monitoring the pH, adjusting the pH to 6.5, then beginning 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) And (3) carrying out solid-liquid separation to obtain lithium-rich liquid and transition metal carbonate: and (3) carrying out suction filtration on the reaction solution in the step (3), preparing deionized water at 50 ℃ for washing the precipitation slag obtained by suction filtration, washing the slag for three times in total with washing water of 5mL/g of slag, merging the washing liquid into the filtrate, collecting the filtrate and the precipitation slag, and drying to obtain a lithium-rich liquid and a carbonate rich in transition metal. Detecting and calculating the lithium, manganese and sodium contents in the filtrate and the precipitation slag jointly, and finding that the lithium-rich liquid has an enrichment rate of lithium of 98.05 percent and a residual concentration of manganese of 5.1mg/L and contains a certain amount of sodium element; and drying, weighing, dissolving and detecting the ion content in the dissolved solution to find that main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.39% of the mass of the manganese slag, 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
This example provides a method for separating and recovering lithium and transition metal, which changes the reaction temperature in step three of example 1 to 75 ℃, and does not change the rest steps and process parameters. Detecting and combining the lithium, manganese and sodium contents in the filtrate and the precipitation slag, and finding that the lithium-enriched liquid has an enrichment ratio of 99.13 percent of lithium, a residual concentration of 3.2mg/L of manganese and a certain amount of sodium element; and drying, weighing, dissolving and detecting the ion content in the dissolving solution to find that main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.25 percent of the mass of the manganese slag, sodium accounts for 0.25 percent of the total mass, the total mass accounts for about 0.5 percent, and the enrichment rate of manganese is 99.95 percent. By observing the result after the temperature rise, the inclusion loss of lithium is not difficult to find out to be reduced, because the growth of manganese carbonate crystal nucleus is promoted by high temperature, the filtration performance of slag phase is further optimized, and the enrichment recovery rate of lithium is improved.
Example 3
This example provides a method for separating and recovering lithium and transition metal, in which the reaction end point pH in step three in example 1 is changed to 8, and the rest steps and process parameters are unchanged. Detecting and calculating the lithium, manganese and sodium contents in the filtrate and the precipitation slag jointly, and finding that the lithium-rich liquid has an enrichment rate of 99.24 percent of lithium and a residual concentration of 67.2mg/L of manganese and contains a certain amount of sodium element; and drying, weighing, dissolving and detecting the ion content in the dissolving solution to find that main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.35 percent of the mass of the manganese slag, sodium accounts for 0.43 percent of the total mass and does not exceed 1 percent of the total mass, and the enrichment rate of manganese is 98.13 percent. By lowering the end point pH, it is not difficult to find a decrease in the manganese enrichment rate, since the lower end point pH results in a failure of the manganese to achieve a complete precipitation effect.
Example 4
This example provides a method for separating and recovering lithium and transition metal, in which the reaction time in step three in example 1 is changed to 9h, and the rest steps and process parameters are unchanged. Detecting and calculating the lithium, manganese and sodium contents in the filtrate and the precipitation slag jointly, and finding that the lithium-rich liquid has an enrichment rate of 99.64 percent of lithium and a residual concentration of 8.2mg/L of manganese and contains a certain amount of sodium element; and drying, weighing, dissolving and detecting the ion content in the dissolving solution to find that main impurity elements in the manganese precipitate are lithium and sodium elements, wherein lithium accounts for 0.16 percent of the mass of the manganese slag, sodium accounts for 0.27 percent of the total mass, the total mass is not more than 0.5 percent, and the enrichment ratio of manganese is 99.63 percent. By extending the reaction time, it was found that the enrichment of manganese was reduced and the inclusion loss of lithium was reduced, because sufficient stirring time allowed the nuclei to gradually form so that the filtration performance of the slag phase was sufficiently optimized.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (7)
1. A method for separating lithium from a transition metal, comprising the steps of: preparing saturated strong alkali solution and saturated carbonate solution; (2) Slowly dropping a saturated strong base solution into the mixed salt solution, monitoring the pH of the solution, stopping dropping the saturated strong base solution when the pH of the solution is neutral, starting dropping a saturated carbonate solution until the pH of the solution reaches 8-10, and then stirring for reaction; (3) And (3) carrying out solid-liquid separation on the reaction product obtained in the step (2) to obtain precipitation slag and filtrate, washing the precipitation slag with washing water, merging the washing liquid after washing into the filtrate, and finally drying the filtrate and the precipitation slag to obtain a lithium-rich liquid and carbonate rich in transition metal.
2. The method for separating lithium and transition metal according to claim 1, wherein the concentration of lithium ions in the mixed salt solution in step (1) is 0.5-10 g/L, the concentration of transition metal ions is 2-80 g/L, the transition metal salt is a sulfate or nitrate of transition metal, and the transition metal comprises one or more of nickel, cobalt, manganese and copper valuable transition metals.
3. The method for separating lithium and transition metal according to claim 1, wherein the strong base in step (2) is selected from one of sodium hydroxide and potassium hydroxide or a mixture thereof, and the carbonate is one of potassium carbonate and sodium carbonate or a mixture thereof.
4. The method for separating lithium from transition metal according to claim 1, wherein after the addition of the strong alkali solution in the step (3), the solution pH is 6 to 7 and is kept substantially stable, and then the dropwise addition of the saturated strong alkali solution is stopped.
5. The method of claim 1, wherein the amount of the carbonate material added in the step (3) is 1 to 1.5 times of the theoretical amount, and the rate of the addition of the saturated carbonate is 5 to 50mL/min.
6. The method of claim 1, wherein the reaction is continued after the saturated carbonate solution is added in the step (3), the reaction temperature is maintained at 25-75 ℃, the stirring intensity is 100-500 rpm/min, and the reaction time is 3-9 h.
7. The method for separating lithium and transition metal according to claim 1, wherein the solid-liquid separation in step (4) is performed 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.
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| CN202211662934.2A CN115744992B (en) | 2022-12-23 | 2022-12-23 | Separation method of lithium and transition metal |
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| CN202211662934.2A CN115744992B (en) | 2022-12-23 | 2022-12-23 | Separation method of lithium and transition metal |
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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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