CN117509689A - Preparation method of lithium carbonate - Google Patents
Preparation method of lithium carbonate Download PDFInfo
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- CN117509689A CN117509689A CN202311668239.1A CN202311668239A CN117509689A CN 117509689 A CN117509689 A CN 117509689A CN 202311668239 A CN202311668239 A CN 202311668239A CN 117509689 A CN117509689 A CN 117509689A
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- leaching
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- calcine
- lithium carbonate
- ore pulp
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000571 coke Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001385 heavy metal Inorganic materials 0.000 description 13
- 238000004537 pulping Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a preparation method of lithium carbonate, which comprises the following steps: mixing black powder and coke to obtain a mixture, wherein the black powder comprises a lithium salt positive electrode material and a graphite negative electrode material, the lithium salt positive electrode material comprises at least one element of cobalt, manganese or nickel, and roasting the mixture to obtain calcine, and the calcine comprises Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Taking a part of calcine for size mixing to obtain first ore pulp, leaching Li ions in the first ore pulp by adopting sulfuric acid aqueous solution, regulating the pH value to be 6-7 to obtain second ore pulp, and carrying out solid-liquid separation on the second ore pulp to obtain first leaching liquid and first leaching slag; mixing the first leaching solution with a part of new calcine, regulating the pH value to 10-11 to obtain third ore pulp, and carrying out solid-liquid separation on the third ore pulp to obtain second leaching solution and second leaching residue; and heating the second leaching solution to a temperature of more than 90 ℃, and then adding the second leaching solution into a carbonate solution with a temperature of 80-90 ℃ to obtain a lithium carbonate mixed solution. The preparation method provided by the application is beneficial to reducing the preparation cost and improving the purity of the lithium carbonate.
Description
Technical Field
The invention relates to the technical field of lithium battery material recovery, in particular to a preparation method of lithium carbonate.
Background
The current method for preparing lithium carbonate by recycling the positive electrode material of the lithium battery comprises the following steps: the ammonia roasting converts lithium cobaltate into sulfate, the organic extractant is used for recovering cobalt, the precipitation method is used for recovering lithium in residual liquid, and the lithium is recovered in the form of lithium carbonate. The extraction and separation process flow and equipment are complex, which is not beneficial to reducing the recovery cost, and in addition, the extraction and separation process possibly causes the residue of the extractant, thereby being not beneficial to improving the purity of the lithium carbonate.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of lithium carbonate, which is beneficial to reducing the preparation cost and improving the purity.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing lithium carbonate, comprising the following steps:
step one: mixing black powder and coke to obtain a mixture, wherein the black powder comprises a lithium salt positive electrode material and a graphite negative electrode material, the lithium salt positive electrode material comprises at least one element of cobalt, manganese or nickel, the mixture is placed in an air atmosphere roasting kiln to be roasted to obtain calcine, and the calcine comprises Li 2 CO 3 Roasting at 550-650 deg.c for 40-100 min;
step two: taking a part of the calcine, mixing pulp to obtain first ore pulp, leaching Li ions in the first ore pulp by adopting sulfuric acid aqueous solution, regulating the pH value to be 6-7 to obtain second ore pulp, and carrying out solid-liquid separation on the second ore pulp to obtain first leaching liquid and first leaching slag;
step three: mixing the first leaching solution with a part of new calcine, regulating the pH value to 10-11 to obtain third ore pulp, and carrying out solid-liquid separation on the third ore pulp to obtain second leaching solution and second leaching residue;
step four: and heating the second leaching solution to a temperature of more than 90 ℃ and then adding the second leaching solution into a carbonate solution to obtain a lithium carbonate mixed solution, wherein the temperature of the carbonate solution is 80-90 ℃.
In some possible embodiments, the step four further includes:
and (3) reacting the lithium carbonate mixed solution at the reaction temperature of 80-90 ℃ for 60-90 minutes.
In some possible embodiments, the ratio of the black powder to the coke is 4 by mass: 1-6:1.
in some possible embodiments, the firing temperature is 550-600 ℃ and the firing time is 40-60 minutes.
In some possible embodiments, in step two, the aqueous sulfuric acid solution has a concentration of 1.5-2mol/L and the Li ion concentration is 18-24g/L, and in step four, the carbonate solution has a concentration of 340-360g/L.
In some possible embodiments, the ratio of the second pulp to the calcine in step three is 5 by mass: 1-6:1.
in some possible embodiments, in the fourth step, the duration of the addition of the second leaching solution is controlled to be 60-90 minutes.
In some possible embodiments, the third step further includes:
washing the second leaching residue by adopting sulfuric acid aqueous solution to obtain slag and washing liquid;
the preparation method further comprises the following steps:
returning the washing liquid to the second step to carry out slurry mixing on the calcine by using the washing liquid, and repeating the second step to the fourth step.
In some possible embodiments, in the third step, the concentration of the sulfuric acid aqueous solution is 0.15 to 0.2mol/L, and the ratio of the second leaching residue to the sulfuric acid aqueous solution is 1 by mass: 5.
compared with the prior art, the invention has the beneficial effects that:
in the application, the black powder obtained by disassembling the lithium battery comprises a graphite negative electrode material and a lithium salt positive electrode material, the lithium salt positive electrode material comprises at least one element of cobalt, manganese or nickel, the calcine containing lithium carbonate is obtained after the black powder and coke are subjected to reduction roasting, a part of the calcine reacts with sulfuric acid to enable cations (including LI ions) in the calcine to leach out to obtain reaction ore pulp, the reaction ore pulp and a part of new calcine undergo a displacement reaction, and the heavy metal elements (such as cobalt, manganese or nickel) can form carbonate precipitation and precipitation, so that the purity of the finally prepared lithium carbonate is improved. In addition, the calcine containing lithium carbonate is used as the impurity removing agent for heavy metals, and an additional extracting agent or precipitating agent is not needed to be added, so that other impurities cannot be introduced, and the preparation cost of the lithium carbonate is reduced.
The invention is described in further detail below with reference to the drawings and the detailed description.
Drawings
Fig. 1 is a flowchart of a method for preparing lithium carbonate according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without undue burden, are within the scope of the present application.
The terms first, second and the like in the description and in the claims of the present application and in the above-described figures, are used for distinguishing between different objects and not for describing a particular sequential order. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion.
Referring to fig. 1, an embodiment of the present application provides a method for preparing lithium carbonate, including the steps of:
step one: and mixing black powder and coke to obtain a mixture, wherein the black powder comprises a lithium salt anode material and a graphite cathode material, and the lithium salt anode material comprises at least one heavy metal element of cobalt, manganese or nickel. The mixture is placed in an air atmosphere roasting kiln for roasting to obtain calcine, the roasting temperature is 550-650 ℃, the roasting time is 40-100 minutes, and the calcine comprises Li 2 CO 3 . In this step, the lithium salt of the positive electrode material is converted into Li 2 CO 3 . Exemplary, the black powder can be obtained by disassembling waste lithium batteriesThe cell obtained, exemplary, lithium salt positive electrode material may include at least one of lithium cobaltate, lithium manganate, or lithium nickel cobalt manganate. That is, after calcination, lithium cobaltate, lithium manganate or lithium nickel cobalt manganate can be converted into Li 2 CO 3 。
In some embodiments, the ratio of the black powder to the coke is 4 by mass: 1-6:1, the ratio of the two is favorable for improving the conversion rate of the lithium salt anode material.
Further, the roasting temperature is 550-600 ℃, and the roasting time is 40-60 minutes. At this temperature and time, li in the black powder can be sufficiently reacted to form Li 2 CO 3 Too high a temperature may cause volatilization loss of Li and hardening of materials, while too low a temperature may greatly lengthen the reaction time.
Step two: taking a part of the calcine for pulping to obtain first ore pulp, wherein the pure water and the calcine can be used for pulping, and the mass ratio of the pure water to the calcine can be 2:1 to 3: and 1, leaching Li ions in the first ore pulp by adopting sulfuric acid aqueous solution, regulating the pH value to be 6-7 to obtain second ore pulp, and carrying out solid-liquid separation on the second ore pulp to obtain a first leaching solution and a first leaching slag. In this step, li 2 CO 3 The second slurry includes trace amounts of heavy metal ions, such as at least one of nickel (Ni) element, cobalt (Co) element, or manganese (Mn) element, dissolved by the sulfuric acid aqueous solution, and thus the first leachate may include lithium sulfate and heavy metal ions. Illustratively, the aqueous sulfuric acid solution and the first slurry may be added to the leaching tank to react, and agitation may be performed during the reaction, and illustratively, the agitation time may be 8-12 hours.
In some embodiments, in the present step, the first leaching residue may be washed with pure water during the solid-liquid separation, and the ratio of pure water to the first leaching residue may be 5 by mass: 1.
in some embodiments, in this step, the aqueous sulfuric acid solution has a concentration of 1.5-2mol/L and the Li ion concentration is 18-24g/L.
Step three: and (3) taking the first leaching solution and a part of new calcine to carry out pulp mixing, regulating the pH value to be 10-11 to obtain third ore pulp, and carrying out solid-liquid separation on the third ore pulp to obtain second leaching solution and second leaching residues. In the step, the combination tendency of carbonate and heavy metal ions is larger, so that the heavy metal ions and lithium ions are exchanged to obtain corresponding heavy metal carbonate precipitates. Thus, the second leach residue comprises heavy metal carbonates, the second leach solution being enriched in lithium salts.
In some embodiments, the ratio of the second pulp to the calcine used in this step is 5 by mass: 1-6:1, the setting of the proportion of the two is beneficial to improving the precipitation rate of heavy metals, thereby being beneficial to reducing the heavy metal content of the final lithium carbonate product.
In some embodiments, the second leaching residue is washed with an aqueous sulfuric acid solution to obtain slag and a washing liquid, which is returned to the second step to slurry the calcine with the washing liquid. And part of lithium ions may be carried on the surface of the second leaching residue, and the washing liquid is returned to the step two, so that the recovery rate of the lithium ions is further improved.
In some embodiments, in this step, the concentration of the aqueous sulfuric acid solution is 0.15 to 0.2mol/L, and the ratio of the second leaching residue to the aqueous sulfuric acid solution of this step is 1 by mass: 5.
step four: and heating the second leaching solution to a temperature of more than 90 ℃ and then adding the second leaching solution into a carbonate solution to obtain a lithium carbonate mixed solution, wherein the temperature of the carbonate solution is 80-90 ℃. Illustratively, the carbonate solution may include Na 2 CO 3 Solutions or K 2 CO 3 At least one of the solutions. The temperature setting in the fourth step is favorable for improving the precipitation amount of lithium carbonate.
In some embodiments, in this step, the carbonate solution has a concentration of 340-360g/L, and the control of the concentration is advantageous for further increasing the precipitation amount of lithium carbonate.
In some embodiments, the duration of the addition of the second leaching solution is controlled to be 60-90 minutes. The precipitation amount of lithium carbonate is further improved by the synergistic effect of the concentration of the reactant and the reaction time.
In some embodiments, the step further comprises: and (3) reacting the lithium carbonate mixed solution at the reaction temperature of 80-90 ℃ for 60-90 minutes. The precipitation amount of lithium carbonate can be further increased by the reaction.
When the washing liquid is produced in the third step, the preparation method further comprises: and returning the washing liquid to the second step to carry out slurry mixing on the calcine by using the washing liquid, and repeating the second step to the fourth step, so that lithium ions in the washing liquid can be precipitated.
When the lithium carbonate powder is required to be prepared, solid-liquid separation can be carried out on the lithium carbonate mixed solution to obtain lithium carbonate filter residues, and the lithium carbonate filter residues are dried to obtain the lithium carbonate powder.
In the application, the black powder obtained by disassembling the lithium battery comprises a graphite negative electrode material and a lithium salt positive electrode material, the lithium salt positive electrode material comprises at least one element of cobalt, manganese or nickel, the calcine containing lithium carbonate is obtained after the black powder and coke are subjected to reduction roasting, a part of the calcine reacts with sulfuric acid to enable metal ions (including Li ions) in the calcine to leach out to obtain reaction ore pulp, the reaction ore pulp and a part of new calcine undergo a displacement reaction, and the heavy metal elements (such as cobalt, manganese or nickel) can form carbonate precipitation and precipitation, so that the purity of the finally prepared lithium carbonate is improved. In addition, the calcine containing lithium carbonate is used as the impurity removing agent for heavy metals, and an additional extracting agent or precipitating agent is not needed to be added, so that other impurities cannot be introduced, and the preparation cost of the lithium carbonate is reduced.
Specific:
example 1:
(1) The method comprises the steps of selecting a NCM523 positive electrode material lithium ion battery to recycle lithium carbonate, taking a lithium battery with graphite (C) as a negative electrode material as a recycling raw material, fully mixing black powder prepared by disassembling a waste lithium battery with coke to obtain a mixture, wherein the mass ratio of the black powder to the coke is 5:1, specifically, the mass of the black powder is 100g, and the mass of the coke is 20g. The mixture is placed in an air atmosphere roasting kiln to be roasted to obtain calcine, and the calcine is roasted60 minutes in between, the roasting temperature is 600 ℃, namely the calcine comprises Li 2 CO 3 。
(2) And (3) one-stage pulping leaching: and (3) mixing a part of the calcine with pure water to obtain first ore pulp, wherein in the step, the mass of the calcine is 113.1g, and the mass of the water is 200g. And leaching Li ions in the first ore pulp by using 2mol/L sulfuric acid aqueous solution to obtain second ore pulp, and regulating the pH value of the first ore pulp and the sulfuric acid aqueous solution to 6 after stirring and reacting in a leaching tank for 12 hours. Specifically, the concentration of Li ions was 17.2g/L. In this step, the ratio of the sum of pure water and sulfuric acid aqueous solution to the calcine is 1 by mass: 2. and carrying out solid-liquid separation on the second ore pulp to obtain a first leaching solution and a first leaching residue. Washing the first leaching residue by pure water, wherein the solid-liquid ratio of the first leaching residue to the pure water is 1:5.
(3) Two-stage pulping leaching: and taking the first leaching solution and a part of new calcine to carry out pulp mixing, and regulating the pH value to 10.4 to obtain third ore pulp. Specifically, the mass of the first leaching solution is 67.8g, and the mass of the calcine is 22.6g, so that the ratio of the second pulp to the calcine used in this step is 5 by mass: 1. and obtaining a second leaching solution and second leaching residues after the solid-liquid separation of the third ore pulp. And washing the second leaching residue by using 2mol/L sulfuric acid to obtain slag and washing liquid. In this step, the solid-to-liquid ratio of the sulfuric acid aqueous solution to the second leaching residue was 1 by mass: 5. the washing liquid returns to one section of pulping leaching and new calcine pulping.
(4) Precipitating lithium: heating the second leaching solution to 95 ℃ and adding the second leaching solution into Na 2 CO 3 In the solution, na 2 CO 3 The temperature of the solution was 90℃and Na 2 CO 3 The concentration of the solution was 360g/L. The adding time of the second leaching solution is controlled to be 60 minutes, and the adding amount is controlled to be equal to Na 2 CO 3 The volume ratio of the solution is 4:1. and after the second leaching solution is added, the system is stirred and reacts for 60 minutes under heat preservation.
And after the washing liquid returns to one-stage pulping leaching and new calcine pulping, all the steps of one-stage pulping leaching can be continuously completed, and the third step and the fourth step are repeated.
Example 2:
the difference from example 1 is that the mixture is placed in an air atmosphere kiln to calcine for 40 minutes, and in one stage of pulping leaching, the pH is adjusted to 7.
Example 3:
the difference from example 1 is that in one stage pulping leaching the pH is adjusted to 7.
Example 4:
the difference from example 1 is that lithium carbonate is recovered by selecting a lithium ion battery using waste NCM523, NCM811 and lithium cobaltate as a positive electrode material.
Comparative example 1:
(1) The method comprises the steps of selecting a NCM523 positive electrode material lithium ion battery to recycle lithium carbonate, taking a lithium battery with graphite (C) as a negative electrode material as a recycling raw material, fully mixing black powder prepared by disassembling a waste lithium battery with coke to obtain a mixture, wherein the mass ratio of the black powder to the coke is 5:1, specifically, the mass of the black powder is 100g, and the mass of the coke is 20g. And (3) placing the mixture into an air atmosphere roasting kiln to obtain calcine, wherein the roasting time is 60 minutes, and the roasting temperature is 600 ℃.
(2) And (3) one-stage pulping leaching: and (3) mixing a part of the calcine with pure water to obtain first ore pulp, wherein in the step, the mass of the calcine is 113.1g, and the mass of the water is 200g. And leaching Li ions in the first ore pulp by using 2mol/L sulfuric acid aqueous solution to obtain second ore pulp, and regulating the pH value of the first ore pulp and the sulfuric acid aqueous solution to 6 after stirring and reacting in a leaching tank for 12 hours. Specifically, the concentration of Li ions was 17.2g/L. In this step, the ratio of the sum of pure water and sulfuric acid aqueous solution to the calcine is 1 by mass: 2. and carrying out solid-liquid separation on the second ore pulp to obtain a first leaching solution and a first leaching residue. Washing the first leaching residue by pure water, wherein the solid-liquid ratio of the first leaching residue to the pure water is 1:5.
(3) Precipitating lithium: heating the first leaching solution to 95 ℃ and adding the first leaching solution into Na 2 CO 3 In the solution, na 2 CO 3 The temperature of the solution was 90℃and Na 2 CO 3 The concentration of the solution was 360g/L. The adding time of the second leaching solution is controlled to be 60 minutes, and the adding amount of the second leaching solution is controlled to be equal to Na 2 CO 3 The volume ratio of the solution is 4:1. and after the second leaching solution is added, the system is stirred and reacts for 60 minutes under heat preservation.
This example differs from example 1 in that the two stage leaching pulping step was omitted and the first leach solution was used as the lithium precipitation precursor solution.
Comparative example 2:
the difference from example 1 is that the mixture was calcined in step (1) in an air atmosphere kiln at a calcination temperature of 800 minutes to obtain calcine.
Comparative example 3:
the difference from example 1 is that the mixture was calcined in step (1) in an air atmosphere kiln for 120 minutes.
Comparative example 4:
the difference from example 1 is that the pH of the first slurry is adjusted to 9 in step (2) by leaching with 2mol/L sulfuric acid aqueous solution.
The method is used for testing the content of Li ions in the Li-containing solution through an inductively coupled plasma atomic emission spectrometer-Avio 200, and an acid-base titration method is used for testing the recovery rate of lithium and the content of lithium carbonate.
The test results of the above examples and comparative examples are shown in the following table.
According to the test results, the preparation method has good recovery rate for Li of the lithium ion battery, and the product has higher purity, and the leaching solution obtained by the process can be used as a Li precipitation precursor solution for preparing battery-grade Li 2 CO 3 And (5) a product.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. A method for preparing lithium carbonate, which is characterized by comprising the following steps:
step one: mixing black powder and coke to obtain a mixture, wherein the black powder comprises a lithium salt positive electrode material and a graphite negative electrode material, the lithium salt positive electrode material comprises at least one element of cobalt, manganese or nickel, the mixture is placed in an air atmosphere roasting kiln to be roasted to obtain calcine, and the calcine comprises Li 2 CO 3 Roasting at 550-650 deg.c for 40-100 min;
step two: taking a part of the calcine, mixing pulp to obtain first ore pulp, leaching Li ions in the first ore pulp by adopting sulfuric acid aqueous solution, regulating the pH value to be 6-7 to obtain second ore pulp, and carrying out solid-liquid separation on the second ore pulp to obtain first leaching liquid and first leaching slag;
step three: mixing the first leaching solution with a part of new calcine, regulating the pH value to 10-11 to obtain third ore pulp, and carrying out solid-liquid separation on the third ore pulp to obtain second leaching solution and second leaching residue;
step four: and heating the second leaching solution to a temperature of more than 90 ℃ and then adding the second leaching solution into a carbonate solution to obtain a lithium carbonate mixed solution, wherein the temperature of the carbonate solution is 80-90 ℃.
2. The method for preparing lithium carbonate according to claim 1, wherein the fourth step further comprises:
and (3) reacting the lithium carbonate mixed solution at the reaction temperature of 80-90 ℃ for 60-90 minutes.
3. The method for producing lithium carbonate according to claim 1, wherein a ratio of the black powder to the coke is 4 by mass: 1-6:1.
4. the method for preparing lithium carbonate according to claim 3, wherein the firing temperature is 550 to 600 ℃ and the firing time is 40 to 60 minutes.
5. The method for producing lithium carbonate according to claim 1, wherein in the second step, the concentration of the aqueous sulfuric acid solution is 1.5 to 2mol/L, the concentration of Li ions is 18 to 24g/L, and in the fourth step, the concentration of the carbonate solution is 340 to 360g/L.
6. The method for producing lithium carbonate according to claim 5, wherein the ratio of the second pulp to the calcine in step three is 5 by mass: 1-6:1.
7. the method of producing lithium carbonate according to claim 6, wherein in the fourth step, the continuous addition time of the second leaching solution is controlled to be 60 to 90 minutes.
8. The method of producing lithium carbonate according to any one of claims 1 to 7, wherein the third step further comprises:
washing the second leaching residue by adopting sulfuric acid aqueous solution to obtain slag and washing liquid;
the preparation method further comprises the following steps:
returning the washing liquid to the second step to carry out slurry mixing on the calcine by using the washing liquid, and repeating the second step to the fourth step.
9. The method for producing lithium carbonate according to claim 8, wherein in the third step, the concentration of the aqueous sulfuric acid solution is 0.15 to 0.2mol/L, and the ratio of the second leaching residue to the aqueous sulfuric acid solution is 1 by mass: 5.
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