CN115893455A - Method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid - Google Patents
Method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002386 leaching Methods 0.000 title claims abstract description 116
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 41
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000001556 precipitation Methods 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 238000001728 nano-filtration Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003337 fertilizer Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000003516 soil conditioner Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 239000011575 calcium Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical group [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- 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 2
- 230000009466 transformation Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid, and belongs to the technical field of lithium carbonate preparation. The method of the invention comprises the following steps: s1: calcining the spodumene raw material, and crushing to a certain granularity by using a ball mill; s2: and (2) adding water into the spodumene ore subjected to ball milling in the step (S1) for pulping, adding sulfuric acid into the pulp for secondary reverse leaching of sulfuric acid, and filtering to obtain secondary leaching liquid and secondary leaching residues. Compared with the traditional process, the method has the advantages of short process flow, low consumption of the soda liquid alkali and/or the soda, small amount of slag generated in the production process and high recovery rate of the metallic lithium.
Description
Technical Field
The invention belongs to the technical field of lithium carbonate preparation, and relates to a method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid.
Background
The sulfuric acid roasting process is a common method for preparing lithium carbonate in most of the industries at present, and the production process begins with lithiumite (0.7-1.3% Li) 2 O) obtaining lithium concentrate by flotation process (5-6% Li) 2 O), performing high-temperature crystal form transformation roasting transformation on the spodumene concentrate in a rotary kiln, transforming the crystal phase of the spodumene concentrate into a beta type, performing sulfating roasting to extract lithium, reacting sulfuric acid with alkali metals such as lithium, sodium, potassium and the like in the ore to generate corresponding sulfate, converting the lithium into a lithium sulfate form to be leached, cooling and neutralizing, and filtering to obtain a lithium sulfate solution. And then adding sodium hydroxide for causticizing to obtain a sodium sulfate solution, freezing to remove the sodium sulfate to obtain a lithium hydroxide solution, evaporating and centrifuging to obtain lithium hydroxide, and introducing carbon dioxide into the lithium hydroxide solution to obtain lithium carbonate. The method has the advantages of low energy consumption, small material flow, high production efficiency and the like. However, the method has the defects of long production flow, more consumption of impurity removal auxiliary materials, large slag yield, low lithium recovery rate, incapability of classifying and recycling byproducts and high production cost.
In the traditional lithium extraction process for treating the spodumene by the sulfuric acid method, sulfur dioxide gas is generated to pollute air in the sulfating roasting process after the spodumene is roasted, leachate is obtained after the acidized roasted spodumene is leached for one time, the pH value of the leachate is less than or equal to 0.5, a large amount of lime milk is needed to neutralize residual acid and soda for adjusting the pH value and removing impurities, the auxiliary material cost is increased, and a large amount of calcium sulfate precipitation slag is additionally generated by introducing calcium. Furthermore, one leaching does not ensure that a large amount of the metal in the acidified spodumene is leached into solution, resulting in a large amount of metal loss.
Therefore, the development of a new process and a new technology for extracting lithium from the spodumene has great significance for the development and application of the spodumene and the promotion of the development of the new energy lithium battery industry.
Disclosure of Invention
In order to solve the defects of the existing sulfuric acid roasting leaching technology, the invention develops a method for producing battery-grade lithium carbonate by using spodumene through sulfuric acid pressure secondary reverse leaching, the method takes spodumene as a raw material, the spodumene is directly calcined, sulfuric acid is used for secondary reverse leaching after ball milling to a certain particle size, metal metals such as lithium, aluminum and the like in the spodumene are fully leached, the pH value of a leachate obtained through the secondary reverse leaching is more than or equal to 2.5, the alkali consumption required for chemical impurity removal of a monovalent ion liquid mainly containing lithium sulfate is less after separation of a nanofiltration membrane, and the obtained impurity removal slag is returned to the front end for secondary reverse leaching of sulfuric acid, so that the lithium loss rate is reduced. In addition, the multivalent ion liquid mainly containing aluminum sulfate is subjected to chemical precipitation, so that aluminum ions in the high-valence liquid are recycled, and the resource utilization maximization is realized. The materials used in the invention are common industrialized products, are easy to purchase and have low price, the whole process flow is short, the working procedures are simple, and industrialization is easy to realize.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for producing battery-grade lithium carbonate by using pressurized secondary reverse leaching of spodumene sulfuric acid comprises the following steps:
s1: calcining the spodumene raw material, and crushing to a certain granularity by using a ball mill;
s2: adding water into the spodumene ore subjected to ball milling in the step S1 for pulping, adding sulfuric acid into the pulp for secondary reverse leaching of sulfuric acid, and filtering to obtain secondary leaching liquid and secondary leaching residues;
s3: filtering the secondary leaching solution by using a nanofiltration membrane to obtain Li 2 SO 4 Monovalent ion liquid mainly containing Al 2 (SO 4 ) 3 A predominantly multivalent ionic liquid;
s4: for the said Li 2 SO 4 Carrying out chemical impurity removal on the main monovalent ionic liquid to obtain impurity-removed liquid and impurity-removed slag;
s5: carrying out lithium precipitation reaction on the solution after impurity removal by using a soda solution, and filtering to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
s6: adding Al to 2 (SO 4 ) 3 The main multivalent ion solution is prepared by chemical precipitation of aluminum with soda ash solution, and separation to obtain aluminum hydroxide and Na 2 SO 4 A solution;
s7: the lithium precipitation mother liquor and the Na are mixed 2 SO 4 The solution is concentrated and crystallized to obtain Na 2 SO 4 。
As an embodiment of the invention, in step S1, the calcining temperature is 1000-1200 ℃ and the time is 1-5 h, and the particle size refers to the average particle size of less than 74 μm.
As an embodiment of the invention, in the step S2, the water is added for beating, and the liquid-solid mass ratio is 3-6.
As an embodiment of the present invention, the method further comprises: in the step S2, after the water is added for pulping, new sulfuric acid is adopted for primary leaching, and a solid-liquid mixture obtained by reaction is filtered to obtain primary leaching residue and primary leaching liquid; the primary leaching residue is used as active silica residue to prepare a soil conditioner or a silicon fertilizer for recycling, and the primary leaching solution is used for secondary leaching of sulfuric acid; filtering a solid-liquid mixture obtained after the sulfuric acid is leached for the second time to obtain the secondary leaching residue and the secondary leaching liquid; returning the secondary leaching residue as a raw material to sulfuric acid for primary leaching, wherein a secondary leaching solution is used for the separation of the nanofiltration membrane;
the dosage of the new sulfuric acid in the primary leaching of the sulfuric acid is 80 to 120 weight percent of the required theoretical amount calculated according to the main elements participating in the leaching reaction, and the dosage of the sulfuric acid in the secondary leaching of the sulfuric acid is 20 to 50 weight percent of the theoretical amount calculated according to the main elements participating in the leaching reaction; the primary acid leaching reaction temperature and the secondary acid leaching reaction temperature are respectively and independently selected from any value between 100 ℃ and 180 ℃, the primary acid leaching reaction time and the secondary acid leaching reaction time are respectively and independently selected from any value between 1h and 6h, and the pH value of the secondary leaching solution is more than or equal to 2.5.
As an embodiment of the invention, in step S3, the nanofiltration membrane separation is multi-stage nanofiltration, the stage number is 2 to 7, and the nanofiltration pressure is 2.0 to 8.0Mpa;
the compound is represented by Li 2 SO 4 Li in main monovalent ion liquid 2 SO 4 The mass concentration of the Al is 10-80g/L 2 (SO 4 ) 3 Al in polyvalent ionic liquid 2 (SO 4 ) 3 The mass concentration of (b) is 10-80g/L.
In step S4, the materials used for chemical impurity removal are NaOH, liOH and Na as an embodiment of the present invention 2 CO 3 The chemical impurity removal reaction end point pH is 10-12, the temperature is 50-80 ℃, and the time is 1-3 h.
As an embodiment of the invention, in step S5, the lithium precipitation reaction temperature is 60-80 ℃, the dosage of the soda ash solution is 100-110 wt% of the theoretical amount required by the precipitation reaction of Li and carbonate in the solution after impurity removal, and the lithium precipitation reaction time is 1-2 h.
As an embodiment of the invention, in step S6, the end point pH value of the chemical aluminum deposition reaction is 3-7, the temperature is 50-90 ℃, and the time is 1-2 h.
As an embodiment of the present invention, in step S7, the temperature of the evaporation concentration in step S7 is 70 to 110 ℃ and the crystallization temperature is-5 to 40 ℃.
In step S7, as an embodiment of the present invention, the impurity-removed slag in step S4 is returned to the ball-milled spodumene in step S2.
The technical scheme provided by the invention at least brings the following beneficial effects:
the traditional sulfuric acid process is improved, the raw ore can be directly leached after being calcined, flotation is not needed, a secondary reverse leaching process of sulfuric acid is innovatively utilized, so that the amount of leaching residues generated in a leaching process is lower, the leaching rate of metals in the spodumene ore is higher, the pH value of a leaching solution is improved, and the consumption of soda ash or liquid caustic soda required for subsequently improving the pH value is reduced; nanofiltration equipment is introduced in the process to separate monovalent liquid and high-valence liquid, the consumption of soda ash, lithium hydroxide or liquid caustic soda required by impurity removal of the monovalent liquid after separation is lower, the amount of impurity-removing residues is less, and the monovalent liquid is circularly used in a front-end leaching working section, so that the loss rate of lithium is reduced, and meanwhile, the high-valence ionic liquid as a byproduct is also treated and recovered. Compared with the traditional process, the method has the advantages of short process flow, low consumption of the soda ash liquid alkali and/or the soda ash, small amount of slag generated in the production process and high recovery rate of the metal lithium.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid in one embodiment of the invention.
Detailed Description
To make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The analysis results of main elements (non-oxygen elements) of spodumene used in the examples of the present invention are shown in Table 1.
TABLE 1
Example 1
A method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid comprises the following detailed steps:
s1: calcining the spodumene raw materials in the table 1 at 1000 ℃ for 3h, and ball-milling the calcined spodumene raw materials (containing raw ores) until the average particle size is less than 74 mu m;
s2: adding water into the spodumene ore subjected to ball milling in the step S1, pulping according to a liquid-solid mass ratio of 3; recycling the primary leaching residue, wherein the primary leaching solution is used for secondary leaching of sulfuric acid; filtering a solid-liquid mixture obtained after the sulfuric acid is leached for the second time to obtain secondary leaching residue and secondary leaching liquid, and returning the secondary leaching residue as a raw material to the sulfuric acid for primary leaching;
wherein the new sulfuric acid dosage in the primary sulfuric acid leaching is calculated as 110wt% of the theoretical amount according to main elements participating in leaching reaction (Li \ Na \ K \ Al \ Fe \ Ca), the sulfuric acid dosage in the secondary sulfuric acid leaching is calculated as 40wt% of the theoretical amount according to the main elements participating in leaching reaction (the sulfuric acid dosage calculation mode is the same as the primary leaching, the primary leaching reaction temperature and the secondary leaching reaction temperature are both 160 ℃, the primary leaching reaction time and the secondary leaching reaction time are both 2h, and a solid-liquid mixture obtained by reaction is filtered to obtain leachate and leaching slag, wherein the primary leaching slag is comprehensively recycled, and the pH of the secondary leaching is 2.5;
s3: filtering the secondary leachate obtained in the step S2 by using a nanofiltration membrane, wherein the filtration pressure of the nanofiltration membrane is 3.5Mpa, and the grade is 3, so as to obtain the Li 2 SO 4 Monovalent ion liquid mainly containing Al 2 (SO 4 ) 3 A predominantly multivalent ionic liquid;
s4: li obtained in step S3 2 SO 4 Performing chemical impurity removal on the main monovalent ionic liquid by using a combination of liquid caustic soda and soda ash to obtain impurity-removed liquid and impurity-removed slag, wherein the impurity-removed slag returns to the sulfuric acid reverse secondary leaching process of the step S2, the reaction end point pH of the impurity removal is controlled to be 10, the impurity removal temperature is 70 ℃, and the reaction time is 1h;
s5: adding sodium carbonate into the impurity-removed solution obtained in the step S4 to perform lithium precipitation reaction to obtain battery-grade lithium carbonate and lithium precipitation mother solution; the sodium carbonate accounts for 105wt% of theoretical amount required by calculation of precipitation reaction of Li and carbonate in the solution after impurity removal, the temperature for precipitating lithium is 65 ℃, and the reaction time for precipitating lithium is 1h;
s6: al obtained in step S2 2 (SO 4 ) 3 Using a soda solution to carry out chemical aluminum precipitation on the main multivalent ion solution, controlling the temperature to be 65 ℃, the end point pH =6 and the reaction time to be 1h, and separating to obtain aluminum hydroxide and Na 2 SO 4 A solution;
s7: the lithium precipitation mother liquor obtained in the step S5 and the stepNa from S6 2 SO 4 The solution is concentrated and crystallized to obtain Na 2 SO 4 The negative pressure evaporation concentration temperature is 90 ℃, and the crystallization temperature is 20 ℃.
Li obtained in this example 2 CO 3 The purity of (2) was 99.58% and the yield of lithium was 91.28%.
Example 2
Battery grade lithium carbonate was produced using the method of example 1, except that:
in the step S1, the calcining temperature is 1050 ℃, and the calcining time is 2 hours;
in the step S2, adding water into the spodumene ground ball-milled in the step S1 and pulping according to a liquid-solid mass ratio of 4; wherein, the new sulfuric acid dosage in the primary sulfuric acid leaching is calculated as 100wt% of the theoretical quantity required according to the main elements (Li \ Na \ K \ Al \ Fe \ Ca) participating in the leaching reaction, the sulfuric acid dosage in the secondary sulfuric acid leaching is calculated as 30wt% of the theoretical quantity according to the main elements participating in the leaching reaction (the same sulfuric acid dosage is leached in the same way), the primary leaching reaction temperature and the secondary leaching reaction temperature are both 160 ℃, the primary leaching reaction time and the secondary leaching reaction time are both 2h, and the solid-liquid mixture obtained by the reaction is filtered to obtain leachate and leaching residues, wherein the primary leaching residues are comprehensively recycled, and the pH of the secondary leaching solution is 3;
in the step S5, the lithium precipitation temperature is 70 ℃ and the lithium precipitation reaction time is 1.5h, wherein the sodium carbonate accounts for 108wt% of the theoretical amount required by the calculation of the precipitation reaction of Li and carbonate in the solution after impurity removal;
in the step S7, the negative pressure concentration temperature is 95 ℃, and the crystallization temperature is 30 ℃;
li obtained in this example 2 CO 3 The purity of (D) was 99.56%, and the lithium yield was 91.50%.
Example 3
Battery grade lithium carbonate was produced using the method of example 1, except that:
in the step S1, the calcining temperature is 1100 ℃, and the calcining time is 1.5h;
in the step S2, adding water into the spodumene ore subjected to ball milling in the step S1 and pulping according to a liquid-solid mass ratio of 5; wherein the new sulfuric acid dosage in the primary sulfuric acid leaching is calculated to be 120wt% of the theoretical amount according to the main elements (Li \ Na \ K \ Al \ Fe \ Ca) participating in the leaching reaction, the sulfuric acid dosage in the secondary sulfuric acid leaching is calculated to be 40wt% of the theoretical amount according to the main elements participating in the leaching reaction (the sulfuric acid dosage calculation mode is the same as the primary leaching), the primary leaching reaction temperature and the secondary leaching reaction temperature are both 170 ℃, and the primary leaching reaction time and the secondary leaching reaction time are both 1.5h;
in the step S5, the lithium deposition temperature is 75 ℃, and the time is 2h;
li obtained in this example 2 CO 3 The purity of (D) was 99.60% and the yield was 90.10%.
Example 4
Battery grade lithium carbonate was produced using the method of example 1, except that:
in the step S2, the new sulfuric acid dosage in the primary sulfuric acid leaching is calculated as 90wt% of the theoretical amount according to the main elements (Li \ Na \ K \ Al \ Fe \ Ca) participating in the leaching reaction, and the sulfuric acid dosage in the secondary sulfuric acid leaching is calculated as 50wt% of the theoretical amount according to the main elements participating in the leaching reaction (the same leaching is carried out in a sulfuric acid dosage calculation mode);
li obtained in this example 2 CO 3 The purity of (D) was 99.68%, and the yield was 90.20%.
Example 5
Battery grade lithium carbonate was produced as in example 1, except that:
in the step S5, the lithium deposition temperature is 80 ℃ and the time is 1.5h, wherein the sodium carbonate accounts for 110wt% of the theoretical amount required by the calculation of the precipitation reaction of Li and carbonate in the solution after impurity removal.
Li obtained in this example 2 CO 3 The purity of (D) was 99.70%, and the yield was 90.70%.
Comparative example 1
Battery grade lithium carbonate was produced using the method of example 1, except that:
s1: the spodumene raw materials in Table 1 were calcined at 900 ℃ for 3 hours, and the calcined spodumene (containing raw ore) was ball-milled so that the average particle size of the spodumene was less than 74 μm.
Li obtained in this example 2 CO 3 The purity of (D) was 99.74% and the yield was 53.10%.
Comparative example 2
Battery grade lithium carbonate was produced using the method of example 1, except that:
s1: the spodumene raw material in table 1 was calcined at 1300 ℃ for 3 hours, and the calcined spodumene (containing raw ore) was ball-milled so that the average particle size of the spodumene was less than 74 μm.
Li of the present example 2 CO 3 The purity of (D) was 99.70%, and the yield was 75.10%.
Comparative example 3
Battery grade lithium carbonate was produced using the method of example 1, except that:
in the step S2, the new sulfuric acid dosage in the primary sulfuric acid leaching is calculated as 115wt% of the theoretical required amount according to the main elements (Li \ Na \ K \ Al \ Fe \ Ca) participating in the leaching reaction, the secondary leaching is not carried out, and the pH of the obtained leachate is 0.5.
Li obtained in this example 2 CO 3 The purity of (D) was 99.61%, and the yield was 80.6%.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for producing battery-grade lithium carbonate by carrying out sulfuric acid pressure secondary reverse leaching on spodumene, which is characterized by comprising the following steps:
s1: calcining the spodumene raw material, and crushing to a certain granularity by using a ball mill;
s2: adding water into the spodumene ore subjected to ball milling in the step S1 for pulping, adding sulfuric acid into the pulp for secondary reverse leaching of sulfuric acid, and filtering to obtain secondary leaching liquid and secondary leaching residues;
s3: filtering the secondary leachate by using a nanofiltration membrane to obtain Li 2 SO 4 Monovalent ion liquid mainly containing Al 2 (SO 4 ) 3 A predominantly multivalent ionic liquid;
s4: for the said Li 2 SO 4 Is mainly oneCarrying out chemical impurity removal on the valence ion liquid to obtain impurity-removed liquid and impurity-removed slag;
s5: carrying out lithium precipitation reaction on the solution after impurity removal by using a sodium carbonate solution, and filtering to obtain battery-grade lithium carbonate and lithium precipitation mother liquor;
s6: adding Al to 2 (SO 4 ) 3 The main multivalent ion solution is prepared by chemical precipitation of aluminum with soda ash solution, and separation to obtain aluminum hydroxide and Na 2 SO 4 A solution;
s7: the lithium precipitation mother liquor and the Na are mixed 2 SO 4 The solution is concentrated and crystallized to obtain Na 2 SO 4 。
2. The method according to claim 1, wherein in step S1, the calcining temperature is 1000-1200 ℃ and the time is 1-5 h, and the particle size refers to the average particle size of less than 74 μm.
3. The method according to claim 1, wherein in the step S2, the water is added for beating, and the liquid-solid mass ratio is 3-6.
4. The method of claim 1, further comprising: in the step S2, after the water is added for pulping, new sulfuric acid is adopted for primary leaching, and a solid-liquid mixture obtained by reaction is filtered to obtain primary leaching residue and primary leaching liquid; the primary leaching residue is used as active silica residue to prepare a soil conditioner or a silicon fertilizer for recycling, and the primary leaching solution is used for secondary leaching of sulfuric acid; filtering a solid-liquid mixture obtained after the sulfuric acid is leached for the second time to obtain the secondary leaching residue and the secondary leaching liquid; returning the secondary leaching residue as a raw material to sulfuric acid for primary leaching;
the dosage of the new sulfuric acid in the primary leaching of the sulfuric acid is 80 to 120 weight percent of the required theoretical amount calculated according to the main elements participating in the leaching reaction, and the dosage of the sulfuric acid in the secondary leaching of the sulfuric acid is 20 to 50 weight percent of the theoretical amount calculated according to the main elements participating in the leaching reaction; the primary acid leaching reaction temperature and the secondary acid leaching reaction temperature are respectively and independently selected from any value between 100 and 180 ℃, the primary acid leaching reaction time and the secondary acid leaching reaction time are respectively and independently selected from any value between 1 and 6 hours, and the pH value of the secondary leachate is more than or equal to 2.5.
5. The method according to claim 1, wherein in step S3, the nanofiltration membrane separation is a multi-stage nanofiltration with a stage number of 2-7 and a nanofiltration pressure of 2.0-8.0Mpa;
the compound is represented by Li 2 SO 4 Li in main monovalent ion liquid 2 SO 4 The mass concentration of the Al is 10-80g/L 2 (SO 4 ) 3 Al in polyvalent ionic liquid 2 (SO 4 ) 3 The mass concentration of (A) is 10-80g/L.
6. The method of claim 1, wherein in step S4, the substances used for chemical impurity removal are NaOH, liOH and Na 2 CO 3 The chemical impurity removal reaction end point pH is 10-12, the temperature is 50-80 ℃, and the time is 1-3 h.
7. The method according to claim 1, wherein in step S5, the lithium precipitation reaction temperature is 60-80 ℃, the amount of the soda ash solution is 100-110 wt% of the theoretical amount required by the calculation of the precipitation reaction of Li and carbonate in the solution after impurity removal, and the lithium precipitation reaction time is 1-2 h.
8. The method of claim 1, wherein in step S6, the final pH value of the chemical aluminum deposition reaction is 3-7, the temperature is 50-90 ℃, and the time is 1-2 h.
9. The method according to claim 1, wherein the temperature of the evaporation concentration in step S7 is 70-110 ℃ and the crystallization temperature is-5-40 ℃.
10. The method of claim 1, wherein in step S7, the impurity-removed slag in step S4 is returned to the ball-milled spodumene in step S2.
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| CN114854986A (en) * | 2022-05-24 | 2022-08-05 | 四川顺应锂材料科技有限公司 | Method for producing lithium carbonate by leaching spodumene ore with nitric acid |
| CN115286019A (en) * | 2022-09-14 | 2022-11-04 | 四川顺应锂材料科技有限公司 | Method for producing high-purity lithium carbonate from spodumene |
| CN115321563A (en) * | 2022-08-05 | 2022-11-11 | 四川顺应锂材料科技有限公司 | Method for producing battery-grade lithium carbonate by leaching spodumene ore with nitric acid under pressure |
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| CN114854986A (en) * | 2022-05-24 | 2022-08-05 | 四川顺应锂材料科技有限公司 | Method for producing lithium carbonate by leaching spodumene ore with nitric acid |
| CN115321563A (en) * | 2022-08-05 | 2022-11-11 | 四川顺应锂材料科技有限公司 | Method for producing battery-grade lithium carbonate by leaching spodumene ore with nitric acid under pressure |
| CN115286019A (en) * | 2022-09-14 | 2022-11-04 | 四川顺应锂材料科技有限公司 | Method for producing high-purity lithium carbonate from spodumene |
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