CN116835548A - Method for extracting phosphorus and lithium salt in lithium-phosphorus-aluminum stone by comprehensive wet method - Google Patents
Method for extracting phosphorus and lithium salt in lithium-phosphorus-aluminum stone by comprehensive wet method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 42
- 239000011574 phosphorus Substances 0.000 title claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 28
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 28
- 239000004575 stone Substances 0.000 title claims description 7
- -1 lithium-phosphorus-aluminum Chemical compound 0.000 title description 6
- 238000002386 leaching Methods 0.000 claims abstract description 70
- 239000002253 acid Substances 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 14
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 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 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 38
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting phosphorus and lithium salt in lithium-ion battery through wet comprehensive utilization, which is used for leaching lithium, phosphorus and aluminum in lithium-ion battery through two-stage countercurrent of high-temperature low-acid and high-temperature high-acid; adding ferric sulfate solution into the low-acid leaching solution, and regulating the pH value of the solution to 1.2-2.5 to obtain ferric phosphate precipitate; neutralizing the solution after phosphorus precipitation with alkali until the pH value of the final solution is 4-7 to precipitate aluminum and impurity elements, thereby obtaining pure lithium salt solution; finally adding saturated concentration sodium carbonate or sodium phosphate solution to precipitate and separate lithium; based on the method, the valuable elements are directly leached in two stages without pretreatment of high Wen Huofa, so that the investment is low, the energy consumption is low and the comprehensive utilization rate is high.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of nonferrous metal mineral resources, in particular to a method for extracting phosphorus and lithium salt in lithium-phosphorus bauxite by wet comprehensive utilization.
Background
Lithium is the lightest metal, and lithium metal, and alloys and compounds thereof are widely used in the fields of nuclear power generation, light-weight high-specific strength alloys, high-energy batteries and the like. With the development of new energy automobiles, energy storage and other technologies, lithium becomes an indispensable component in the new energy automobiles;
global lithium resources are abundant and are mainly distributed in america, australia, asia and africa, such as: lithium-containing salt lake brine such as a villiaumite basin of boiivia, a silver peak in nevada, a silvery lake in california, a colhan salt lake in green sea in China, and a Chai Dan salt lake; lattice Lin Pushen lithuite, zimbabwe and lithium-phosphate bauxite of nano-belite in the western australia, and the like. The lithium extraction method of spodumene, petalite and lepidolite has been widely reported, but researches on the extraction of lithium in the lithium-ion battery are carried out freshly;
patent CN109019643B (a process for extracting lithium salt from phospholithiumstone) adopts inorganic salt for roasting, selectively dissolves lithium, and then obtains lithium salt through impurity removal, concentration and lithium precipitation treatment; literature (research on the process of preparing lithium carbonate from phospholithiumite, mixing phospholithiumite and sulfuric acid, namely 2019,34 (11): 7-9), roasting at a high temperature of 800 ℃, leaching, purifying twice, precipitating lithium with saturated sodium carbonate solution, wherein the roasting temperature is high, and valuable element phosphorus enters a slag phase and cannot be effectively recovered;
patent CN201811109575.1 (a method for preparing lithium-containing compounds from lithium-containing bauxite) adopts high-temperature heat treatment (including roasting and/or microwave induction, the roasting temperature is 600-1100 ℃) to generate an aluminum phosphate phase and a soluble lithium phase, and the lithium-containing solution and aluminum phosphate slag are obtained through acid leaching; dissolving aluminum slag in acid, adding an iron source, and adjusting the pH value to generate ferric phosphate; the scheme needs high-temperature pretreatment, has complicated working procedures, large investment and high energy consumption;
in order to realize the efficient extraction and comprehensive utilization of phosphorus and lithium in the lithium-ion battery, the technology of the patent provides a method for comprehensively utilizing the phosphorus and extracting lithium salt in the lithium-ion battery by a wet method, and has important significance for the low-energy-consumption treatment and the high-value utilization of components of the lithium-ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provide a method for comprehensively utilizing and extracting phosphorus and lithium salt in lithium-ion phosphate by a wet method.
In order to solve the technical problems, the technical scheme provided by the invention is that the method for extracting phosphorus and lithium salt in lithium-ion phosphate by comprehensively utilizing wet method comprises the following steps:
step 1) after crushing and grinding the lithium-ion battery, leaching lithium, phosphorus and aluminum in the lithium-ion battery by adopting two-stage high-temperature leaching processes, wherein the two-stage high-temperature leaching processes comprise two processes of high-temperature low-acid and high-temperature high-acid countercurrent leaching, and the method specifically comprises the following steps:
after high-temperature low-acid leaching, carrying out liquid-solid separation, and carrying out open-circuit extraction on the leaching liquid to utilize phosphorus and lithium;
the leaching slag enters a high-temperature high-acid leaching process, so that the leaching rate of lithium, phosphorus and aluminum is further improved;
after high-temperature high-acid leaching, liquid-solid separation is carried out, the leaching liquid returns to the high-temperature low-acid process of the lithium-ion-exchange-metal-aluminum-stone in the next tank, and the acid consumption is reduced, wherein the leaching slag is mainly SiO 2 And CaSO 4 The phases are present.
Step 2) adding ferric sulfate solution into the leaching solution obtained by the high-temperature low-acid leaching separation in the step 1 to precipitate phosphorus, and performing liquid-solid separation to obtain ferric phosphate precipitate and sulfate solution containing lithium and aluminum;
step 3) adding alkali liquor into the sulfate solution containing lithium and aluminum obtained in the step 2 to neutralize and precipitate aluminum and impurity elements, and obtaining solution containing lithium sulfate and aluminum oxide slag after liquid-solid separation;
and 4) adding saturated sodium carbonate or sodium phosphate solution into the solution containing lithium sulfate obtained in the step 3 to precipitate lithium, thereby obtaining lithium salt precipitate and sodium sulfate mother liquor.
Further, the temperature of the high-temperature low-acid leaching process in the step 1 is 75-95 ℃, the concentration of sulfuric acid at the leaching end point is 5-25 g/L, and the stirring time is 0.5-5 h; the temperature of the high-temperature high-acid leaching process is 80-98 ℃, the concentration of sulfuric acid at the leaching end point is 50-120 g/L, and the stirring time is 0.5-5 h.
Further, the molar ratio (nFe: nP) of iron in the ferric sulfate to phosphorus in the high-temperature low-acid leaching solution in the step 2 is 0.95-1.0, the end point pH value of the solution is 1.2-2.5, the temperature is 30-90 ℃, and the time is 0.5-5 h.
Further, the alkali in the step 3 is used for neutralizing and precipitating aluminum and impurity elements, wherein the alkali can be Na 2 CO 3 、NaHCO 3 NaOH and Ca (OH) 2 One of (a)One or more than two kinds of the materials, the pH value of the precipitation end point is 4-7, the precipitation temperature is 30-90 ℃, and the precipitation time is 0.5-5 h.
Further, the solution end point pH value of the saturated sodium carbonate or sodium phosphate solution precipitated lithium salt in the step 4 is 9.5-13.5, the temperature is 30-98 ℃ and the time is 0.5-5 h.
Compared with the prior art, the invention has the advantages that: the invention leaches lithium, phosphorus and aluminum in the lithium-phosphorus-aluminum stone through two sections of countercurrent of high temperature low acid and high temperature high acid; adding ferric sulfate solution into the low-acid leaching solution, and regulating the pH value of the solution to 1.2-2.5 to obtain ferric phosphate precipitate; neutralizing the solution after phosphorus precipitation with alkali until the pH value of the final solution is 4-7 to precipitate aluminum and impurity elements, thereby obtaining pure lithium salt solution; finally adding saturated concentration sodium carbonate or sodium phosphate solution to precipitate and separate lithium; based on the method, the valuable elements are directly leached in two stages without pretreatment of high Wen Huofa, so that the investment is low, the energy consumption is low and the comprehensive utilization rate is high.
Drawings
Fig. 1 is a process flow diagram of a method for extracting phosphorus and lithium salts in lithium-ion battery by wet comprehensive utilization of the invention.
Detailed Description
The method for extracting phosphorus and lithium salt in lithium-ion battery by wet comprehensive utilization of the present invention is described in further detail below with reference to examples.
The lithium-phosphorus-aluminum stone in the embodiment of the invention is crushed, ground and then 90% of the crushed lithium-phosphorus-aluminum stone is screened by a 200-mesh sieve, and the main components comprise, by mass, li2.98%, P17.3%, al12.0%, ca0.45%, na0.32%, K0.56%, mg0.012%, fe0.38% and the balance Si and O.
The chemical reagents employed in the examples of the present invention were all commercially available.
Example 1
(1) The leaching temperature of the high-temperature low-acid is 90 ℃, the concentration of sulfuric acid at the leaching end point is 15g/L, and the stirring leaching time is 2h; the high-temperature high-acid leaching temperature is 98 ℃, the concentration of sulfuric acid at the leaching end point is 120g/L, and the stirring leaching time is 2h. According to the contents of Li, P and Al in the high-temperature high-acid filter residues, the leaching rates of Li, P and Al are calculated to be 96.31%, 97.18% and 96.12% respectively;
(2) Based on the content of phosphorus in the high-temperature low-acid leaching solution, the molar ratio (nFe: nP) of iron in ferric sulfate to phosphorus in the high-temperature low-acid leaching solution is 1.0, sodium carbonate is added to adjust the final pH value to 1.6, the temperature is 80 ℃, and the time is 2 hours. Washing the ferric phosphate precipitate with deionized water for 3 times, drying at 120 ℃, and calcining at 780 ℃ for 2 hours to obtain a ferric phosphate product. Wherein the iron content and the phosphorus content are 36.16 percent and 20.28 percent respectively, n (Fe/P) = 0.9887, and the rest impurity elements and the physical properties meet the industry standard;
(3) Precipitating ferric phosphate to obtain lithium and aluminum-containing sulfate mother liquor, adding saturated Na 2 CO 3 The solution is neutralized to precipitate aluminum and impurity elements, the precipitation end point pH value is 6, the precipitation temperature is 80 ℃, and the time is 2 hours. The neutralization filtrate is a mixed solution of lithium sulfate and sodium sulfate, and contains impurity elements of aluminum and phosphorus<0.0005g/L；
(4) Adding saturated sodium carbonate into the mixed solution of lithium sulfate and sodium sulfate to precipitate lithium salt, wherein the solution has an end point pH value of 12.5, a temperature of 90 ℃ and a time of 2 hours. Washing the lithium salt precipitate with deionized water for 3 times, and drying at 120deg.C for 7h to obtain lithium carbonate product, li 2 CO 3 Content of>99.82% of impurity elements meet the requirements of battery grade lithium carbonate products.
Example 2
(1) The leaching temperature of the high-temperature low-acid is 80 ℃, the concentration of sulfuric acid at the leaching end point is 25g/L, and the stirring leaching time is 4 hours; the high-temperature high-acid leaching temperature is 95 ℃, the concentration of sulfuric acid at the leaching end point is 100g/L, and the stirring leaching time is 3h. According to the contents of Li, P and Al in the high-temperature high-acid filter residues, the leaching rates of Li, P and Al are calculated to be 95.83%, 96.42% and 96.33% respectively;
(2) Based on the phosphorus content in the high-temperature low-acid leaching solution, the molar ratio (nFe: nP) of iron in ferric sulfate to phosphorus in the high-temperature low-acid leaching solution is 0.98, and the end pH value is 2.0 when sodium hydroxide is added to adjust the temperature to 70 ℃ for 3 hours. Washing the ferric phosphate precipitate with deionized water for 4 times, drying at 110 ℃, and calcining at 750 ℃ for 4 hours to obtain a ferric phosphate product. Wherein the contents of iron and phosphorus are 35.88 percent and 20.18 percent respectively, n (Fe/P) = 0.9859, and the rest impurity elements and physical properties meet the industry standard;
(3) Sinking and sinkingPrecipitating ferric phosphate to obtain lithium and aluminum-containing sulfate mother liquor, adding saturated Na 2 HCO 3 The solution is neutralized to precipitate aluminum and impurity elements, the precipitation end point pH value is 5.6, the precipitation temperature is 60 ℃, and the time is 3 hours. The neutralization filtrate is a mixed solution of lithium sulfate and sodium sulfate, and contains impurity elements of aluminum and phosphorus<0.0007g/L；
(4) And adding saturated sodium phosphate into the mixed solution of lithium sulfate and sodium sulfate to precipitate lithium salt, wherein the solution has an end point pH value of 12, a temperature of 95 ℃ and a time of 3 hours. Washing the lithium salt precipitate with deionized water for 4 times, and drying at 120deg.C for 5 hr to obtain lithium carbonate product, li 2 CO 3 Content of>99.85 percent of impurity elements meet the requirements of battery grade lithium carbonate products.
Example 3
(1) The leaching temperature of the high-temperature low-acid is 80 ℃, the concentration of sulfuric acid at the leaching end point is 12g/L, and the stirring leaching time is 4 hours; the high-temperature high-acid leaching temperature is 90 ℃, the concentration of sulfuric acid at the leaching end point is 90g/L, and the stirring leaching time is 4h. According to the contents of Li, P and Al in the high-temperature high-acid filter residues, the leaching rates of Li, P and Al are calculated to be 95.42%, 96.42% and 95.78% respectively;
(2) Based on the phosphorus content in the high-temperature low-acid leaching solution, the molar ratio (nFe: nP) of iron in ferric sulfate to phosphorus in the high-temperature low-acid leaching solution is 0.99, ammonia water is added to adjust the final pH value to 1.8, the temperature is 60 ℃, and the time is 4 hours. Washing the ferric phosphate precipitate with deionized water for 5 times, drying at 80 ℃, and calcining at 600 ℃ for 6 hours to obtain a ferric phosphate product. Wherein the contents of iron and phosphorus are 36.05 percent, 20.58 percent, n (Fe/P) = 0.9714, and the rest impurity elements and physical properties meet the industry standard;
(3) Precipitating ferric phosphate to obtain mother liquor containing lithium and aluminum, and adding saturated Ca (OH) 2 The solution is neutralized to precipitate aluminum and impurity elements, the precipitation end point pH value is 6.0, the precipitation temperature is 60 ℃, and the time is 4 hours. The neutralization filtrate is a mixed solution of lithium sulfate and sodium sulfate, and contains impurity elements of aluminum and phosphorus<0.0001g/L；
(4) And adding saturated sodium carbonate into the mixed solution of lithium sulfate and sodium sulfate to precipitate lithium salt, wherein the solution has an end point pH value of 13, a temperature of 85 ℃ and a time of 2 hours. Washing the lithium salt precipitate with deionized water for 3 times, and baking at 80deg.CDrying for 12h to obtain a lithium carbonate product, li 2 CO 3 Content of>99.80 percent of impurity elements meet the requirements of battery grade lithium carbonate products.
The invention and its embodiments have been described above with no limitation, and the actual construction is not limited to the embodiments of the invention as shown in the drawings. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Claims (5)
1. The method for extracting the phosphorus and the lithium salt in the lithium-phosphorus bauxite by comprehensive wet method is characterized by comprising the following steps:
step 1) after crushing and grinding the lithium-ion battery, leaching lithium, phosphorus and aluminum in the lithium-ion battery by adopting two-stage high-temperature leaching processes, wherein the two-stage high-temperature leaching processes comprise two processes of high-temperature low-acid and high-temperature high-acid countercurrent leaching, and the method specifically comprises the following steps:
after high-temperature low-acid leaching, carrying out liquid-solid separation, and carrying out open-circuit extraction on the leaching liquid to utilize phosphorus and lithium;
the leaching slag enters a high-temperature high-acid leaching process, so that the leaching rate of lithium, phosphorus and aluminum is further improved;
after high-temperature high-acid leaching, liquid-solid separation is carried out, the leaching liquid returns to the high-temperature low-acid process of the lithium-ion-exchange-metal-aluminum-stone in the next tank, and the acid consumption is reduced, wherein the leaching slag is mainly SiO 2 And CaSO 4 The phases are present.
Step 2) adding ferric sulfate solution into the leaching solution obtained by the high-temperature low-acid leaching separation in the step 1 to precipitate phosphorus, and performing liquid-solid separation to obtain ferric phosphate precipitate and sulfate solution containing lithium and aluminum;
step 3) adding alkali liquor into the sulfate solution containing lithium and aluminum obtained in the step 2 to neutralize and precipitate aluminum and impurity elements, and obtaining solution containing lithium sulfate and aluminum oxide slag after liquid-solid separation;
and 4) adding saturated sodium carbonate or sodium phosphate solution into the solution containing lithium sulfate obtained in the step 3 to precipitate lithium, thereby obtaining lithium salt precipitate and sodium sulfate mother liquor.
2. The method for extracting phosphorus and lithium salt in lithium-ion battery cell by comprehensive wet utilization according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature low-acid leaching process in the step 1 is 75-95 ℃, the concentration of sulfuric acid at the leaching end point is 5-25 g/L, and the stirring time is 0.5-5 h; the temperature of the high-temperature high-acid leaching process is 80-98 ℃, the concentration of sulfuric acid at the leaching end point is 50-120 g/L, and the stirring time is 0.5-5 h.
3. The method for extracting phosphorus and lithium salt in lithium-ion battery cell by comprehensive wet utilization according to claim 1, wherein the method comprises the following steps: the molar ratio (nFe: nP) of iron in the ferric sulfate to phosphorus in the high-temperature low-acid leaching solution in the step 2 is 0.95-1.0, the end point pH value of the solution is 1.2-2.5, the temperature is 30-90 ℃ and the time is 0.5-5 h.
4. The method for extracting phosphorus and lithium salt in lithium-ion battery cell by comprehensive wet utilization according to claim 1, wherein the method comprises the following steps: the alkali in the step 3 neutralizes and precipitates aluminum and impurity elements, wherein the alkali can be Na 2 CO 3 、NaHCO 3 NaOH and Ca (OH) 2 One or more than two of the above materials, the pH value of the precipitation end point is 4-7, the precipitation temperature is 30-90 ℃, and the precipitation time is 0.5-5 h.
5. The method for extracting phosphorus and lithium salt in lithium-ion battery cell by comprehensive wet utilization according to claim 1, wherein the method comprises the following steps: the end point pH value of the solution of the saturated sodium carbonate or sodium phosphate solution precipitated lithium salt in the step 4 is 9.5-13.5, the temperature is 30-98 ℃ and the time is 0.5-5 h.
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