CN116179857A - Method for extracting lithium from waste lithium molecular sieve - Google Patents
Method for extracting lithium from waste lithium molecular sieve Download PDFInfo
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- CN116179857A CN116179857A CN202310151737.2A CN202310151737A CN116179857A CN 116179857 A CN116179857 A CN 116179857A CN 202310151737 A CN202310151737 A CN 202310151737A CN 116179857 A CN116179857 A CN 116179857A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 102
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 79
- 239000000243 solution Substances 0.000 claims abstract description 78
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000009270 solid waste treatment Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 208000004434 Calcinosis Diseases 0.000 abstract 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 52
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 238000009616 inductively coupled plasma Methods 0.000 description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 9
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 7
- 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 7
- 239000000047 product Substances 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of recovery of lithium molecular sieves, and particularly relates to a method for extracting lithium from waste lithium molecular sieves. The lithium extraction method adopts a low-temperature salt leaching process, consumes less auxiliary raw materials and has low energy consumption: grinding the waste lithium molecular sieve, sieving, adding sodium salt solution for leaching, adjusting the pH value of the lithium leaching solution to be 5-6 by using acid liquor after filtering, preserving heat for 0.5-1h at 60-90 ℃ to remove silicon and aluminum, performing precise filtration to obtain primary clean liquid, adding sodium carbonate and sodium hydroxide into the primary clean liquid, heating to 80-90 ℃, preserving heat for 0.5-1h to deposit calcium and magnesium, and performing precise filtration to obtain lithium-containing clean liquid; lithium carbonate is then deposited. The lithium extraction method is a high-efficiency selective lithium extraction process, the single lithium leaching rate is more than 98%, and silicon and aluminum are leached in a small amount, so that great convenience is provided for the next impurity removal and purification, and the technical economy is remarkable.
Description
Technical Field
The invention belongs to the technical field of recovery of lithium molecular sieves, and particularly relates to a method for extracting lithium from waste lithium molecular sieves.
Background
The lithium molecular sieve is mainly used for pressure swing adsorption oxygen generating devices, and the adsorption performance of the lithium molecular sieve is reduced after the lithium molecular sieve is repeatedly used for a plurality of times, so that the lithium molecular sieve needs to be eliminated from the economic benefit. In recent years, with the increasing demand for oxygen for household and medical use, a large amount of lithium molecular sieves are used for producing oxygen, which in turn results in a large amount of waste lithium molecular sieves being produced each year.
The lithium molecular sieve is a lithium X-type aluminosilicate crystal, wherein the lithium content is about 4 percent, which is far higher than the lithium content in two kinds of lithium ores, namely spodumene and lepidolite, and has high recovery value. Because the lithium molecular sieve is aluminosilicate, the substance is easily damaged by acid or alkali, so that lithium, silicon and aluminum in the substance exist in a free state in a solution, and a great amount of silicon and aluminum impurities are wrapped in a product in the process of precipitating lithium carbonate, so that the purity of the product is low, and the technical problem of how to selectively extract lithium from the waste lithium molecular sieve economically and simply has become one technical problem.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for efficiently recovering lithium from a waste lithium molecular sieve, and the method is used for efficiently extracting lithium without basically extracting silicon and aluminum.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for extracting lithium from waste lithium molecular sieves comprises the following steps:
(1) Pretreatment of raw materials: grinding the waste lithium molecular sieve, and sieving (preferably sieving with a 100-mesh sieve);
(2) Lithium leaching: adding 20-35 wt% sodium salt solution into the sieved lithium molecular sieve powder, stirring and mixing uniformly, heating to 30-80 ℃ for leaching, wherein the molar ratio of sodium in the sodium salt solution to lithium in the lithium molecular sieve is (2-5): 1 (preferably 4:1), leaching time is 1-3h;
(3) Separating leaching liquid: after leaching, carrying out solid-liquid separation by using a filtering device to obtain filter residues and lithium leaching liquid, wherein the lithium leaching liquid enters a primary impurity removing procedure of the step (4), the filter residues are leached by water, leaching liquid is returned to be used for preparing sodium salt solution, and the leached filter residues are subjected to solid waste treatment;
(4) Primary impurity removal: adjusting the pH value of the lithium leaching solution to be 5-6 by using acid liquor, stirring and heating to 65-80 ℃, then preserving heat for 0.5-1h at 65-80 ℃ to remove silicon and aluminum, and performing precise filtration to obtain primary clean liquid;
(5) Secondary impurity removal: adding sodium carbonate and sodium hydroxide into the primary clean liquid according to the content of calcium and magnesium in the primary clean liquid, heating to 80-90 ℃, preserving heat for 0.5-1h, depositing calcium and magnesium, and performing precise filtration to obtain a lithium-containing clean liquid;
(6) Precipitating lithium carbonate: and (3) increasing the concentration of lithium (calculated by Li ions) of the lithium-containing clean solution to 30-35g/L through evaporation concentration, adding a sodium carbonate solution with the concentration of 250-300g/L into the solution to deposit lithium carbonate, washing the obtained lithium carbonate with hot water, and drying to obtain a lithium carbonate product.
Further, in the step (2), the sodium salt solution is a sodium chloride solution, a sodium sulfate solution or a sodium nitrate solution.
Further, in the step (4), the acid liquor is hydrochloric acid, sulfuric acid or nitric acid with the concentration of 2-4 mol/L.
Further, the conditions of the drying in the step (6) are as follows: baking at 150deg.C for 2 hr.
Further, the leaching conditions in the step (2) are as follows: leaching at 60-70deg.C for 1.5-2 hr.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the traditional ore lithium extraction process, the low-temperature salt leaching process is adopted for extracting lithium, so that auxiliary raw materials are less consumed, the energy consumption is low, and the traditional ore lithium extraction acid leaching, salt leaching and alkaline leaching processes consume more auxiliary raw materials, require high-temperature reaction, have serious equipment corrosion and have high energy consumption;
2. compared with the common aqueous solution exchange method, the lithium extraction process is a high-efficiency lithium extraction process, the single lithium leaching rate can reach more than 98 percent, the single exchange rate of the common aqueous solution exchange method is only 20-30 percent, the common aqueous solution exchange method needs to use high-concentration salt solution for continuous and repeated exchange, the salt solution utilization rate is lower, the consumption is large (Li Zhiliang, zhi Jianping and Zhang Yulin, the initial material is used for Li + 、Ca 2+ Preparation of Mixed Low silicon X-type molecular sieves (LSX) and Effect of adsorption Performance [ j ]]Inorganic materials journal, vol.23, no.5, sep., 2008);
3. the lithium extraction method is a high-efficiency selective lithium extraction process, the single lithium leaching rate is more than 98%, and silicon and aluminum are leached in a small amount, so that great convenience is provided for the next impurity removal and purification, and the technical economy is remarkable.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to specific examples.
The spent lithium molecular sieves used in the examples below were all adsorbents removed from the pressure swing adsorption oxygenerator of the Legend gas group and had a lithium content of 4.15wt%.
The specific operation of the microfiltration in the following examples: spreading three layers of medium-speed filter paper with the thickness of 12.5cm on a circular funnel, cutting part of medium-speed filter paper with the thickness of 12.5cm into fragments, soaking the fragments into pure water to obtain paper pulp, spreading the paper pulp on the filter paper of the funnel, compacting the edges of the paper pulp by using a glass rod, vacuum-filtering to form a filter cake, and vacuum-filtering.
Example 1 a method for extracting lithium from a waste lithium molecular sieve comprises the following specific steps:
200g of waste lithium molecular sieve is weighed, ground and sieved by a 100-mesh sieve, then mixed with 25wt% of sodium chloride solution according to the molar ratio of sodium to lithium ions of 4:1, fully stirred into slurry, heated to 60 ℃, subjected to heat preservation leaching for 2h at the temperature, filtered to obtain 780ml of lithium chloride leaching solution, the filter residues are leached by 800ml of cold pure water to obtain 800ml of lithium chloride leaching solution, the lithium ion content in the lithium chloride leaching solution and the lithium chloride leaching solution is detected by ICP (inductively coupled plasma) to be 9.54g/L and 0.53g/L respectively, the leaching rate of lithium is calculated to be 98.2% (the leaching rate of lithium in the invention=the percentage of lithium content in the lithium chloride leaching solution and the waste lithium molecular sieve), the lithium chloride leaching solution is returned to the previous stage to prepare the sodium chloride solution, and the filter residues after pure water leaching are subjected to solid waste treatment;
the pH value of the obtained lithium chloride leaching solution is regulated to be 6.0 by hydrochloric acid with the concentration of 2mol/L, the temperature is raised to 80 ℃, after the solution is stirred for 0.5h at the temperature to remove silicon and aluminum, the solution is precisely filtered to obtain primary filtrate, the content of calcium ions and magnesium ions in the primary filtrate is 0.2219g/L and 0.2353g/L respectively by ICP, 1g of sodium carbonate and 2g of sodium hydroxide are added into the primary filtrate, the temperature is raised to 80 ℃, after the solution is stirred for 0.5h at the temperature to remove calcium and magnesium, the solution is precisely filtered to obtain lithium chloride clean solution, the lithium ion concentration in the lithium chloride clean solution is measured by ICP to be 9.43g/L, the obtained lithium chloride clean solution is evaporated and concentrated to be 30g/L of lithium ion concentration, then 230ml of sodium carbonate solution with the concentration of 300g/L is added into the solution, and the obtained lithium carbonate is dried for 2 times by hot water washing (the hot water washing temperature is 70-80 ℃ and the same below) and then is dried for 2h at 150 ℃. The dried sample had a lithium carbonate content of 99.4%, a silicon content of 15.8ppm and an aluminum content of 4.6ppm.
Example 2 a method for extracting lithium from a spent lithium molecular sieve, comprising the following steps: :
200g of waste lithium molecular sieve is weighed, ground and sieved by a 100-mesh sieve, then mixed with 25wt% sodium sulfate solution according to the molar ratio of sodium ions of 4:1, fully stirred into slurry, heated to 70 ℃, stirred and leached for 1.5h at the temperature, filtered to obtain 1360ml of lithium sulfate leaching solution, filter residues are leached by 1400ml of cold pure water to obtain 1390ml of lithium sulfate washing solution, the lithium ion concentration in the lithium sulfate leaching solution and the lithium sulfate washing solution is detected by ICP to be 5.41g/L and 0.351g/L respectively, and the lithium leaching rate is calculated to be 98.1%. Regulating pH of the obtained lithium sulfate leaching solution to 5.0 by using 2mol/L sulfuric acid, heating to 70 ℃, preserving heat and stirring for 0.5h at the temperature to remove silicon and aluminum, performing precise filtration, detecting filtrate by using ICP to obtain a filtrate with calcium ion content of 0.1665g/L and magnesium ion content of 0.1765g/L, adding 1.2g sodium carbonate and 2.4g sodium hydroxide into the filtrate, heating to 80 ℃, stirring for 0.5h at the temperature to remove calcium and magnesium, performing precise filtration to obtain a lithium sulfate clean solution, detecting by using ICP to obtain a lithium ion concentration of 5.62g/L in the clean solution, evaporating and concentrating the lithium sulfate clean solution to obtain a lithium ion concentration of 32g/L, adding 270ml sodium carbonate solution with the concentration of 250g/L into the clean solution, washing the obtained product by using hot water twice, and drying at 150 ℃ for 2h. The dried sample had a lithium carbonate content of 99.2%, a silicon content of 21.5ppm and an aluminum content of 5.3ppm.
Example 3 a method for extracting lithium from a spent lithium molecular sieve, comprising the following steps: :
200g of waste lithium molecular sieve is weighed, the mixture is ground and passes through a 100-mesh sieve, 25wt% sodium nitrate solution is fully stirred according to the molar ratio of sodium ions to lithium ions of 4:1, the temperature is raised to 65 ℃, stirring and leaching are carried out for 2h at the temperature, 1650ml of lithium nitrate leaching solution is obtained after filtering, 1700ml of lithium nitrate washing solution is obtained by leaching filter residues with 1700ml of cold pure water, the lithium ion concentration in the lithium nitrate leaching solution and the lithium nitrate washing solution is respectively 4.6g/L and 0.165g/L through ICP detection, and the calculated lithium leaching rate is 98.5%. Regulating pH of the obtained lithium nitrate leaching solution to 5.5 by using 2mol/L nitric acid, heating to 65 ℃, keeping the temperature at 65 ℃ and stirring for 0.5h to remove silicon and aluminum, performing precise filtration, detecting the content of calcium and magnesium ions in the filtrate by using ICP to obtain 0.1601g/L and 0.1059g/L respectively, adding 1.4g sodium carbonate and 1.8g sodium hydroxide into the filtrate, heating to 70 ℃ after the addition, keeping the temperature at 70 ℃ for 0.5h to remove calcium and magnesium, performing precise filtration to obtain a lithium nitrate clean solution, detecting the lithium ion concentration in the lithium nitrate clean solution by using ICP to obtain 4.75g/L, concentrating the clean solution to the lithium ion concentration of 35g/L, adding 200ml of sodium carbonate solution with the concentration of 350g/L into the clean solution to precipitate lithium carbonate, washing the obtained product with hot water for 2 times, and drying at 150 ℃ for 2h. The dried sample contained 99.5% lithium carbonate, 12.4ppm silicon and 2.8ppm aluminum.
Example 4 a method for extracting lithium from waste lithium molecular sieves comprises the following specific steps:
200g of waste lithium molecular sieve is weighed, ground and sieved by a 100-mesh sieve, and then fully stirred and mixed with 25wt% of sodium chloride solution according to the molar ratio of sodium ions of 3:1 to form slurry, the slurry is heated to 60 ℃, the slurry is subjected to heat preservation leaching for 2 hours at 60 ℃, 650ml of lithium chloride leaching solution is obtained after filtration, 660ml of cold pure water is used for leaching filter residues to obtain 650ml of lithium chloride washing solution, the lithium ion concentration in the lithium chloride leaching solution and the lithium chloride washing solution is respectively 10.7g/L and 0.5662g/L through ICP detection, and the leaching rate of lithium in the step is 91.6 percent, so that the leaching requirement is basically met; impurity removal stage: regulating pH of the obtained lithium chloride leaching solution to 6.0 by using 2mol/L hydrochloric acid, heating to 80 ℃, stirring at 80 ℃ for 0.5h to remove silicon and aluminum, performing precise filtration, detecting the filtrate by ICP to obtain a solution with calcium and magnesium ion content of 0.2322g/L and 0.2615g/L respectively, adding 0.8g sodium carbonate and 1.7g sodium hydroxide into the filtrate, heating to 80 ℃, stirring at 80 ℃ for 0.5h to remove calcium and magnesium, performing precise filtration to obtain a lithium chloride clean solution, detecting by ICP to obtain a lithium ion concentration of 11.2g/L in the lithium chloride clean solution, concentrating the clean solution to a lithium ion concentration of 30g/L, adding 190ml of a sodium carbonate solution with a concentration of 300g/L into the clean solution to precipitate lithium carbonate, washing the obtained product by 2 times of hot water and drying at 150 ℃ for 2h. The dried sample contained 99.5% lithium carbonate, 11.6ppm silicon and 2.5ppm aluminum.
Comparative example 1:
200g of waste lithium molecular sieve is weighed, ground and sieved by a 100-mesh sieve, and then fully stirred and mixed with 25wt% sodium chloride solution according to the molar ratio of sodium ions of 1.4:1 to form slurry, the slurry is heated to 60 ℃, then the slurry is subjected to heat preservation and leaching for 2 hours to obtain 300ml of lithium chloride leaching solution, 300ml of lithium chloride washing solution is obtained after filtration, the lithium ion concentration in the lithium chloride washing solution is respectively 18.6g/L and 1.81g/L through ICP detection, the leaching rate of lithium is 76.8%, the leaching rate is low, the economical efficiency is poor, the obtained lithium chloride leaching solution is heated to 80 ℃ after the pH value is regulated to 6.0 by 2mol/L of hydrochloric acid, silicon and aluminum are removed by stirring at 80 ℃ for 0.5 hours, the content of calcium and magnesium ions is respectively 0.3774g/L and 0.5g/L after ICP detection, the lithium carbonate content in the filtrate is heated to 80 ℃ after the ICP detection, the lithium ion concentration is respectively 18.6g/L and the sodium hydroxide concentration in the lithium chloride washing solution is 1.5 g/L, the lithium ion concentration in the lithium carbonate washing solution is obtained after the lithium ion concentration is detected to be 180.5 g/L, the lithium ion concentration is detected to be 180.2 g, the lithium ion concentration in the lithium carbonate solution is washed to be 20 g, and the lithium ion concentration is detected to be 3g by 3.5 g, the lithium concentration is detected to be 3g by 3g, and the lithium ion concentration is detected to be 3.5 g by 3. The dried sample contained 99.4% lithium carbonate, 8.3ppm silicon and 1.6ppm aluminum.
Comparative example 2:
the same waste lithium molecular sieve as in example 1 is selected, the leaching temperature is changed to be the normal temperature (25 ℃) for leaching for 2 hours, other conditions are the same as in example 1, lithium chloride leaching solution is obtained by filtering, lithium chloride washing liquid is obtained by leaching filter residues, the leaching rate of lithium is 88.69%, the leaching rate is low, and the economical efficiency is poor.
Comparative example 3:
the same waste lithium molecular sieve as in example 1 is selected, the leaching time is only changed to 1h, other conditions are the same as in example 1, the lithium chloride leaching solution is obtained by filtering, the filter residue is leached to obtain the lithium chloride washing solution, the leaching rate of lithium in the step is 83.6%, the leaching rate is lower, and the economical efficiency is poor.
Comparative example 4:
the same waste lithium molecular sieve as in example 1 is selected, except that the type of leaching agent is changed during leaching, sulfuric acid is used for replacing sodium chloride, other conditions are the same as in example 1, 200g of waste lithium molecular sieve is ground and passes through a 100-mesh sieve, then the waste lithium molecular sieve and 183ml of sulfuric acid with the mass concentration of 25% are fully stirred and mixed into slurry according to the molar ratio of hydrogen ions to lithium ions of 4:1, leaching is carried out for 2 hours after the temperature is raised to 60 ℃, and as the reaction progresses, the lithium molecular sieve is gradually broken, and the system is in a colloid shape and is difficult to filter in the later leaching period.
Claims (5)
1. A method for extracting lithium from waste lithium molecular sieves comprises the following steps:
(1) Pretreatment of raw materials: grinding and sieving the waste lithium molecular sieve;
(2) Lithium leaching: adding a sodium salt solution with the concentration of 20-35 wt% into the sieved lithium molecular sieve, stirring and mixing uniformly, heating to 30-80 ℃ for leaching, wherein the molar ratio of sodium in the sodium salt solution to lithium in the lithium molecular sieve is (2-5): 1, leaching for 1-3h;
(3) Separating leaching liquid: after leaching, carrying out solid-liquid separation to obtain filter residues and lithium leaching liquid, wherein the lithium leaching liquid enters a primary impurity removing procedure of the step (4), the filter residues are leached by water, leaching liquid returns to prepare sodium salt solution, and the leached filter residues are subjected to solid waste treatment;
(4) Primary impurity removal: adjusting the pH value of the lithium leaching solution to be 5-6 by using acid liquor, stirring and heating to 65-80 ℃, then preserving heat for 0.5-1h at 65-80 ℃ to remove silicon and aluminum, and performing precise filtration to obtain primary clean liquid;
(5) Secondary impurity removal: adding sodium carbonate and sodium hydroxide into the primary clean liquid according to the content of calcium and magnesium in the primary clean liquid, heating to 80-90 ℃, preserving heat for 0.5-1h, depositing calcium and magnesium, and performing precise filtration to obtain a lithium-containing clean liquid;
(6) Precipitating lithium carbonate: and (3) increasing the lithium concentration of the lithium-containing clean liquid to 30-35g/L through evaporation concentration, adding a sodium carbonate solution with the concentration of 250-300g/L into the clean liquid to deposit lithium carbonate, washing the obtained lithium carbonate with hot water, and drying to obtain a lithium carbonate product.
2. The method of claim 1, wherein the sodium salt solution in step (2) is a sodium chloride solution, a sodium sulfate solution, or a sodium nitrate solution.
3. The method according to claim 1, wherein the acid solution in the step (4) is hydrochloric acid, sulfuric acid or nitric acid having a concentration of 2 to 4 mol/L.
4. The method of claim 1, wherein the conditions of the drying in step (6) are: baking at 150deg.C for 2 hr.
5. The method according to claim 2, wherein the leaching conditions in step (2) are: leaching at 60-70deg.C for 1.5-2 hr.
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