CN117466318A - Method for extracting lithium carbonate from lithium ore - Google Patents
Method for extracting lithium carbonate from lithium ore Download PDFInfo
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- CN117466318A CN117466318A CN202311391112.XA CN202311391112A CN117466318A CN 117466318 A CN117466318 A CN 117466318A CN 202311391112 A CN202311391112 A CN 202311391112A CN 117466318 A CN117466318 A CN 117466318A
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- lithium
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- carbonate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 58
- 239000000706 filtrate Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 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 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052629 lepidolite Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 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
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to the technical field of lithium carbonate preparation, and particularly discloses a method for extracting lithium carbonate from lithium ores. The method comprises the following steps: crushing lithium ore, adding sodium sulfate, calcium oxide, graphite powder and carbon fiber, and mixing to obtain a mixed material; under the protection of inert gas, heating and roasting the mixed material, cooling, introducing oxygen-containing gas for treatment, and cooling to room temperature to obtain a roasted material; adding ethanol into the roasting material, mixing, ball milling, heating to remove ethanol to obtain fine powder; leaching the fine powder to obtain a lithium leaching solution; and removing impurities from the lithium leaching solution, precipitating lithium, filtering, washing and drying to obtain lithium carbonate. The roasting material obtained by the method is free of sintering, is convenient for ball milling, and has the average granularity of the obtained fine powder less than 50 mu m, is convenient for leaching lithium, has the leaching rate of lithium more than 98%, is convenient for precipitating lithium, increases the yield of lithium carbonate, ensures the purity of the lithium carbonate to be more than 99.5%, and has market application and economic value.
Description
Technical Field
The present application relates to the field of lithium carbonate preparation technology, and more particularly, to a method for extracting lithium carbonate from lithium ores.
Background
Lithium carbonate is an inorganic compound and is also an important chemical raw material. With the development of new energy sources in China, the lithium carbonate is taken as a basic raw material, and the production and the demand of the lithium carbonate are continuously increased. Lithium carbonate is mainly extracted from lithium ore or salt lake brine. For extracting lithium carbonate from lithium ore, lepidolite, spodumene, petalite and the like are often adopted for the lithium ore, and the extraction method mainly comprises a sulfate method, a limestone sintering method, a sulfuric acid method and the like. The method comprises the steps of extracting lithium carbonate from lithium ores by a sulfate method, crushing the lithium ores to obtain powder, adding sodium sulfate into the powder, roasting at high temperature to enable the lithium ores to react with the sodium sulfate to obtain roasted materials, grinding the roasted materials to obtain fine powder, leaching the fine powder, removing impurities, and precipitating lithium to obtain the lithium carbonate. In actual processing, the applicant finds that powder and sodium sulfate are easy to sinter at high temperature roasting, so that the grinding of the roasted material is seriously affected, the lithium leaching rate is reduced, and the yield of lithium carbonate is further reduced.
Disclosure of Invention
In order to reduce the occurrence of sintering of the roasted material and improve the lithium leaching rate, the application provides a method for extracting lithium carbonate from lithium ores.
In a first aspect, the present application provides a method for extracting lithium carbonate from lithium ore, which adopts the following technical scheme:
a method of extracting lithium carbonate from lithium ore, comprising the steps of:
s1, crushing and sieving lithium ores to obtain powder;
s2, adding sodium sulfate, calcium oxide, graphite powder and carbon fiber into the powder, and mixing to obtain a mixed material;
s3, under the protection of inert gas, heating the mixed material to 1000-1100 ℃, carrying out heat preservation treatment for 3-5 hours, then cooling to 340-360 ℃, then introducing oxygen-containing gas, carrying out heat preservation treatment for 1-3 hours, and then cooling to room temperature to obtain a roasting material;
s4, adding ethanol into the roasting material, mixing, performing ball milling, and heating to remove the ethanol to obtain fine powder;
s5, leaching the fine powder by using sulfuric acid solution to obtain lithium leaching solution;
s6, removing impurities from the lithium leaching solution, precipitating lithium by adopting a carbonate solution, filtering, washing and drying to obtain lithium carbonate.
According to the method for extracting lithium carbonate from lithium ore, the sintering condition of the mixed material is greatly improved, the roasting material is free of sintering, ball milling is facilitated, the average granularity of fine powder is less than 50 mu m, lithium leaching is facilitated, the lithium leaching rate is more than 98%, lithium precipitation is facilitated, the yield of lithium carbonate is increased, the purity of lithium carbonate is more than 99.5%, and good performance is shown.
Sodium sulfate is used in the powder, which is capable of reacting with the powder and forming lithium sulfate. Graphite powder and carbon fiber are used in the powder, the graphite powder is in a particle shape, the carbon fiber is in a needle shape, and the synergistic effect between the graphite powder and the carbon fiber is utilized to greatly improve the heat conductivity of the mixed material, reduce the occurrence of sintering and overburning, and ensure that the baked material is not sintered. Then cooling and introducing oxygen-containing gas, enabling graphite powder and carbon fiber to react with oxygen to generate gas, enabling the generated gas to form a pore channel, increasing the fluffiness of the roasting material, facilitating ball milling, reducing the granularity of fine powder, facilitating lithium leaching, improving the lithium leaching rate, increasing the yield of lithium carbonate, and having market application and economic value.
Optionally, the mass content of lithium oxide in the lithium ore is 0.5-1.5%; the 100-mesh screen allowance of the powder is less than or equal to 1 percent; the granularity of the graphite powder is 50-100 mu m; the carbon fiber has a diameter of 1-10 μm and a length of 100-500 μm.
Through adopting above-mentioned technical scheme, inject the lithium oxide content in the lithium ore, control stir of lithium oxide content, and then reduce and influence the effect because of stirring too greatly, increase the stability of extracting lithium carbonate, guarantee the quality of lithium carbonate.
And the 100-mesh screen residue of the powder is limited, so that the mixing and roasting of the follow-up raw materials are facilitated. The particle size of the graphite powder, the diameter and the length of the carbon fiber are limited, so that the uniformity of raw material mixing is improved, and the use effect of the graphite powder and the carbon fiber is enhanced.
Optionally, in the step S2, the weight ratio of the powder, the sodium sulfate, the calcium oxide, the graphite powder and the carbon fiber is 40 (20-30)/(4-6)/(1-2).
By adopting the technical scheme, the weight ratio of the powder, the sodium sulfate, the calcium oxide, the graphite powder and the carbon fiber is limited, so that the reaction of the powder and the sodium sulfate is facilitated, the heat transfer efficiency is increased by utilizing the graphite powder and the carbon fiber, the temperature is convenient to control, the sintering condition is reduced, the subsequent ball milling is facilitated, the granularity of the fine powder is reduced, and the lithium leaching rate is improved.
Optionally, in the step S4, the weight ratio of the ball milling medium, the roasting material and the ethanol in the ball milling treatment is (3-5) (1-3) (1-2).
By adopting the technical scheme, the weight ratio of the ball milling medium, the roasting material and the ethanol is limited, the ball milling medium is used for ball milling the roasting material, cracks are generated under the grinding and impact force of the roasting material, and the cracks continue to diffuse and break to form small particles. Ethanol is matched, the ethanol can rapidly enter crack gaps to block crack closure, so that the cracks rapidly spread, and the ball milling efficiency is greatly improved.
In various embodiments, the weight ratio of ball milling media, roasting material, ethanol is 4:2:1, which may also be set to 3:1:1, 3:1:2, 3:3:1, 3:3:2, 5:1:1, 5:1:2, 5:3:1, 5:3:2, etc., as desired.
Optionally, in the step S4, in the ball milling treatment, the rotating speed is 400-600r/min, and the ball milling time is 60-80min. Preferably, the rotating speed is 500r/min, and the ball milling time is 70min.
By adopting the technical scheme, the rotating speed and the ball milling time in the ball milling treatment are limited, so that the control of the ball milling treatment is facilitated.
Optionally, the ball milling medium is zirconia balls, and the diameter of the zirconia balls is 10-50mm. Preferably, the zirconia balls have a diameter of 20mm.
By adopting the technical scheme, the ball milling medium material and the diameter are limited, so that the ball milling medium is convenient to select.
Optionally, step S5 specifically includes: adding 50-60% sulfuric acid solution into the fine powder, heating to 100-120deg.C, stirring for 4-6 hr, and filtering to obtain primary leaching residue and primary leaching filtrate;
then adding 50-60% sulfuric acid solution into the primary leaching filter residue, heating to 100-120 ℃, stirring for 2-4h, and filtering to obtain a secondary leaching filter residue and a secondary leaching filtrate;
adding 50-60% sulfuric acid solution into the second-stage leaching filter residue, heating to 100-120 ℃, stirring for 1-3h, and filtering to obtain a third-stage leaching filter residue and a third-stage leaching filtrate;
then, washing the three-stage leaching filter residues by adopting a sulfuric acid solution with the mass concentration of 5-15%, and filtering to obtain a washing liquid;
and mixing the primary leaching filtrate, the secondary leaching filtrate, the tertiary leaching filtrate and the washing liquid to obtain the lithium leaching solution.
By adopting the technical scheme, the sulfuric acid solution is adopted for three times of soaking, and the sulfuric acid solution is matched for washing, so that lithium sulfate in the fine powder is fully leached, and the lithium leaching rate is improved.
Further, in the step S5, the sulfuric acid solution is used in an amount of 800-1200g in the filtration treatment of the primary leaching residue. Preferably, the sulfuric acid solution is used in an amount of 900-1100g. More preferably, the sulfuric acid solution is used in an amount of 1000g.
In the filtering treatment of the obtained secondary leaching filter residue, the usage amount of the sulfuric acid solution is 800-1200g. Preferably, the sulfuric acid solution is used in an amount of 900-1100g. More preferably, the sulfuric acid solution is used in an amount of 1000g.
In the filtering treatment of the three-stage leaching filter residue, the usage amount of the sulfuric acid solution is 800-1200g. Preferably, the sulfuric acid solution is used in an amount of 900-1100g. More preferably, the sulfuric acid solution is used in an amount of 1000g.
Further, in step S5, the washing times are one to five times, and the amount of sulfuric acid solution used per washing is 300-800g. Preferably, the number of times of washing is three, and the amount of sulfuric acid solution used per washing is 500g.
Optionally, step S6 specifically includes: adding alkali into the lithium leaching solution to adjust the pH value to 7.5-8, filtering, adding polyacrylamide solution for mixing, adding alkali to adjust the pH value to 12.5-13, filtering, evaporating and concentrating, cooling to room temperature, adding disodium ethylenediamine tetraacetate solution for mixing, cooling to 5-15 ℃, filtering, heating to 90-100 ℃, adding saturated sodium carbonate solution until no precipitate is generated, stirring for 2h, filtering at 90-100 ℃, washing, and drying to obtain lithium carbonate.
By adopting the technical scheme, the pH value is adjusted to 7.5-8 by adding alkali into the lithium leaching solution, so that iron ions and aluminum ions can form precipitation, and the iron ions and the aluminum ions can be removed by matching with filtration. Adding polyacrylamide, regulating pH to 12.5-13, precipitating ferrous ion, calcium ion, magnesium ion and manganese ion, flocculating with polyacrylamide, and filtering to remove ferrous ion, calcium ion, magnesium ion and manganese ion. Because calcium hydroxide formed by calcium ions is slightly soluble in water, calcium hydroxide and calcium ions still remain, at the moment, evaporation concentration is carried out, calcium hydroxide is separated out, disodium ethylenediamine tetraacetate is added, and the calcium ions can be chelated and stably dispersed in water, and the calcium hydroxide is further removed by matching with filtration, so that a small amount of calcium ions are chelated and stably dispersed in water. And then heating, adding sodium carbonate, forming lithium carbonate precipitate by sodium carbonate and lithium sulfate, and washing by matching with filtration to obtain the lithium carbonate. In the present application, the purity of lithium carbonate is greater than 99% by the mutual coordination of the steps.
Further, in the washing of step S6, ethanol is firstly adopted for washing one to five times, the consumption of ethanol for each washing is 300-800g, then deionized water with the temperature of 90-100 ℃ is adopted for washing one to five times, and the consumption of deionized water for each washing is 300-800g. More preferably, ethanol is used for three times, the amount of ethanol used for each washing is 500g, and deionized water at 95 ℃ is used for three times, and the amount of deionized water used for each washing is 500g.
Optionally, in step S6, evaporating and concentrating, cooling to room temperature to obtain a concentrated solution, wherein the mass concentration of lithium ions in the concentrated solution is 0.5-1%.
By adopting the technical scheme, the concentrated solution contains a large amount of lithium sulfate, lithium ions in the concentrated solution are limited, the control of evaporation concentration is convenient, and the subsequent lithium precipitation is also convenient.
Optionally, in the step S6, the mass concentration of polyacrylamide in the polyacrylamide solution is 0.05-0.1%, and the weight ratio of the lithium leaching solution to the polyacrylamide solution is 100 (1-2);
the mass concentration of the disodium edetate in the disodium edetate solution is 0.01-0.05%, and the weight ratio of the lithium leaching solution to the disodium edetate solution is 100 (1-2).
By adopting the technical scheme, the usage amount of polyacrylamide and disodium ethylenediamine tetraacetate is limited, so that the impurity removal treatment of the lithium leaching solution is facilitated.
In summary, the present application has at least the following beneficial effects:
the method for extracting lithium carbonate from lithium ore uses sodium sulfate in powder material, so that lithium sulfate is formed conveniently. The graphite powder and the carbon fiber are used in the powder, the synergistic effect between the graphite powder and the carbon fiber is utilized, the heat conductivity of the mixed material is greatly improved, the occurrence of overburning is reduced, the oxygen-containing gas is introduced after the mixed material is matched with the roasting, the graphite powder and the carbon fiber can react with oxygen to generate gas to form pore channels, the fluffiness of the roasted material is increased, the roasted material is free from sintering, the ball milling is convenient, the granularity of fine powder is reduced, the average granularity of the fine powder is less than 50 mu m, the leaching of lithium is convenient, the lithium leaching rate is more than 98%, the lithium precipitation is convenient, the yield of lithium carbonate is increased, the purity of the lithium carbonate is more than 99.5%, and the mixed material has market application and economic value.
Detailed Description
In order that the present application may be more readily understood, the following examples are presented in conjunction with the following detailed description, which are intended to be illustrative only and are not intended to limit the scope of application of the present application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Examples
Example 1
A method of extracting lithium carbonate from lithium ore, comprising the steps of:
s1, crushing lepidolite, and sieving with a 100-mesh sieve to obtain powder, wherein the sieve residue of the powder is 0.3%, and the mass content of lithium oxide is 0.85%.
S2, taking 400g of the powder obtained in the step S1, adding 250g of sodium sulfate, 50g of calcium oxide, 50g of graphite powder and 15g of carbon fiber into the powder, and stirring for 20min to obtain a mixed material.
Wherein the granularity of the graphite powder is 80 mu m and is selected from Hebei Jiukang mineral products Limited; the carbon fiber has a diameter of 7 μm and a length of 400 μm and is selected from the group consisting of new east material (Guangdong) Inc.
And S3, heating the mixed material obtained in the step S2 to 1050 ℃ under the protection of nitrogen, and carrying out heat preservation treatment for 4 hours. Then cooling to 350 ℃, introducing air, and carrying out heat preservation treatment for 2 hours. And then cooling to 25 ℃ to obtain the roasting material.
S4, taking the roasting material obtained in the step S3, adding ethanol into the roasting material, and stirring for 20min. Then ball milling is carried out for 70min at the rotating speed of 500 r/min. Then heating to 80 ℃, preserving heat for 2 hours, and cooling to 25 ℃ to obtain fine powder.
In the ball milling treatment, the ball milling medium is zirconia balls, the diameter of the zirconia balls is 20mm, and the weight ratio of the ball milling medium, the roasting material and the ethanol is 4:2:1.
S5, taking the fine powder obtained in the step S4, adding 1000g of sulfuric acid solution with the mass concentration of 55% into the fine powder, heating to 120 ℃, stirring for 5 hours, and filtering to obtain primary leaching filter residues and primary leaching filtrate.
Then 1000g of sulfuric acid solution with the mass concentration of 55% is added into the primary leaching filter residue, the temperature is raised to 120 ℃, stirring treatment is carried out for 3 hours, and filtration is carried out, thus obtaining secondary leaching filter residue and secondary leaching filtrate.
And then 1000g of sulfuric acid solution with the mass concentration of 50-60% is added into the secondary leaching filter residue, the temperature is raised to 120 ℃, stirring treatment is carried out for 2 hours, and the tertiary leaching filter residue and tertiary leaching filtrate are obtained after filtration.
And then, washing the three-stage leaching filter residue for three times by adopting a sulfuric acid solution with the mass concentration of 10%, wherein the sulfuric acid solution used in each washing is 500g, and filtering to obtain a washing solution.
And mixing the primary leaching filtrate, the secondary leaching filtrate, the tertiary leaching filtrate and the washing liquid, and stirring for 10min to obtain the lithium leaching solution.
S6, taking the lithium leaching solution obtained in the step S5, adding a saturated sodium hydroxide solution into the lithium leaching solution, adjusting the pH value to 8, and filtering to obtain primary impurity removal filter residues and primary impurity removal filtrate.
Then adding polyacrylamide solution with the mass concentration of 0.05% into the primary impurity removal filtrate, stirring for 20min, adding saturated sodium hydroxide solution, adjusting the pH value to 13, and filtering to obtain secondary impurity removal filter residues and secondary impurity removal filtrate.
Evaporating and concentrating the secondary impurity-removing filtrate, cooling to 25 ℃ to obtain concentrated solution, wherein the mass concentration of lithium ions in the concentrated solution is 0.9%, then adding disodium ethylenediamine tetraacetate solution with the mass concentration of 0.02%, stirring for 20min, cooling to 15 ℃, and filtering to obtain tertiary impurity-removing filter residues and tertiary impurity-removing filtrate.
Heating the tertiary impurity removal filtrate to 95 ℃, adding saturated sodium carbonate solution until no precipitate is generated, stirring for 2 hours, and filtering to obtain lithium carbonate precipitate.
Then, the washing was performed three times with ethanol, and 500g of ethanol was used for each washing. And then washing three times with deionized water at 95 ℃ with 500g of deionized water used for each washing. And then drying at the temperature of 100 ℃ to obtain lithium carbonate.
Wherein the weight ratio of the lithium leaching solution to the polyacrylamide solution is 100:1, and the average molecular weight of the polyacrylamide in the polyacrylamide solution is 1000 ten thousand daltons; the weight ratio of the lithium leaching solution to the disodium edetate solution is 100:1.
Example 2
A method for extracting lithium carbonate from lithium ore is different from example 1 in that sodium sulfate, calcium oxide, graphite powder and carbon fiber are used in different amounts in step S2.
Specifically, the amount of sodium sulfate used was 200g, the amount of calcium oxide used was 60g, the amount of graphite powder used was 60g, and the amount of carbon fiber used was 10g.
Example 3
A method for extracting lithium carbonate from lithium ore is different from example 1 in that sodium sulfate, calcium oxide, graphite powder and carbon fiber are used in different amounts in step S2.
Specifically, the amount of sodium sulfate used was 300g, the amount of calcium oxide used was 40g, the amount of graphite powder used was 40g, and the amount of carbon fiber used was 20g.
Comparative example
Comparative example 1
A method for extracting lithium carbonate from lithium ore, which is different from example 1 in the steps of step S2 and step S3.
The step S2 specifically comprises the following steps: 400g of the powder obtained in the step S1 is taken, 250g of sodium sulfate and 50g of calcium oxide are added into the powder, and stirring treatment is carried out for 20min, so as to obtain a mixed material.
The step S3 specifically comprises the following steps: and (3) heating the mixed material obtained in the step (S2) to 1050 ℃, and carrying out heat preservation treatment for 4 hours. Then cooling to 350 ℃, and preserving heat for 2 hours. And then cooling to 25 ℃ to obtain the roasting material.
Comparative example 2
A method for extracting lithium carbonate from lithium ore, which is different from example 1 in the steps of step S2 and step S3.
The step S2 specifically comprises the following steps: 400g of the powder obtained in the step S1 is taken, 250g of sodium sulfate and 50g of calcium oxide are added into the powder, and stirring treatment is carried out for 20min, so as to obtain a mixed material.
The step S3 specifically comprises the following steps: and (3) heating the mixed material obtained in the step (S2) to 850 ℃, and carrying out heat preservation treatment for 4 hours. Then cooling to 350 ℃, and preserving heat for 2 hours. And then cooling to 25 ℃ to obtain the roasting material.
Comparative example 3
A method of extracting lithium carbonate from lithium ore, which is different from example 1 in the step of step S3.
The step S3 specifically comprises the following steps: and (3) heating the mixed material obtained in the step (S2) to 1050 ℃, and carrying out heat preservation treatment for 4 hours. Then cooling to 350 ℃, and preserving heat for 2 hours. And then cooling to 25 ℃ to obtain the roasting material.
Comparative example 4
A method for extracting lithium carbonate from lithium ore, which is different from example 1 in that carbon fiber is replaced with an equal amount of graphite powder in step S2.
Comparative example 5
A method for extracting lithium carbonate from lithium ore, which is different from example 1 in that graphite powder is replaced with an equal amount of carbon fiber in step S2.
Performance test
(1) The calcined materials obtained in step S3 of examples 1 to 3 and comparative examples 1 to 5 were used as samples, and the sintering conditions of the samples were observed and recorded, and the detection results are shown in Table 1.
(2) The fine powders obtained in step S4 of examples 1 to 3 and comparative examples 1 to 5 were each used as a sample, and the average particle size of the samples was measured, and the measurement results are shown in Table 1.
(3) The lithium leaching solutions obtained in the steps S5 of examples 1 to 3 and comparative examples 1 to 5 were taken as samples, and the lithium ion content in the samples was measured, and the lithium leaching rate was calculated in combination with the mass content of lithium oxide in lepidolite of 0.85%, and the measurement results are shown in Table 1.
(4) The lithium carbonate obtained in step S6 of examples 1 to 3 and comparative examples 1 to 5 was used as a sample, and the purity of lithium carbonate in the sample was measured, and the measurement results are shown in Table 1.
TABLE 1 detection results
As can be seen from Table 1, the method for extracting lithium carbonate has no sintering condition of the roasting material, and is convenient for ball milling. The fine powder has lower granularity, the average granularity is 38-48 mu m, and the leaching of lithium is convenient. Meanwhile, the lithium ion battery also has higher lithium leaching rate, the lithium leaching rate is 98.2-98.9%, the lithium deposition is convenient, the yield of lithium carbonate is increased, the purity of the lithium carbonate is more than 99.5%, the lithium ion battery shows good performance, and the market demand is met.
In the method of comparative example 1, graphite powder and carbon fiber are not used in the raw materials of the mixture, the roasting temperature is 1050 ℃, and no oxygen-containing gas is introduced after roasting; in the method of comparative example 2, graphite powder and carbon fiber are not used in the raw materials of the mixture, the roasting temperature is 850 ℃, and no oxygen-containing gas is introduced after the roasting. It can be seen that lowering the firing temperature can improve the firing conditions of the fired material to some extent, thereby lowering the average particle size of the fine powder, but too low a firing temperature may affect the reaction of the lithium ore and sodium sulfate, rather reducing the lithium leaching rate. In the method of comparative example 3, graphite powder and carbon fiber are used as raw materials of the mixture, the roasting temperature is 1050 ℃, and no oxygen-containing gas is introduced after roasting. From this, it can be seen that the use of graphite powder and carbon fiber in the raw material of the mixture can also improve the sintering condition of the calcined material well, and also increase the lithium leaching rate. In the method of example 1, graphite powder and carbon fiber are used as raw materials of the mixture, the roasting temperature is 1050 ℃, and oxygen-containing gas is introduced after roasting. Therefore, on one hand, graphite powder and carbon fiber are used in the mixed raw materials, and on the other hand, oxygen-containing gas is introduced after roasting, so that the roasted materials are free from sintering through the cooperation of the graphite powder and the carbon fiber, the granularity of fine powder is greatly reduced, and the lithium leaching rate is greatly improved.
Example 1 and comparative examples 4-5 were compared. Graphite powder was used as a raw material for the mixture of comparative example 4; carbon fibers were used as the raw material of the blend of comparative example 5; graphite powder and carbon fiber were used together as raw materials for the mixture in example 1. From the above, graphite powder and carbon fiber are used in the mixed raw materials, and the average particle size of the fine powder is less than 50 μm and the lithium leaching rate is more than 98% by utilizing the synergistic effect of the graphite powder and the carbon fiber, so that the extraction effect on extracting lithium carbonate from lithium ore is better.
It should be noted that the above-described embodiments are only for explaining the present application, and do not constitute any limitation to the present application. The present application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the present application as defined within the scope of the claims of the present application, and the invention may be modified without departing from the scope and spirit of the present application. Although the present application is described herein with reference to particular methods, materials and embodiments, the present application is not intended to be limited to the particular examples disclosed herein, but rather, the present application is intended to extend to all other methods and applications having the same functionality.
Claims (10)
1. A method for extracting lithium carbonate from lithium ore, characterized by: the method comprises the following steps:
s1, crushing and sieving lithium ores to obtain powder;
s2, adding sodium sulfate, calcium oxide, graphite powder and carbon fiber into the powder, and mixing to obtain a mixed material;
s3, under the protection of inert gas, heating the mixed material to 1000-1100 ℃, carrying out heat preservation treatment for 3-5 hours, then cooling to 340-360 ℃, then introducing oxygen-containing gas, carrying out heat preservation treatment for 1-3 hours, and then cooling to room temperature to obtain a roasting material;
s4, adding ethanol into the roasting material, mixing, performing ball milling, and heating to remove the ethanol to obtain fine powder;
s5, leaching the fine powder by using sulfuric acid solution to obtain lithium leaching solution;
s6, removing impurities from the lithium leaching solution, precipitating lithium by adopting a carbonate solution, filtering, washing and drying to obtain lithium carbonate.
2. A method of extracting lithium carbonate from lithium ore according to claim 1, wherein: the mass content of lithium oxide in the lithium ore is 0.5-1.5%; the 100-mesh screen allowance of the powder is less than or equal to 1 percent; the granularity of the graphite powder is 50-100 mu m; the carbon fiber has a diameter of 1-10 μm and a length of 100-500 μm.
3. A method of extracting lithium carbonate from lithium ore according to claim 1, wherein: in the step S2, the weight ratio of the powder, sodium sulfate, calcium oxide, graphite powder and carbon fiber is 40 (20-30), 4-6 and 1-2.
4. A method of extracting lithium carbonate from lithium ore according to claim 1, wherein: in the step S4, in the ball milling treatment, the weight ratio of the ball milling medium, the roasting material and the ethanol is (3-5): 1-3): 1-2.
5. The method for extracting lithium carbonate from lithium ore according to claim 4, wherein: in the step S4, the rotating speed is 400-600r/min and the ball milling time is 60-80min in the ball milling treatment.
6. The method for extracting lithium carbonate from lithium ore according to claim 4, wherein: the ball milling medium is zirconia balls, and the diameter of the zirconia balls is 10-50mm.
7. A method of extracting lithium carbonate from lithium ore according to claim 1, wherein: the step S5 specifically comprises the following steps: adding 50-60% sulfuric acid solution into the fine powder, heating to 100-120deg.C, stirring for 4-6 hr, and filtering to obtain primary leaching residue and primary leaching filtrate;
then adding 50-60% sulfuric acid solution into the primary leaching filter residue, heating to 100-120 ℃, stirring for 2-4h, and filtering to obtain a secondary leaching filter residue and a secondary leaching filtrate;
adding 50-60% sulfuric acid solution into the second-stage leaching filter residue, heating to 100-120 ℃, stirring for 1-3h, and filtering to obtain a third-stage leaching filter residue and a third-stage leaching filtrate;
then, washing the three-stage leaching filter residues by adopting a sulfuric acid solution with the mass concentration of 5-15%, and filtering to obtain a washing liquid;
and mixing the primary leaching filtrate, the secondary leaching filtrate, the tertiary leaching filtrate and the washing liquid to obtain the lithium leaching solution.
8. A method of extracting lithium carbonate from lithium ore according to claim 1, wherein: the step S6 specifically comprises the following steps: adding alkali into the lithium leaching solution to adjust the pH value to 7.5-8, filtering, adding polyacrylamide solution for mixing, adding alkali to adjust the pH value to 12.5-13, filtering, evaporating and concentrating, cooling to room temperature, adding disodium ethylenediamine tetraacetate solution for mixing, cooling to 5-15 ℃, filtering, heating to 90-100 ℃, adding saturated sodium carbonate solution until no precipitate is generated, stirring for 2h, filtering at 90-100 ℃, washing, and drying to obtain lithium carbonate.
9. A method of extracting lithium carbonate from lithium ore according to claim 8, wherein: in the step S6, evaporating and concentrating, and cooling to room temperature to obtain a concentrated solution, wherein the mass concentration of lithium ions in the concentrated solution is 0.5-1%.
10. A method of extracting lithium carbonate from lithium ore according to claim 8, wherein: in the step S6, the mass concentration of polyacrylamide in the polyacrylamide solution is 0.05-0.1%, and the weight ratio of the lithium leaching solution to the polyacrylamide solution is 100 (1-2);
the mass concentration of the disodium edetate in the disodium edetate solution is 0.01-0.05%, and the weight ratio of the lithium leaching solution to the disodium edetate solution is 100 (1-2).
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