CN117107073B - Method for extracting lithium from lithium-containing ore - Google Patents
Method for extracting lithium from lithium-containing ore Download PDFInfo
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- CN117107073B CN117107073B CN202311193658.4A CN202311193658A CN117107073B CN 117107073 B CN117107073 B CN 117107073B CN 202311193658 A CN202311193658 A CN 202311193658A CN 117107073 B CN117107073 B CN 117107073B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 165
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000002386 leaching Methods 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 63
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 37
- 239000011707 mineral Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 17
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 16
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940087291 tridecyl alcohol Drugs 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- 235000010755 mineral Nutrition 0.000 claims description 32
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 30
- 238000000354 decomposition reaction Methods 0.000 claims description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 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 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011775 sodium fluoride Substances 0.000 claims description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 21
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- 229910001760 lithium mineral Inorganic materials 0.000 description 21
- 239000000126 substance Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 235000012241 calcium silicate Nutrition 0.000 description 6
- 229910052918 calcium silicate Inorganic materials 0.000 description 6
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 6
- 229910052642 spodumene Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010456 wollastonite Substances 0.000 description 4
- 229910052882 wollastonite Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical group CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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
- C22B1/02—Roasting processes
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
-
- 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
Abstract
The application relates to the technical field of extracting lithium from minerals, and particularly discloses a method for extracting lithium from lithium-containing ores, which comprises the following operation steps: roasting lithium-containing mineral powder with the particle size of 200-300 meshes at 850-1050 ℃ for 1-2 hours, cooling to 23+/-2 ℃, adding organic acid, carrying out mixed grinding, adding a composite surfactant with the mass of 0.1-0.5% of the mass of the lithium-containing mineral powder, adding water and a catalyst, carrying out leaching reaction at 40-80 ℃, filtering, and collecting filtrate to obtain a lithium-containing extracting solution; the compound surfactant is a mixture of cetyl trimethyl ammonium bromide and isomeric tridecyl alcohol polyoxyethylene ether; the mass ratio of the organic acid to the lithium-containing mineral powder is 1: (4-6); the mass ratio of the lithium-containing mineral powder to the water is 1: (1-2). By adopting the method for extracting lithium from the lithium-containing ore, the leaching rate of lithium is up to 99.8%, and the leaching rate of lithium is improved.
Description
Method field
The present application relates to the technical field of mineral extraction of lithium, and more particularly, to a method for extracting lithium from lithium-containing ores.
Background method
Lithium is the lightest metal in nature, has unique physical and chemical characteristics of high specific heat, high conductivity, strong electrochemical activity and the like, and is widely applied to the fields of lithium ion batteries, ceramics, glass, grease, raw aluminum production, polymers and the like. With the rapid development of new energy automobiles and energy storage industries, lithium demand increases year by year. Thus, lithium resources face serious problems in terms of sustainable supply.
Currently natural lithium resources are generally divided into three major categories: salt lake brine, rock and clay. Currently, the most exploited lithium resources worldwide are salt lake brine and lithium-containing ores. The lithium-containing ore mainly comprises spodumene, lithium-aluminum, lepidolite, petalite and the like, wherein the extraction of lithium from the spodumene is common.
In the related art, the method for extracting lithium from ores mainly comprises direct acid leaching, auxiliary roasting, chlorination and vulcanization. In the existing acid leaching process, inorganic acid (such as sulfuric acid) is generally selected as a leaching agent, and the defects of high acid consumption, serious equipment corrosion, environmental pollution, high cost and the like exist. The assisted firing process includes the addition of one or more additives during firing to increase lithium extraction, while impurity ions make subsequent purification more difficult. In the chlorination or sulfidation process, the sample is in HCl or SO 2 Roasting in an atmosphere, and then water leaching the chlorinated or sulfated lithium clay sample. In addition to the severe corrosion of acid gas to equipment in the chlorination or vulcanization method, impurity elements such as calcium and magnesium can enter into solution together with lithium ions, so that the elements are difficult to separate later, weak acid is also selected as a leaching agent, but in the weak acid, the lithium ions are difficult to leach, and the leaching rate of lithium is low.
Disclosure of Invention
In order to increase the leaching rate of lithium in lithium-containing ores, the present application provides a method for extracting lithium from lithium-containing ores.
In a first aspect, the present application provides a method for extracting lithium from a lithium-containing ore, using the following method scheme:
a method for extracting lithium from a lithium-containing ore, comprising the following operative steps: roasting lithium-containing mineral powder with the particle size of 200-300 meshes at 850-1050 ℃ for 1-2 hours, cooling to 23+/-2 ℃, adding organic acid, carrying out mixed grinding, adding a composite surfactant with the mass of 0.1-0.5% of the mass of the lithium-containing mineral powder, adding water and a catalyst, carrying out leaching reaction at 40-80 ℃, filtering, and collecting filtrate to obtain a lithium-containing extracting solution;
the compound surfactant is a mixture of cetyl trimethyl ammonium bromide and isomeric tridecyl alcohol polyoxyethylene ether;
the mass ratio of the organic acid to the lithium-containing mineral powder is 1: (4-6); the mass ratio of the lithium-containing mineral powder to the water is 1: (1-2).
By adopting the scheme, the lithium-containing mineral powder is roasted at 850-1050 ℃ so as to expand the crystal structure of the lithium mineral powder, activate the lithium mineral powder, facilitate the reaction of the lithium mineral powder and organic acid to generate soluble lithium compounds and separate lithium metal. The composite surfactant is added to improve the dispersion uniformity of the lithium mineral powder in the reaction system, thereby promoting the leaching reaction.
The mixed grinding adopts a ball milling mode, so that the lithium-containing mineral powder can be activated, the surface activity, chemical adsorptivity and crystal structure of the lithium-containing mineral powder can be changed, the solubility of the lithium-containing mineral powder can be improved, and the lithium-containing mineral powder and other raw materials can be mutually fused and embedded to be successfully mixed.
The compound surfactant is a mixture of cetyl trimethyl ammonium bromide and fatty alcohol polyoxyethylene ether, the cetyl trimethyl ammonium bromide is stable in an acid solution, and after the isomeric tridecyl alcohol polyoxyethylene ether is added, the surfactant of the cetyl trimethyl ammonium bromide is improved, so that the system is finer and more uniform, and the leaching reaction is facilitated.
As preferable: the mass ratio of the lithium-containing mineral powder to the catalyst is 1: (1.5-2.5).
By adopting the scheme, the mass ratio of the lithium-containing mineral powder to the catalyst is adjusted, so that the leaching of lithium ions from the lithium-containing mineral powder can be promoted.
As preferable: the catalyst is a compound of sodium fluoride and sodium fluosilicate.
By adopting the scheme, the sodium fluoride has larger solubility to organic matters, can promote the reaction while being used as a solvent, is not easy to cause side reaction, and can improve the leaching rate of the lithium ions leached by the organic acid. The leaching rate of lithium ions can be further improved by adding sodium fluosilicate.
As preferable: the mass ratio of the sodium fluoride to the sodium fluosilicate is 1: (1-3).
By adopting the scheme, the mass ratio of the sodium fluoride to the sodium fluosilicate is adjusted, so that the solubility of organic matters can be further improved, and the leaching rate of lithium ions is improved.
As preferable: the mass ratio of the cetyl trimethyl ammonium bromide to the isomeric tridecyl alcohol polyoxyethylene ether is 1; (2-4).
By adopting the scheme, the mass ratio of the cetyl trimethyl ammonium bromide to the isomeric tridecyl alcohol polyoxyethylene ether is adjusted, so that the dispersion uniformity of the lithium mineral powder in a reaction system can be further improved, and the leaching reaction is promoted.
As preferable: adding a decomposition accelerator accounting for 20-50% of the mass of the lithium-containing mineral powder in the roasting process of the lithium-containing mineral powder; the decomposition accelerator comprises the following raw materials in parts by weight: 20-35 parts of calcium carbonate, 10-20 parts of calcium chloride and 20-30 parts of polymethyl methacrylate.
By adopting the scheme, the decomposition accelerator is added in the roasting process, so that the lithium mineral powder can be fully decomposed, and the ion exchange reaction is facilitated. Wherein SiO in calcium carbonate and lithium mineral powder 2 Generating calcium metasilicate, and under the lower roasting temperature, carrying out secondary reaction on the calcium metasilicate and calcium carbonate to generate wollastonite carbonate, so that the content of the calcium metasilicate is reduced, thereby promoting the full decomposition of minerals and being beneficial to the ion exchange reaction; in addition, the carbon wollastonite is a low-solubility substance, and generates a liquid phase during the solid phase reaction, so that the activity of the reactant can be improved, the roasting reaction is promoted, and the roasting conversion rate of spodumene is improved. Furthermore, the calcium carbonate can convert harmful gases into solids, thereby reducing emission. Calcium chloride is added in the process of roasting lithium mineral powder, so that the leaching rate of lithium ions can be improved.
The calcium carbonate and the calcium chloride can destroy the original stable chemical structure of the lithium mineral powder, and can be matched with the addition of polymethyl methacrylate to manufacture holes in the lithium mineral powder, so that the lithium mineral powder with higher chemical activity and looser structure is obtained, the decomposition of the lithium mineral powder during roasting is facilitated, and the leaching rate of lithium ions is improved.
As preferable: the polymethyl methacrylate accounts for 50-80% of the total mass of the calcium carbonate and the calcium chloride.
By adopting the scheme, the dosage relation among polymethyl methacrylate, calcium carbonate and calcium chloride is adjusted, the stable chemical structure is destroyed firstly by better matching, holes are manufactured, the decomposition effect of lithium mineral powder is improved, and the leaching rate of lithium ions is improved.
As preferable: mixing the lithium-containing mineral powder with coal gangue before roasting; the mixing amount of the gangue is 10-20% of the mass of the lithium-containing mineral powder.
By adopting the scheme, the gangue and the lithium-containing mineral powder are roasted together, so that the extrusion molding of the material is facilitated, and the coal or the gangue in the molded material adopts an spontaneous combustion mode in the roasting process, so that the material is uniformly roasted, and no clamping phenomenon exists. The control of the mixing amount of the gangue is more beneficial to the even roasting of the materials, thereby improving the leaching rate of lithium ions.
As preferable: the cooling adopts rapid cooling, and the cooling rate is 20-10 ℃/s.
By adopting the scheme, rapid cooling is adopted for cooling, the cooling rate is controlled to be 20-10 ℃/s, the baked lithium mineral powder can be further kept in a thermal stress state, and the lithium mineral powder has higher activity when being mixed and ground with organic acid, so that the leaching rate of lithium ions is improved.
As preferable: the organic acid is at least one of oxalic acid, tartaric acid and sulfuric acid.
The organic acid can improve the leaching rate of lithium ions when one or more of oxalic acid, tartaric acid and sulfuric acid are selected.
In summary, the present application includes at least one of the following beneficial method effects:
(1) According to the method and the raw materials for extracting lithium, the leaching rate of lithium is 97.1-97.8%, and the leaching rate of lithium is improved.
(2) According to the method, the mixture of sodium fluoride and sodium fluosilicate is used as a catalyst, and the mass ratio of the sodium fluoride and the sodium fluosilicate is adjusted, so that the leaching rate of lithium is 98.7-99.1%, and the leaching rate of lithium is further improved.
(3) According to the method, the lithium leaching rate is 99.5% by adjusting the mass ratio of the cetyl trimethyl ammonium bromide serving as the composite surfactant to the isomeric tridecyl alcohol polyoxyethylene ether, so that the lithium leaching rate is further improved.
(4) According to the method, the decomposition accelerator is added in the process of roasting the lithium-containing mineral powder, and the doping amount of each raw material is controlled, so that the leaching rate of lithium is 99.6%, and the leaching rate of lithium is further improved.
(5) According to the method, the leaching rate of lithium is 99.7% by mixing the lithium-containing mineral powder with the coal gangue before roasting, so that the leaching rate of lithium is further improved.
(6) According to the lithium leaching device, the leaching rate of lithium is 99.8% by controlling the cooling rate, so that the leaching rate of lithium is further improved.
Detailed Description
The present application is described in further detail below in connection with specific examples.
The following raw materials are all commercial products, and are fully disclosed in the present application, and should not be construed as limiting the sources of the raw materials. The method comprises the following steps: the lithium-containing mineral powder is spodumene with the particle size of 200 meshes; the organic acid is solid oxalic acid, and the content of effective substances is 99.6%; the catalyst is calcium fluoride, and the content of effective substances is 99%; cetyl trimethyl ammonium bromide with 99% active substance content; the content of the effective substances of the isomeric tridecanol polyoxyethylene ether is 99 percent; sodium fluoride with 99% active matter content; sodium fluosilicate with 99% active matter content; calcium carbonate with a particle size of 200 meshes; calcium chloride, the content of active substances is 74%; polymethyl methacrylate with an active substance content of 99%; the content of the coal gangue and the silicon dioxide is 56 percent, and the content of the alumina is 29.6 percent.
Example 1
The method for extracting lithium from lithium-containing ore of example 1, comprising the following operational steps:
roasting 1kg of lithium-containing mineral powder (spodumene) with the particle size of 200 meshes at 1000 ℃ for 1h, cooling to 23 ℃ at 5 ℃/s, adding 200g of organic acid (oxalic acid), carrying out mixed grinding, adding 3g of composite surfactant, adding 1.5L of water and 1kg of catalyst (calcium fluoride), carrying out leaching reaction at 60 ℃, filtering, and collecting filtrate to obtain the lithium-containing extract.
Wherein the composite surfactant is 1.5g of cetyl trimethyl ammonium bromide and 1.5g of isomeric tridecanol polyoxyethylene ether.
Examples 2 to 5
Examples 2 to 5 differ from example 1 in the method of extracting lithium from lithium-containing ores in that the catalyst amounts were 666g, 500g, 400g and 333g, respectively, and the other operations were the same as in example 1.
Examples 6 to 10
Examples 6 to 10 differ from example 3 in the method of extracting lithium from lithium-containing ores in that the catalyst is a complex of sodium fluoride and sodium fluosilicate, the doping amounts of sodium fluoride and sodium fluosilicate are 334g and 166g, 250g and 500g, 166g and 334g, 125g and 375g, 111g and 375g, respectively, and the rest of the procedure is the same as that of example 3.
Examples 11 to 14
Examples 11 to 14 differ from example 8 in the amount of cetyl trimethylammonium bromide blended with the isomeric tridecanol polyoxyethylene ethers of 1.66g and 3.34g, 1.25g and 3.75g, 1g and 4g, 0.83g and 1.17g, respectively, and the remainder of the procedure is as in example 3.
Example 15
Example 15 differs from example 12 in the method of extracting lithium from lithium-containing ore in that 350g of decomposition accelerator was added during the roasting of the lithium-containing ore powder, the specific blending amount of the raw materials of the decomposition accelerator is shown in table 1, and the rest of the operations are the same as in example 12.
Example 16
Example 16 differs from example 15 in the method of extracting lithium from lithium-containing ore in that the respective raw materials of the decomposition accelerator are blended in amounts, specifically as shown in table 1, and the rest of the operations are the same as example 15.
TABLE 1 amounts of raw materials (kg) of decomposition promoters
| Example 15 | Example 16 | |
| Calcium carbonate | 30 | 30 |
| Calcium chloride | 15 | 15 |
| Polymethyl methacrylate | 20 | 29.25 |
Example 17
Example 17 differs from example 16 in the method of extracting lithium from a lithium-containing ore by mixing with 250g of coal gangue before roasting the lithium-containing ore powder, and the rest of the procedure is the same as in example 16.
Example 18
Example 18 differs from the method of extracting lithium from lithium-containing ore in example 17 in that rapid cooling is employed for cooling at a cooling rate of 15 deg.c/s, and the rest of the procedure is the same as in example 16.
Comparative example 1
The method of extracting lithium from lithium-containing ore of comparative example 1 is different from example 1 in that a complex surfactant is not added, the complex surfactant is replaced with cetyltrimethylammonium bromide in equal amount, and the rest of the operations are the same as in example 1.
Comparative example 2
The method of extracting lithium from lithium-containing ore of comparative example 2 was different from example 1 in that the complex surfactant was not added, the complex surfactant was replaced with isotridecyl alcohol polyoxyethylene ether in equal amount, and the rest of the operations were the same as those of example 1.
Comparative example 3
The method of extracting lithium from lithium-containing ore of comparative example 3 is different from example 1 in that no catalyst is added, and the rest of the operations are the same as example 1.
Performance detection
The lithium-containing extracts obtained in examples 1 to 18 and comparative examples 1 to 3 were examined by the following methods, and the specific examination results are shown in Table 2.
TABLE 2 Performance test results for different lithium containing extracts
The test results in Table 2 show that the leaching rate of lithium is up to 99.8% by adopting the method for extracting lithium from the lithium-containing ore, and the leaching rate of lithium is improved.
In combination with the performance test data of examples 1-5, the method for extracting lithium from the lithium-containing ores of examples 2-4 is adopted, the leaching rate of lithium is 97.1-97.8%, and the leaching rate is higher than that of examples 1 and 5, and the mass ratio of the catalyst to the lithium-containing ore powder is 1: (1.5-2.5) is more suitable, and the leaching rate of lithium is improved. May be associated with adjusting the mass ratio of the lithium-containing ore powder to the catalyst to facilitate leaching of lithium ions from the lithium-containing ore powder.
In combination with the performance test data of examples 6-10, the method for extracting lithium from the lithium-containing ores of examples 7-9 is adopted, the leaching rate of lithium is 98.7-99.1%, which is higher than that of examples 6 and 10, and the mass ratio of the sodium fluoride to the sodium fluosilicate is 1 when the catalyst is a mixture of the sodium fluoride and the sodium fluosilicate: (1-3) is more suitable, and the leaching rate of lithium is improved. The organic acid can be dissolved with sodium fluoride to be used as a solvent, the reaction can be promoted, side reactions are not easy to occur, and the leaching rate of the lithium ions leached by the organic acid can be improved. The leaching rate of lithium ions can be further improved by adding sodium fluosilicate, and the mass ratio of sodium fluoride to sodium fluosilicate can be adjusted, so that the solubility of organic matters can be further improved, and the leaching rate of lithium ions is improved.
The combination of the performance detection data of the examples 8 and the examples 11-14 shows that the leaching rate of lithium is 99.2-99.4% by adopting the method for extracting lithium from the lithium-containing ores of the examples 11-13, which is higher than that of the examples 9 and the examples 14, and the mass ratio of hexadecyl trimethyl ammonium bromide to isotridecyl alcohol polyoxyethylene ether is 1; (2-4) is more suitable, and the leaching rate of lithium is improved. The compound surfactant is a mixture of cetyl trimethyl ammonium bromide and fatty alcohol polyoxyethylene ether, the cetyl trimethyl ammonium bromide is stable in an acid solution, and after the isomeric tridecyl alcohol polyoxyethylene ether is added, the surfactant of the cetyl trimethyl ammonium bromide is improved, so that the system is finer and more uniform, the leaching reaction is facilitated, the mass ratio of the cetyl trimethyl ammonium bromide to the isomeric tridecyl alcohol polyoxyethylene ether is regulated, the dispersion uniformity of lithium mineral powder in the reaction system can be further improved, and the leaching reaction is promoted.
In combination with the performance test data of example 15 and example 12, the method for extracting lithium from the lithium-containing ore of example 15 is adopted, and the leaching rate of lithium is 99.5% and higher than that of example 12, which shows that the leaching rate of lithium can be improved by adding a decomposition accelerator in the process of roasting the lithium-containing ore powder. The decomposition accelerator is possibly added in the roasting process, so that the full decomposition of the lithium mineral powder can be promoted, and the ion exchange reaction is facilitated. Wherein SiO in calcium carbonate and lithium mineral powder 2 Generating calcium metasilicate, and under the lower roasting temperature, carrying out secondary reaction on the calcium metasilicate and calcium carbonate to generate wollastonite carbonate, so that the content of the calcium metasilicate is reduced, thereby promoting the full decomposition of minerals and being beneficial to the ion exchange reaction; in addition, the carbon wollastonite is a low-solubility substance, and generates a liquid phase during the solid phase reaction, so that the activity of the reactant can be improved, the roasting reaction is promoted, and the roasting conversion rate of spodumene is improved. Furthermore, the calcium carbonate can convert harmful gases into solids, thereby reducing emission. Calcium chloride is added in the process of roasting lithium mineral powder, so that the leaching rate of lithium ions can be improved.
According to the combination of the performance detection data of the example 16 and the example 15, the leaching rate of lithium is 99.6% by adopting the method for extracting lithium from the lithium-containing ore of the example 15, which is higher than that of the example 12, and the leaching rate of lithium can be improved by indicating that polymethyl methacrylate in the decomposition accelerator of the example 16 accounts for 65% of the total mass of calcium carbonate and calcium chloride. The method is possibly related to adjusting the dosage relation among polymethyl methacrylate, calcium carbonate and calcium chloride, and better matching firstly destroys a stable chemical structure and then prepares holes, so that the decomposition effect of lithium mineral powder is improved, and the leaching rate of lithium ions is improved.
The combination of the performance test data of example 17 and example 16 shows that the leaching rate of lithium is 99.7% by adopting the method for extracting lithium from the lithium-containing ore of example 17, which is higher than that of example 16, and the leaching rate of lithium can be improved by mixing the lithium-containing ore powder with coal gangue before roasting. The method is possible to bake the gangue and the lithium-containing mineral powder together, which is beneficial to extrusion molding of materials, and the coal or the gangue in the molded materials adopts a spontaneous combustion mode in the baking process, so that the materials are uniformly baked, and no clamping phenomenon exists. The control of the mixing amount of the gangue is more beneficial to the even roasting of materials, thereby improving the leaching rate of lithium ions.
By combining the performance detection data of example 17 and example 18, the method for extracting lithium from the lithium-containing ore of example 15 is adopted, the leaching rate of lithium is 99.8 percent and is higher than that of example 18, which shows that the rapid cooling is adopted for cooling, the cooling rate is 15 ℃/s, and the leaching rate of lithium can be improved. The method can be used for cooling rapidly, and the cooling rate is controlled to be 20-10 ℃/s, so that the roasted lithium mineral powder can be further kept in a thermal stress state, and has higher activity when being mixed with organic acid, thereby improving the leaching rate of lithium ions.
In addition, according to the performance detection data of comparative examples 1-3 and example 1, the leaching rate of lithium can be improved to different degrees by adding the catalyst and the composite surfactant during the mixing and grinding.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and a person skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. A method for extracting lithium from a lithium-containing ore, comprising the steps of: roasting lithium-containing mineral powder with the particle size of 200-300 meshes at 850-1050 ℃ for 1-2 hours, cooling to 23+/-2 ℃, adding organic acid, carrying out mixed grinding, adding a composite surfactant with the mass of 0.1-0.5% of the mass of the lithium-containing mineral powder, adding water and a catalyst, carrying out leaching reaction at 40-80 ℃, filtering, and collecting filtrate to obtain a lithium-containing extracting solution;
the compound surfactant is a mixture of cetyl trimethyl ammonium bromide and isomeric tridecyl alcohol polyoxyethylene ether;
the mass ratio of the organic acid to the lithium-containing mineral powder is 1: (4-6); the mass ratio of the lithium-containing mineral powder to the water is 1: (1-2);
the catalyst is a compound of sodium fluoride and sodium fluosilicate, and the mass ratio of the sodium fluoride to the sodium fluosilicate is 1: (1-3).
2. The method for extracting lithium from lithium-containing ore according to claim 1, wherein: the mass ratio of the catalyst to the lithium-containing mineral powder is 1: (1.5-2.5).
3. The method for extracting lithium from lithium-containing ore according to claim 1, wherein: the mass ratio of the cetyl trimethyl ammonium bromide to the isomeric tridecyl alcohol polyoxyethylene ether is 1: (2-4).
4. The method for extracting lithium from lithium-containing ore according to claim 1, wherein a decomposition accelerator accounting for 20-50% of the mass of the lithium-containing ore powder is added during the roasting of the lithium-containing ore powder; the decomposition accelerator comprises the following raw materials in parts by weight: 20-35 parts of calcium carbonate, 10-20 parts of calcium chloride and 20-30 parts of polymethyl methacrylate.
5. The method for extracting lithium from lithium-containing ore according to claim 4, wherein the polymethyl methacrylate is 50 to 80% of the total mass of the calcium carbonate and the calcium chloride.
6. The method for extracting lithium from lithium-containing ore according to claim 1, wherein: mixing the lithium-containing mineral powder with coal gangue before roasting; the mixing amount of the gangue is 10-20% of the mass of the lithium-containing mineral powder.
7. The method of extracting lithium from lithium-containing ore according to claim 1, wherein the cooling is rapid cooling, and the cooling rate is 20-10 ℃/s.
8. The method for extracting lithium from lithium-containing ore according to claim 1, wherein the organic acid is at least one of oxalic acid and tartaric acid.
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| CN116262948A (en) * | 2023-04-17 | 2023-06-16 | 贵州大学 | Method for activating clay type lithium ore and extracting lithium ions |
| CN116287774A (en) * | 2023-01-03 | 2023-06-23 | 中南大学 | Biological extraction method of clay type lithium ore |
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| CN115608519A (en) * | 2022-04-02 | 2023-01-17 | 四川华澄科技有限公司 | Calcium-method vanadium extraction tailings flotation desulfurization collecting agent and preparation method thereof |
| CN116287774A (en) * | 2023-01-03 | 2023-06-23 | 中南大学 | Biological extraction method of clay type lithium ore |
| CN116397108A (en) * | 2023-03-28 | 2023-07-07 | 贵州大学 | Method for extracting lithium from lithium-containing ore |
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