CN116497235A - Method for extracting lithium from low-lithium clay - Google Patents
Method for extracting lithium from low-lithium clay Download PDFInfo
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- CN116497235A CN116497235A CN202310466226.XA CN202310466226A CN116497235A CN 116497235 A CN116497235 A CN 116497235A CN 202310466226 A CN202310466226 A CN 202310466226A CN 116497235 A CN116497235 A CN 116497235A
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- lithium
- roasting
- leaching
- low
- clay
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 143
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000004927 clay Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 134
- 238000002386 leaching Methods 0.000 claims abstract description 105
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 10
- 235000019738 Limestone Nutrition 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 5
- 239000006028 limestone Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000010891 electric arc Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 24
- 238000000605 extraction Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000010413 mother solution Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002585 base Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- -1 and firstly Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 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
- C01D15/02—Oxides; Hydroxides
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- 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
-
- 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 invention discloses a method for extracting lithium from low-lithium clay, which comprises the following steps: crushing the low-lithium clay raw ore by using a crusher to obtain powdery crushed materials, soaking the crushed materials to obtain soaked materials, placing the soaked materials into a fluidized bed furnace for chloridizing roasting to obtain primary roasting materials, introducing the primary roasting materials and additives into an electric arc heater for roasting to obtain secondary roasting materials, leaching the secondary roasting materials at a constant pressure, filtering to obtain leaching liquid and leaching slag, and removing impurities, concentrating, crystallizing and synthesizing the leaching liquid to obtain lithium hydroxide. The method solves the problem of higher price of potassium sulfate in the sulfate process in the traditional process, and can also avoid the problems of large limestone consumption, lower lithium recovery rate and difficult recycling of the roasted slag in the limestone process.
Description
Technical Field
The invention belongs to the field of metallurgical production of lithium ore lithium extraction technology, and particularly relates to a method for extracting lithium from low-lithium clay.
Background
There are two main methods for preparing high purity lithium products: lithium ore extraction and salt lake extraction. The share of the lithium extraction yield of the salt lake is always lower, and the salt lake is limited by the following two aspects: (1) the salt lake of China is concentrated on Qinghai-Tibet plateau, and the region has high altitude, severe climatic conditions and inconvenient traffic. (2) Gao Limei is still in the stage of preliminary exploration compared to brine extraction techniques. Therefore, lithium extraction from ores still takes the dominant role, however, lithium ore resources are limited, and the disadvantages of grade reduction and resource exhaustion are necessarily faced in the future. Thus, the lithium clay extraction technology has become a research hotspot.
At present, the lithium extraction method and research of the lithium-containing clay are less, the chemical components and the tissue structures of the lithium clay are different from those of spodumene and lepidolite, the lithium in the clay ore is mainly stored in the clay mineral, the lithium content of the lithium-containing clay is lower than that of the spodumene lepidolite, the tissue components are more complex, and the lithium-containing clay is not suitable for directly adopting the conventional lithium ore lithium extraction process. Aiming at the recovery of lithium in lithium clay, for example, patent CN114684834A discloses a clay type lithium ore lithium extraction method, which comprises the steps of mixing and roasting lithium clay with sodium carbonate and sodium sulfate, grinding and leaching, wherein the method is used for alkaline corrosion of equipment, needs a large amount of sodium silicate and sodium aluminate to remove silicon aluminum, and has high cost; patent CN111893318A discloses a method for extracting lithium from lithium-containing clay, which adopts a sulfate roasting method, prepares spherical materials after mixing lithium clay and sulfate, and then roasting, crushing and leaching the spherical materials, wherein the method generates a large amount of calcium-silicon waste residues which are difficult to treat, and the content of lithium oxide in the residues reaches 0.2 percent, so that the method is only suitable for clay ores with higher lithium oxide grade; patent CN113955775a discloses a method for extracting lithium carbonate from lithium-rich clay by an acid-base combination method, which comprises the steps of adding a sulfuric acid solution with a certain concentration into the lithium-rich clay for leaching, adding a sodium hydroxide solution into acid leaching residues for alkali leaching, and introducing carbon dioxide gas into the alkali leaching solution to obtain lithium carbonate solid and carbon mother liquor, wherein acid mist is easy to generate by using strong acid, equipment is easy to corrode, and the consumption of acid-base combination resource is relatively large; patent CN115161496a discloses a method for extracting lithium from lithium clay, roasting lithium clay powder, leaching a roasted clinker after grinding, and carrying out solid-liquid separation to obtain a lithium-containing solution and leaching residues, wherein the leaching agent is specifically defined as sodium hydroxide, potassium hydroxide, sodium strong acid salt or potassium strong acid salt, so as to obtain a lithium-rich solution; patent CN114959253a discloses a method for extracting lithium from lithium clay, after pretreating the lithium clay, performing microwave roasting, heat preservation, cooling and grinding to obtain a crushed material, limiting specific conditions of microwave roasting, and then leaching to obtain a lithium-containing leaching solution, wherein the heating equipment of the method is complex, special customization is required, the cost is high, and the capacities of different mediums for absorbing microwaves and the microwave coupling are different; patent CN115287469a discloses a method for selectively extracting lithium from clay-type lithium ores, which comprises the steps of mixing lithium-rich clay powder with a lithium ion exchange solution to prepare slurry, wherein the lithium ion exchange solution is a chloride salt metal solution, then carrying out ultrasonic enhanced leaching reaction, and separating to obtain a lithium extracting solution and filter residues; the lithium extraction solution is extracted, back extracted and deoiled to obtain a lithium chloride refined solution, and the method has no universality and poor selectivity effect on low-lithium clay ores.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for efficiently extracting lithium from low-lithium clay.
The invention is realized by the following technical scheme.
A method for extracting lithium from low-lithium clay, comprising the following steps:
(1) Crushing the low-lithium clay raw ore with the lithium content of 0.10-0.20% by using a crusher to obtain crushed materials;
(2) Soaking the crushed material obtained in the step (1) to obtain a soaked material;
(3) Placing the soaked material obtained in the step (2) into a fluidized bed furnace for chloridizing roasting to obtain a first-stage roasting material;
(4) Introducing the first-stage roasting material and the additive obtained in the step (3) into an arc heater for roasting to obtain a second-stage roasting material;
(5) Mixing the second-stage roasting material obtained in the step (4) with a leaching agent, leaching under normal pressure, and filtering to obtain leaching liquid and leaching slag;
(6) Removing impurities from the obtained leaching solution, concentrating and crystallizing, and synthesizing to obtain lithium hydroxide, wherein the mother solution of the concentrating and crystallizing is recycled to the normal pressure leaching process.
Further, in the step (1), the low-lithium clay raw ore is crushed to 100-200 meshes by a crusher, and preferably, the low-lithium clay raw ore is crushed to 150-200 meshes.
Further, in the step (2), the crushed material is soaked in weak acid, the weak acid is one or a combination of oxalic acid, acetic acid, carbonic acid and silicic acid, the mass ratio of the crushed material to the weak acid is 1:1-4, and the volume concentration of the weak acid is 30-55%.
Wherein, weak acid such as oxalic acid is used for pretreatment of the lithium clay, and firstly, magnesium, potassium, sodium and the like in the lithium clay can leach out a part, and aluminum can not be leached out.
Further, in the step (2), the weak acid is oxalic acid, the volume concentration is 30-55%, preferably, the volume concentration of oxalic acid is 45%, and the mass ratio of the crushed material to oxalic acid is 1:1-2.
Further, in the step (3), the soaking material is put into a fluidized bed furnace for low-temperature chlorination roasting, wherein the chlorination roasting temperature is 300-450 ℃, preferably 400 ℃, and when the roasting temperature reaches 100-120 ℃, chlorine is introduced, the chlorine flow is 20-30mL/s, and the roasting time is 1-3h.
Boiling low-temperature chloridizing roasting: treating the soaked material in a boiling furnace, slowly heating and drying to 100-120 ℃, introducing chlorine to participate in the reaction to form boiling chlorination roasting, and forming multi-component chloride in the step, wherein the chemical bonds of minerals are broken or recombined, and the chemical structure is greatly changed to form a compound which is easier to treat.
Further, in the step (4), a section of roasting material and additives are fed into an arc heater for high-temperature roasting, wherein the working power of the arc heater is 15-30KW, and preferably, the working power is 20-25KW; the heating temperature of the arc heater is 1100-1900 ℃, preferably 1500 ℃.
In the step (4), the temperature can be changed greatly in a very short time under the action of an electric arc, and Li is contained in the process of changing the temperature greatly + The bond is broken, and the metal cation added into the additive replaces Li + Original position, thereby displacing Li + And new compounds are formed.
Further, in the step (4), the additive is one or a combination of more of sodium carbonate, potassium carbonate, sodium chloride, potassium chloride, sodium sulfate and potassium sulfate, the mass ratio of the primary roasting material to the additive is 10:0.2-2, and the mass ratio of the primary roasting material to the additive is preferably 10:0.8-1.2.
Further, in the step (4), the additive is sodium carbonate, and the mass ratio of the primary roasting material to the sodium carbonate is 10:0.8-1.2.
Further, in the step (5), the liquid-solid ratio of the leaching agent to the secondary roasting material in the leaching process is 5-1:1ml/g, preferably 3:1ml/g.
Further, the leaching process uses pure water as a leaching agent.
Further, the concentrated crystallized mother liquor is returned to the leaching process in the step (5).
The beneficial technical effects of the invention are as follows:
the invention adopts a combined process of a fire method and a wet method for smelting, and realizes the high-efficiency extraction of the low-lithium clay based on two-stage reaction of low-temperature chloridizing roasting of a fluidized bed furnace and high-temperature roasting of an electric arc heater. Firstly, the low-lithium clay is soaked in weak acid for mineral, acidizing materials plays a role of pretreatment, and firstly, magnesium, potassium, sodium and other ions are removed to a part, and aluminum is not dissolved out. SecondIntroducing the acidified material into a fluidized bed furnace for low-temperature chlorination roasting, forming multicomponent chloride in this step, breaking or recombining mineral chemical bonds, greatly changing chemical structure to form easier-to-handle compound, introducing the low-temperature one-stage roasting material and additive such as sodium carbonate into an arc heater, under the action of electric arc, the temperature can be changed greatly in a short time, and explosion emits great energy, so that the crystal lattice of lithium clay ore is changed, li + The bond in clay mineral is broken, na in additive + Substituted Li + In the former position, lithium is dissolved out by the action of a leaching agent such as pure water.
The method for efficiently extracting lithium from the low-lithium clay has extremely high leaching rate and recovery rate, can solve the problem of higher price of potassium sulfate in the sulfate method, can avoid the problems of large consumption of limestone, lower recovery rate of lithium, difficult recovery and the like in the limestone method, has the advantages of 95 percent of lithium extraction rate, simple process, wide applicability, unique structure and performance suitable for lithium clay, less investment, high return, high safety and environmental friendliness compared with the sulfuric acid method, the limestone method and the sulfate method adopted for extracting lithium from other ores.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed materials, adding 800ml of oxalic acid with the volume concentration of 45%, and adding the oxalic acid and the crushed materials in a mass ratio of 1:1 for soaking to obtain soaked materials;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 400 ℃, and when the roasting temperature reaches 100 ℃, introducing chlorine, wherein the flow rate of the chlorine is 20-25mL/S, and the roasting time is 1h, so as to obtain a first-stage roasted material;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium carbonate into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 25KW, the ratio of the primary roasting material to sodium carbonate is 10:1, and the roasting temperature is 1100 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating and crystallizing, adding calcium hydroxide, synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Example 2
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed materials, adding 1600ml of 35% acetic acid with the volume concentration, and adding the crushed materials into the crushed materials for soaking to obtain soaked materials, wherein the mass ratio of the acetic acid to the crushed materials is 2:1;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 450 ℃, and when the roasting temperature reaches 110 ℃, introducing chlorine, wherein the chlorine flow is 25-30mL/S, and the roasting time is 1.5h, so as to obtain a first-stage roasted material;
s4: introducing the primary roasting material obtained in the step S3 and potassium carbonate into an arc heater for roasting to obtain a secondary roasting material; the working power of the arc heater is 25KW, the ratio of the primary roasting material to the potassium carbonate is 10:1.5, and the roasting temperature is 1300 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 5:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Example 3
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed materials, adding 2400ml of carbonic acid with the volume concentration of 30%, and adding the carbonic acid into the crushed materials for soaking, wherein the mass ratio of the carbonic acid to the crushed materials is 3:1, so as to obtain soaked materials;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 350 ℃, and when the roasting temperature reaches 120 ℃, chlorine is introduced, the flow rate of the chlorine is 20-30mL/S, and the roasting time is 2 hours, so that a first-stage roasted material is obtained;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium sulfate into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 20KW, the ratio of the primary roasting material to sodium sulfate is 10:1.2, and the roasting temperature is 1500 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 1:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Example 4
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed material, adding 2400ml of silicic acid with the volume concentration of 50%, and adding the silicic acid and the crushed material in a mass ratio of 3:1 for soaking to obtain a soaked material;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 450 ℃, and when the roasting temperature reaches 100 ℃, introducing chlorine with the chlorine flow of 20-30mL/S and the roasting time of 2.5h, so as to obtain a first-stage roasted material;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium chloride into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 20KW, the ratio of the primary roasting material to sodium chloride is 10:0.8, and the roasting temperature is 1700 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Example 5
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed materials, adding 800ml of mixed acid (mixed by oxalic acid and carbonic acid in the same ratio) with the volume concentration of 45%, and adding the mixed acid and the crushed materials in the mass ratio of 1:1 for soaking to obtain soaked materials;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 450 ℃, and when the roasting temperature reaches 100 ℃, introducing chlorine, wherein the flow rate of the chlorine is 20-30mL/S, and the roasting time is 1h, so as to obtain a first-stage roasted material;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium carbonate into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 20KW, the ratio of the primary roasting material to sodium carbonate is 10:1, and the roasting temperature is 1800 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Example 6
Referring to fig. 1, a method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain 800ml of crushed material, adding oxalic acid with the volume concentration of 45% and the mass ratio of oxalic acid to crushed material of 1:1, and soaking to obtain soaked material;
s3: chloridizing and roasting the soaked material obtained in the step S2 in a fluidized bed furnace, wherein the roasting temperature is 450 ℃, and when the roasting temperature reaches 100 ℃, introducing chlorine, wherein the flow rate of the chlorine is 20-30mL/S, and the roasting time is 1h, so as to obtain a first-stage roasted material;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium carbonate into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 20KW, the ratio of the primary roasting material to the mixed additive (mixed by sodium carbonate and potassium carbonate in equal ratio) is 10:1, and the roasting temperature is 1600 ℃;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Comparative example 1
A method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: placing the crushed material obtained in the step S1 into boiling chlorination roasting, wherein the roasting temperature is 450 ℃, introducing chlorine gas when the roasting temperature reaches 100 ℃, and the flow rate of the chlorine gas is 20-30mL/S, and the roasting time is 1h, so as to obtain a first-stage roasting material;
s3: feeding the primary roasting material obtained in the step S2 and sodium carbonate into an arc heater for roasting to obtain a secondary roasting material; the working power of the arc heater is 20KW, and the ratio of the primary roasting material to sodium carbonate is 10:1;
s4: mixing the S3 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s5: and (3) removing impurities from the leaching solution obtained in the step (S4), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Comparative example 2
A method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing the S1 to obtain crushed materials, adding 800ml of 45% oxalic acid for soaking, and adding the oxalic acid and the crushed materials for soaking in a mass ratio of 1:1 to obtain soaked materials;
s3: placing the soaked material obtained in the step S2 into boiling chlorination roasting, wherein the roasting temperature is 450 ℃, introducing chlorine gas when the roasting temperature reaches 100 ℃, and the flow rate of the chlorine gas is 20-30mL/S, and the roasting time is 1h, so as to obtain a first-stage roasting material;
s4: introducing the first-stage roasting material obtained in the step S3 and sodium carbonate into an arc heater for roasting to obtain a second-stage roasting material; the working power of the arc heater is 20KW;
s5: mixing the S4 two-stage roasting material with pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s6: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
Comparative example 3
A method for efficiently extracting lithium from low-lithium clay comprises the following specific embodiments:
s1: crushing 800g of lithium clay raw material by using a crusher to 150-200 meshes to obtain crushed materials;
s2: crushing S1 to obtain crushed materials, adding 800ml of oxalic acid with the volume concentration of 45%, and adding the oxalic acid and the crushed materials in a mass ratio of 1:1 for soaking to obtain soaked materials;
s3: mixing the soaked material and pure water according to a liquid-solid ratio of 3:1, leaching at normal temperature, and filtering after leaching to obtain leaching liquid and leaching slag;
s4: and (3) removing impurities from the leaching solution obtained in the step (S5), concentrating, crystallizing and synthesizing to obtain lithium hydroxide, and recycling the mother solution of the concentrating and crystallizing to normal temperature for leaching.
The components of the lithium clay, leaching residues and leaching liquid are detected by an atomic absorption spectrophotometer according to national standard GB/T15337-2008. Wherein lithium leaching rate = (volume of leaching solution containing lithium)/(lithium concentration in leaching solution)/(mass of lithium clay) percent of lithium in lithium clay), wherein lithium content in lithium clay is 0.15%.
As can be seen from the table, the method for extracting lithium from lithium clay adopts the arc heater to extract lithium from clay-type lithium resources, and the method can generate instant high temperature to enable ions to be rapidly exchanged, and finally the leaching rate of lithium is more than 95%. As is evident from comparison of example 1 and example 2, the chloridizing roasting temperature is slightly better at 450 ℃, and the leaching rate of lithium is 96.82%. In example 3, the power of the arc heater was 20-25KW, and the result showed that the leaching effect of lithium was good at 20KW, and the leaching rate of lithium was 98.54%.
Comparative example 1 did not use weak acid to soak, and the material was directly subjected to boiling low-temperature chloridizing roasting, the leaching rate of lithium was 64.37%, which is significantly lower than that of example lithium. In comparative example 2, sodium carbonate is not added, the sodium carbonate directly enters an arc heater, and then leaching is carried out according to a liquid-solid ratio of 3:1, so that the leaching rate of lithium is only 55.62%, and part of lithium ions in comparative example 2 are not replaced, which indicates that sodium carbonate can be exchanged with lithium ions in the arc heater, so that the leaching rate is improved. Comparative example 3 was found to have a leaching effect inferior to that of example 3 in that low-temperature chlorination firing and arc high-temperature firing were not performed, and the leaching rate was only 15.99%.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.
Claims (10)
1. A method for extracting lithium from low-lithium clay, which is characterized by comprising the following steps:
(1) Crushing the low-lithium clay raw ore to obtain crushed materials;
(2) Soaking the crushed material obtained in the step (1) to obtain a soaked material;
(3) Chloridizing and roasting the soaked material obtained in the step (2) to obtain a first-stage roasting material;
(4) Roasting the first-stage roasting material obtained in the step (3) and the additive to obtain a second-stage roasting material;
(5) Leaching the second-stage roasting material obtained in the step (4), and filtering to obtain leaching liquid and leaching slag;
(6) And synthesizing the obtained leaching solution to obtain lithium hydroxide.
2. The method for extracting lithium from low-lithium clay according to claim 1, wherein the lithium content in the low-lithium clay raw ore is 0.10 to 0.20%.
3. The method for extracting lithium from low-lithium clay according to claim 1, wherein the low-lithium clay raw ore in step (1) is crushed to 100-200 mesh, preferably to 150-200 mesh, by using a crusher.
4. The method for extracting lithium from low-lithium clay according to claim 1, wherein in the step (2), broken materials are soaked in weak acid, the weak acid is one or a combination of oxalic acid, acetic acid, carbonic acid and silicic acid, the mass ratio of the broken materials to the weak acid is 1:1-4, and the volume concentration of the weak acid is 30-55%.
5. The method for extracting lithium from low-lithium clay according to claim 4, wherein the weak acid is oxalic acid, a volume concentration is 30-55%, and a mass ratio of crushed material to oxalic acid is 1:1-2.
6. The method for extracting lithium from low-lithium clay according to claim 1, wherein in the step (3), low-temperature chlorination roasting is adopted, wherein the low-temperature chlorination roasting is carried out by putting soaked materials into a fluidized bed furnace, introducing chlorine when the roasting temperature reaches 100-120 ℃, wherein the chlorine flow is 20-30mL/s, the roasting temperature is 300-450 ℃, and the roasting time is 1-3h.
7. The method for extracting lithium from low-lithium clay according to claim 1, wherein in the step (4), a section of roasting material and an additive are roasted at a high temperature, an arc heater is adopted as equipment for the high-temperature roasting, the working power of the arc heater is 15-30KW, the working power is preferably 20-25KW, and the heating temperature is 1100-1900 ℃.
8. The method for extracting lithium from low-lithium clay according to claim 1, wherein in the step (4), the additive is one or more of sodium carbonate, potassium carbonate, sodium chloride, potassium chloride, sodium sulfate and potassium sulfate, the mass ratio of the primary roasting material to the additive is 10:0.2-2, and preferably the mass ratio of the primary roasting material to the additive is 10:0.8-1.2.
9. The method for extracting lithium from low-lithium clay according to claim 8, wherein the additive is sodium carbonate, and the mass ratio of the primary roasting material to the sodium carbonate is 10:0.8-1.2.
10. The method for extracting lithium from low-lithium clay according to claim 1, wherein in the leaching process in the step (5), a liquid-solid ratio of a leaching agent to a two-stage roasting material is 5-1:1ml/g, and the leaching agent is pure water.
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| CN117025977B (en) * | 2023-10-10 | 2023-12-29 | 矿冶科技集团有限公司 | Method for extracting lithium from phosphorus-containing clay-type lithium ore |
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