CN115466854B - Comprehensive extraction method of lithium ore - Google Patents
Comprehensive extraction method of lithium ore Download PDFInfo
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- CN115466854B CN115466854B CN202211253569.XA CN202211253569A CN115466854B CN 115466854 B CN115466854 B CN 115466854B CN 202211253569 A CN202211253569 A CN 202211253569A CN 115466854 B CN115466854 B CN 115466854B
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- lithium
- iron
- silicate
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- slag
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 118
- 238000000605 extraction Methods 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 179
- 229910052742 iron Inorganic materials 0.000 claims abstract description 90
- 239000002893 slag Substances 0.000 claims abstract description 43
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 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 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052629 lepidolite Inorganic materials 0.000 claims abstract description 10
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 6
- 239000004575 stone Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 6
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 6
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052598 goethite Inorganic materials 0.000 claims description 5
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004110 Zinc silicate Substances 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 claims description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims description 2
- 235000019352 zinc silicate Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 238000001556 precipitation Methods 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004137 mechanical activation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052643 α-spodumene Inorganic materials 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the field of mineral processing, in particular to a comprehensive extraction method of lithium ores. The invention provides a comprehensive extraction method of lithium ores, which comprises the following steps: 1) Mixing lithium ore with silicate, ball milling, roasting, acid leaching, and filtering to obtain lithium-containing filtrate and silicon-rich slag; 2) Carrying out iron removal treatment on the lithium-containing filtrate to obtain a solution and iron slag after iron removal; 3) Mixing the solution after iron removal with carbonate, and precipitating lithium to obtain a lithium-containing compound; the lithium ore is at least one selected from spodumene, lepidolite and lithium porcelain stone. The lithium ore comprehensive extraction method provided by the invention has the advantages that the low-iron silicon slag with improved grade is obtained, and quartz in byproducts is comprehensively recovered; the grade of the silicon-rich slag is greatly improved and the content of iron in the silicon-rich slag is reduced while the excellent lithium extraction rate is obtained.
Description
Technical Field
The invention relates to the field of mineral processing, in particular to a comprehensive extraction method of lithium ores.
Background
The method is characterized in that the method comprises the steps of mixing the solid silicate lithium-containing ore with the salt lake brine type lithium ore, wherein the solid silicate lithium-containing ore is used as a main raw material for extracting lithium from the salt lake. How to develop and utilize the resources has important significance for the development of the lithium industry in China.
At present, spodumene and lepidolite are mainly used for extracting lithium from ores in industry, and different lithium extraction processes are developed for the spodumene and the lepidolite. The lithium extraction process using spodumene as a production raw material mainly comprises two types: the method has the advantages that the natural alpha spodumene is used as a production raw material to directly extract lithium, the production flow is short, a large amount of strong acid and strong alkali are needed to be used, the production cost is high, the pollution is large, and a large amount of reaction slag is generated and is difficult to treat. The other is that alpha spodumene is first converted into beta spodumene through high temperature roasting at 1000-1200 deg.c, and then beta spodumene is used as material for extracting lithium. The method for extracting lithium from lepidolite comprises a sulfate method, a high-pressure alkali boiling method, a sulfuric acid method, a chloride salt method, a mechanical activation method and the like, and is relatively less mature than the lithium extraction process of spodumene.
At present, the existing method realizes the effective extraction of lithium in lithium minerals, but the produced silicon slag has low grade, more iron can be remained, and the iron can not be piled as a byproduct, so that the resource waste is caused.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, although effective extraction of lithium can be realized, the produced silicon slag is low in grade and more iron can be remained, and further to provide a comprehensive extraction method of lithium ore.
The invention provides a comprehensive extraction method of lithium ores, which comprises the following steps:
1) Mixing lithium ore with silicate, ball milling, roasting, acid leaching, and filtering to obtain lithium-containing filtrate and silicon-rich slag;
2) Carrying out iron removal treatment on the lithium-containing filtrate to obtain a solution and iron slag after iron removal;
3) Mixing the solution after iron removal with carbonate, and precipitating lithium to obtain a lithium-containing compound;
the lithium ore is at least one selected from spodumene, lepidolite and lithium porcelain stone.
Preferably, the silicate is at least one selected from sodium silicate, potassium silicate, calcium silicate, magnesium silicate, aluminum silicate, iron silicate, ferrous silicate, zinc silicate, and manganese silicate;
the mass ratio of the lithium ore to the silicate is 1 (0.1-1).
Preferably, in the ball milling step in the step 1), the ball milling time is 0.1-2h, the ball milling rotating speed is 150-600r/min, and the particle size of the ball milled material is 200-400 meshes.
Preferably, the roasting temperature in the roasting step in the step 1) is 500-1200 ℃ and the time is 0.5-3.0h.
Preferably, in the acid leaching step of step 1), the roasted product calcine is immersed in an acid solution, wherein the acid solution comprises hydrochloric acid, and the concentration of the acid solution is 0.5-5.5mol/L.
Optionally, the acid solution and the calcine are added in a ratio of (1-6): 1, and the ratio unit is mL/g.
Preferably, the dipping temperature is 50-100 ℃, the dipping time is 0.5-2h, and the stirring speed is 200-400r/min.
Preferably, in step 2): regulating the pH value of the lithium-containing filtrate obtained in the step 1) to 0-3, adding ferrocyanide to remove iron, and filtering to obtain solution and iron slag after iron removal;
preferably, in the step 2), with respect to the content of iron ions in the lithium-containing filtrate, adding ferrocyanide with an excess coefficient of 1-1.2 for iron removal after regulating the pH value of the lithium-containing filtrate to 0-3, and filtering to obtain solution and iron slag after iron removal;
preferably, the temperature is kept at 20-50 ℃ for 0.5-2.0h in the iron removal process, and the stirring speed is 200-400r/min.
Preferably, the ferrocyanide is at least one selected from sodium ferrocyanide, potassium ferrocyanide and ammonium ferrocyanide.
Preferably, the molar ratio of lithium ions to carbonate in the solution after iron removal in step 3) is 1: (0.5-0.6), wherein the lithium deposition temperature is 90-100 ℃ and the lithium deposition time is 10-120min;
the carbonate salt includes sodium carbonate.
Preferably, the method further comprises the step of reacting the iron slag obtained in the step 2) with alkali liquor to obtain ferrocyanide solution and goethite;
the alkali in the alkali liquor is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water and calcium hydroxide, and the pH value of the reaction solution is 10-14; the adding proportion of alkali liquor and iron slag is (0.8-3): 1, the proportion unit is mL/g; the reaction temperature is 20-90 ℃, the reaction time is 0.5-2.0h, and the stirring speed is 200-400r/min.
The technical scheme of the invention has the following advantages:
the invention provides a comprehensive extraction method of lithium ores, which comprises the following steps: 1) Mixing lithium ore with silicate, ball milling, roasting, acid leaching, and filtering to obtain lithium-containing filtrate and silicon-rich slag; 2) Carrying out iron removal treatment on the lithium-containing filtrate to obtain a solution and iron slag after iron removal; 3) Mixing the solution after iron removal with carbonate, and precipitating lithium to obtain a lithium-containing compound; the lithium ore is at least one selected from spodumene, lepidolite and lithium porcelain stone.
According to the invention, the activities of the lithium ore and the silicate are obviously improved by ball milling after mixing the lithium ore and the silicate, then roasting is carried out, the silicon content in the lithium ore can be regulated and controlled by adding the silicate to promote mineral reconstruction of the lithium ore, lithium atoms in the lithium ore after activation roasting are replaced by cations in the silicate to form free lithium compounds, silicate radicals and Al, mn, zn, ca in the mineral form a high-silicon double-salt regenerated mineral phase, so that the phase combined with lithium in the lithium ore is reconstructed into a lithium silicate phase which is easy to acid leaching, and separation is carried out;
during the acid leaching, the iron is in Fe 3+ The form of the (2) is dissolved out and separated from the silicon slag to obtain low-iron silicon slag with improved grade, which is beneficial to comprehensively recovering quartz in byproducts; and then carrying out iron removal treatment and lithium precipitation on the lithium-containing filtrate, so that the grade of the silicon-rich slag is greatly improved and the content of iron in the silicon-rich slag is reduced while the excellent lithium extraction rate is obtained.
Furthermore, the method comprises the reaction step of the iron slag and the alkali liquor, so that ferrocyanide solution which can be used as the iron remover is obtained, the iron remover can be regenerated and recycled, and the economical efficiency and the environmental protection of the process are improved.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In examples and comparative examples, the extraction rate of lithium=the molar amount of lithium in the lithium-containing filtrate/the molar amount of lithium in the raw material×100%;
leaching rate of iron = molar amount of iron in lithium-containing filtrate/molar amount of iron in raw material x 100%;
iron removal = 100% -molar amount of iron in solution after iron removal/molar amount of iron in lithium-containing filtrate x 100%.
Example 1
The invention provides a comprehensive extraction method of lithium ores, which comprises the following steps:
1) Mixing 40g of lepidolite, 20g of lithium porcelain stone and 40g of sodium silicate, and then placing the mixture into a planetary ball mill for ball milling at a rotating speed of 300r/min for 0.2h for mechanical activation to obtain a mixed material with a particle size of 300 meshes; after ball milling, placing the mixed material into a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain calcine, immersing the calcine in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the temperature of 75 ℃ at the rotating speed of 300r/min, and filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 94.5%, the leaching rate of iron reaches 75%, the grade of silicon dioxide in the silicon-rich slag reaches 57.3%, and the iron content is 0.33%;
2) Adding NaOH solution to enable the pH value of the lithium-containing filtrate obtained in the step 1) to be 2, then adding sodium ferrocyanide with an excess coefficient of 1.05 to carry out iron removal reaction, keeping the temperature at 25 ℃ in the iron removal process, and stirring at 300r/min for 0.5h to obtain solution and iron slag after iron removal; wherein, the removal rate of iron in the filtrate containing lithium reaches 99.2 percent, and the concentration of lithium ions is not changed;
3) Adding sodium carbonate into the solution obtained in the step 2) after iron removal for lithium precipitation, wherein the molar ratio of lithium ions to sodium carbonate in the solution after iron removal is 1:0.55, the reaction temperature of lithium precipitation is 97 ℃, the reaction time is 0.4h, and the yield of lithium carbonate is 80.12 percent;
the comprehensive extraction method of the lithium ore further comprises the step of mixing the iron slag obtained in the step 2) with sodium hydroxide solution for reaction, wherein the pH value of the sodium hydroxide solution is 12, and the ratio of the sodium hydroxide solution to the iron slag is 1ml:1g, the reaction is carried out at a stirring rotation speed of 300r/min, the reaction temperature is 60 ℃, the reaction time is 0.5h, and the sodium ferrocyanide solution and goethite are obtained after the reaction.
Example 2
The invention provides a comprehensive extraction method of lithium ores, which comprises the following steps:
1) Mixing 25g of lepidolite, 25g of lithium porcelain stone and 50g of potassium silicate, and then placing the mixture into a planetary ball mill for ball milling at a rotating speed of 400r/min for 0.2h for mechanical activation to obtain a mixed material with a particle size of 300 meshes; after ball milling, placing the mixed material into a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain calcine, immersing the calcine in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the temperature of 75 ℃ at the rotating speed of 300r/min, and filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 95.5%, the leaching rate of iron reaches 68%, the grade of silicon dioxide in the silicon-rich slag reaches 60.5%, and the iron content is 0.44%;
2) Adding caustic alkali to enable the pH value of the lithium-containing filtrate obtained in the step 1) to be 2, then adding potassium ferrocyanide with an excess coefficient of 1.02 to carry out iron removal reaction, keeping the temperature at 25 ℃ in the iron removal process, and stirring at 300r/min for 0.5h to obtain solution and iron slag after iron removal; wherein, the removal rate of iron in the lithium-containing filtrate reaches 99 percent, and the concentration of lithium ions is not changed;
3) Adding sodium carbonate into the solution obtained in the step 2) after iron removal for lithium precipitation, wherein the molar ratio of lithium ions to sodium carbonate in the solution after iron removal is 1:0.55, the reaction temperature of lithium precipitation is 100 ℃, the reaction time is 0.3h, and lithium carbonate is obtained by reaction, and the yield of the lithium carbonate is 86.79%;
the comprehensive extraction method of the lithium ore further comprises the step of mixing the iron slag obtained in the step 2) with a potassium hydroxide solution for reaction, wherein the pH value of the potassium hydroxide solution is 12, and the ratio of the potassium hydroxide solution to the iron slag is 0.9ml:1g, the reaction is carried out at a stirring rotation speed of 300r/min, the reaction temperature is 80 ℃, the reaction time is 1h, and the potassium ferrocyanide solution and goethite are obtained after the reaction.
Example 3
The invention provides a comprehensive extraction method of lithium ores, which comprises the following steps:
1) Mixing 66.7g of lepidolite and 33.3g of potassium silicate, and placing the mixture into a planetary ball mill for ball milling at a rotating speed of 400r/min for 0.2h for mechanical activation to obtain a mixed material with a particle size of 300 meshes; after ball milling, placing the mixed material into a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain calcine, immersing the calcine in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the temperature of 75 ℃ at the rotating speed of 300r/min, and filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 95.5%, the leaching rate of iron reaches 77%, the grade of silicon dioxide in the silicon-rich slag reaches 63.3%, and the iron content is 0.32%;
2) Adding caustic alkali to enable the pH value of the lithium-containing filtrate obtained in the step 1) to be 3, then adding sodium ferrocyanide with an excess coefficient of 1.1 to carry out iron removal reaction, keeping the temperature at 20 ℃ in the iron removal process, and stirring at 300r/min for 1.5h to obtain solution and iron slag after iron removal; wherein, the removal rate of iron in the filtrate containing lithium reaches 99.5 percent, and the concentration of lithium ions is not changed;
3) Adding sodium carbonate into the solution obtained in the step 2) after iron removal for lithium precipitation, wherein the molar ratio of lithium ions to sodium carbonate in the solution after iron removal is 1:0.55, the reaction temperature of lithium precipitation is 98 ℃, the reaction time is 0.3h, and lithium carbonate is obtained by reaction, and the yield of the lithium carbonate is 82.62%;
the comprehensive extraction method of the lithium ore further comprises the step of mixing the iron slag obtained in the step 2) with sodium hydroxide solution for reaction, wherein the pH value of the sodium hydroxide solution is 14, and the ratio of the potassium hydroxide solution to the iron slag is 1ml:1g, the reaction is carried out at a stirring rotation speed of 300r/min, the reaction temperature is 80 ℃, the reaction time is 0.5h, and the sodium ferrocyanide solution and goethite are obtained after the reaction.
Comparative example 1
This comparative example provides a comprehensive extraction method of lithium ore, which is different from example 1 in that sodium silicate is not added in step 1); the grade of silicon dioxide in the silicon-rich slag is 51.09%, and the iron content is 0.67%; the yield of lithium carbonate prepared in step 3) was 79.72%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (11)
1. The comprehensive extraction method of the lithium ore is characterized by comprising the following steps:
1) Mixing lithium ore with silicate, ball milling, roasting, acid leaching, and filtering to obtain lithium-containing filtrate and silicon-rich slag;
2) Carrying out iron removal treatment on the lithium-containing filtrate to obtain a solution and iron slag after iron removal;
3) Mixing the solution after iron removal with carbonate, and precipitating lithium to obtain a lithium-containing compound;
the lithium ore is at least one selected from spodumene, lepidolite and lithium porcelain stone;
the silicate is at least one selected from sodium silicate, potassium silicate, calcium silicate, magnesium silicate, aluminum silicate, ferric silicate, ferrous silicate, zinc silicate and manganese silicate;
the mass ratio of the lithium ore to the silicate is 1 (0.1-1).
2. The method for comprehensively extracting lithium ore according to claim 1, wherein in the ball milling step of the step 1), the ball milling time is 0.1-2h, the ball milling rotating speed is 150-600r/min, and the particle size of the ball milled material is 200-400 meshes.
3. The method for the comprehensive extraction of lithium ores according to claim 1, wherein the roasting temperature in the roasting step of step 1) is 500-1200 ℃ and the time is 0.5-3.0h.
4. The method for the integrated extraction of lithium ores according to claim 1, wherein the roasting product calcine in the acid leaching step in the step 1) is immersed in an acid solution, the acid solution comprises hydrochloric acid, and the concentration of the acid solution is 0.5-5.5mol/L.
5. The method for the comprehensive extraction of lithium ores according to claim 4, wherein the impregnation temperature is 50-100 ℃, the impregnation time is 0.5-2h, and the stirring speed is 200-400r/min.
6. The method for the integrated extraction of lithium ores according to claim 1, wherein in step 2): regulating the pH value of the lithium-containing filtrate obtained in the step 1) to 0-3, adding ferrocyanide to remove iron, and filtering to obtain solution and iron slag after iron removal.
7. The method for the integrated extraction of lithium ores according to claim 1, wherein in the step 2), ferrocyanide with an excess coefficient of 1-1.2 is added for iron removal after the pH value of the lithium-containing filtrate is regulated to 0-3 relative to the content of iron ions in the lithium-containing filtrate, and the solution and the iron slag after iron removal are obtained through filtration.
8. The method for the integrated extraction of lithium ores according to claim 7, wherein the temperature is maintained at 20-50 ℃ for 0.5-2.0h during the iron removal process, and the stirring speed is 200-400r/min.
9. The method for the integrated extraction of lithium ore according to claim 6, wherein the ferrocyanide is at least one selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide and ammonium ferrocyanide.
10. The method for the integrated extraction of lithium ore according to claim 1, wherein,
the molar ratio of lithium ions to carbonate in the solution after iron removal in step 3) is 1: (0.5-0.6), wherein the lithium deposition temperature is 90-100 ℃, and the lithium deposition time is 10-120min;
the carbonate salt includes sodium carbonate.
11. The method for the comprehensive extraction of lithium ores according to claim 6, further comprising reacting the iron slag obtained in the step 2) with an alkali solution to obtain a ferrocyanide solution and goethite;
the alkali in the alkali liquor is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia water and calcium hydroxide, and the pH value of the reaction solution is 10-14; the adding proportion of alkali liquor and iron slag is (0.8-3): 1, the proportion unit is mL/g; the reaction temperature is 20-90 ℃, the reaction time is 0.5-2.0h, and the stirring speed is 200-400r/min.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB530028A (en) * | 1938-06-22 | 1940-12-03 | Bolidens Gruv Ab | Method of recovering lithium from minerals |
| US3380802A (en) * | 1963-09-30 | 1968-04-30 | Mini Richesses Nature | Carbonatizing roast of lithiumbearing ores |
| CN102690961A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Method for directly extracting lithium by utilizing low-grade alpha-spodumene as raw material |
| CN103320626A (en) * | 2013-06-18 | 2013-09-25 | 赣州有色冶金研究所 | Method and system for recovering lithium, rubidium and/or cesium from lepidolite |
| CN103950956A (en) * | 2014-05-22 | 2014-07-30 | 甘孜州泸兴锂业有限公司 | Process for producing lithium carbonate from spodumene concentrate by sulfuric acid method |
| CN105838895A (en) * | 2016-05-16 | 2016-08-10 | 长沙矿冶研究院有限责任公司 | Method for extracting lithium and manganese from lithium-containing manganese-rich slag |
| CN106591564A (en) * | 2016-12-05 | 2017-04-26 | 天津二八科技股份有限公司 | Roasting additive |
| CN107475537A (en) * | 2017-07-17 | 2017-12-15 | 江西南氏锂电新材料有限公司 | Lithium, rubidium, the method for cesium salt are extracted from lepidolite raw material |
| CN108101077A (en) * | 2017-12-28 | 2018-06-01 | 中国地质科学院矿产综合利用研究所 | Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer |
| CN108277367A (en) * | 2017-01-06 | 2018-07-13 | 中国科学院过程工程研究所 | A method of carrying lithium from containing lithium ore |
| CN108431253A (en) * | 2015-12-22 | 2018-08-21 | 理查德.亨威克 | Lithium is collected from silicate mineral |
| CN110396610A (en) * | 2019-07-29 | 2019-11-01 | 中国科学院过程工程研究所 | A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral |
| CN110526250A (en) * | 2019-09-27 | 2019-12-03 | 福州大学 | A kind of silicates acid system containing lithium ore directly proposes the method for comprehensive utilization of lithium |
| CN110885090A (en) * | 2019-12-31 | 2020-03-17 | 江西南氏锂电新材料有限公司 | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method |
| KR20200069054A (en) * | 2018-12-06 | 2020-06-16 | 주식회사 에코프로이노베이션 | Preparation method of lithium hydroxide from lithium concentration by calcination with sodium sulfate |
| CN113174480A (en) * | 2021-04-02 | 2021-07-27 | 北京科技大学 | Method for extracting lithium, rubidium and cesium from lithium, rubidium and cesium-containing silicate minerals |
| WO2022126053A2 (en) * | 2020-11-04 | 2022-06-16 | Basf Corporation | Methods of obtaining water for downstream processes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017136328A1 (en) * | 2016-02-01 | 2017-08-10 | Northwestern University | Compounds for lithium extraction via ion exchange |
| CA3143966C (en) * | 2019-06-21 | 2023-12-12 | Xerion Advanced Battery Corp. | Methods for extracting lithium from spodumene |
| JP2023529444A (en) * | 2020-06-09 | 2023-07-10 | ライラック ソリューションズ，インク． | Lithium extraction in presence of scale material |
-
2022
- 2022-10-13 CN CN202211253569.XA patent/CN115466854B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB530028A (en) * | 1938-06-22 | 1940-12-03 | Bolidens Gruv Ab | Method of recovering lithium from minerals |
| US3380802A (en) * | 1963-09-30 | 1968-04-30 | Mini Richesses Nature | Carbonatizing roast of lithiumbearing ores |
| CN102690961A (en) * | 2012-06-28 | 2012-09-26 | 贵州开磷（集团）有限责任公司 | Method for directly extracting lithium by utilizing low-grade alpha-spodumene as raw material |
| CN103320626A (en) * | 2013-06-18 | 2013-09-25 | 赣州有色冶金研究所 | Method and system for recovering lithium, rubidium and/or cesium from lepidolite |
| CN103950956A (en) * | 2014-05-22 | 2014-07-30 | 甘孜州泸兴锂业有限公司 | Process for producing lithium carbonate from spodumene concentrate by sulfuric acid method |
| CN108431253A (en) * | 2015-12-22 | 2018-08-21 | 理查德.亨威克 | Lithium is collected from silicate mineral |
| CN105838895A (en) * | 2016-05-16 | 2016-08-10 | 长沙矿冶研究院有限责任公司 | Method for extracting lithium and manganese from lithium-containing manganese-rich slag |
| CN106591564A (en) * | 2016-12-05 | 2017-04-26 | 天津二八科技股份有限公司 | Roasting additive |
| CN108277367A (en) * | 2017-01-06 | 2018-07-13 | 中国科学院过程工程研究所 | A method of carrying lithium from containing lithium ore |
| CN107475537A (en) * | 2017-07-17 | 2017-12-15 | 江西南氏锂电新材料有限公司 | Lithium, rubidium, the method for cesium salt are extracted from lepidolite raw material |
| CN108101077A (en) * | 2017-12-28 | 2018-06-01 | 中国地质科学院矿产综合利用研究所 | Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer |
| KR20200069054A (en) * | 2018-12-06 | 2020-06-16 | 주식회사 에코프로이노베이션 | Preparation method of lithium hydroxide from lithium concentration by calcination with sodium sulfate |
| CN110396610A (en) * | 2019-07-29 | 2019-11-01 | 中国科学院过程工程研究所 | A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral |
| CN110526250A (en) * | 2019-09-27 | 2019-12-03 | 福州大学 | A kind of silicates acid system containing lithium ore directly proposes the method for comprehensive utilization of lithium |
| CN110885090A (en) * | 2019-12-31 | 2020-03-17 | 江西南氏锂电新材料有限公司 | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method |
| WO2022126053A2 (en) * | 2020-11-04 | 2022-06-16 | Basf Corporation | Methods of obtaining water for downstream processes |
| CN113174480A (en) * | 2021-04-02 | 2021-07-27 | 北京科技大学 | Method for extracting lithium, rubidium and cesium from lithium, rubidium and cesium-containing silicate minerals |
Non-Patent Citations (3)
| Title |
|---|
| Processing of lithium ores: Industrial technologies and case studies – A review;Dmytro Yelatontsev等;《Hydrometallurgy》;第201卷;全文 * |
| 典型锂矿石提锂技术研究进展;田键等;《湖北大学学报》;第42卷(第01期);全文 * |
| 矿石资源中锂的提取与回收研究进展;苏慧等;《化工学报》;第70卷(第01期);全文 * |
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