CN115466854A - Comprehensive extraction method for lithium ore - Google Patents
Comprehensive extraction method for lithium ore Download PDFInfo
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- CN115466854A CN115466854A CN202211253569.XA CN202211253569A CN115466854A CN 115466854 A CN115466854 A CN 115466854A CN 202211253569 A CN202211253569 A CN 202211253569A CN 115466854 A CN115466854 A CN 115466854A
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- China
- Prior art keywords
- lithium
- iron
- silicate
- solution
- slag
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 124
- 238000000605 extraction Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 163
- 229910052742 iron Inorganic materials 0.000 claims abstract description 82
- 239000002893 slag Substances 0.000 claims abstract description 45
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 14
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 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 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 12
- 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
- 239000000047 product Substances 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
- 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
- 230000008021 deposition Effects 0.000 claims description 5
- 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
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 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
- 230000001105 regulatory effect Effects 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
- 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
- 230000001276 controlling effect Effects 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
- 238000005470 impregnation Methods 0.000 claims 2
- MIQKWQQWHUBLIM-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Mn+2].[Zn+2] Chemical compound [Si]([O-])([O-])([O-])[O-].[Mn+2].[Zn+2] MIQKWQQWHUBLIM-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 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
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide 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
- 239000012267 brine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 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
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Classifications
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- 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 ore. The invention provides a comprehensive extraction method of lithium ore, which comprises the following steps: 1) Mixing lithium ore and 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 an iron-removed solution and iron slag; 3) Mixing the solution after iron removal and carbonate, and then precipitating lithium to obtain a lithium-containing compound; the lithium ore Dan Xuanzi is at least one of spodumene, lepidolite and lithium porcelain stone. The comprehensive extraction method for lithium ore provided by the invention can be used for obtaining the low-iron silicon slag with improved grade, and is beneficial to comprehensively recovering quartz in byproducts; the grade of the silicon-rich slag is greatly improved while the excellent lithium extraction rate is obtained, and the content of iron in the silicon-rich slag is reduced.
Description
Technical Field
The invention relates to the field of mineral processing, in particular to a comprehensive extraction method of lithium ore.
Background
The lithium resource is a large country of lithium resources, the lithium resource exists in solid silicate lithium-containing ores and salt lake brine lithium ores, the geographical location of lithium-containing salt lakes in the salt lake brine lithium ores in China is remote, the altitude is high, the effective development time is short, the magnesium-lithium ratio of the salt lake brine lithium ores in the lithium-containing salt lakes is high, and the separation is difficult, so the solid silicate lithium-containing ores become the main raw materials for extracting lithium in China. 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 aiming at the spodumene and the lepidolite. The lithium extraction process using spodumene as a production raw material mainly comprises two types: one kind of method is to directly extract lithium by using natural alpha spodumene as a production raw material, and the method has short production flow, but needs to use a large amount of strong acid and strong alkali, has higher production cost and large pollution, and also generates a large amount of reaction slag which is difficult to treat. The other is that alpha spodumene is first high temperature roasted to convert into beta spodumene 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 soda boiling method, a sulfuric acid method, a chloride method, a mechanical activation method and the like, and is underdeveloped relative to 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 silicon slag can not be piled up as a byproduct, thereby causing resource waste.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that in the prior art, although effective extraction of lithium can be realized, the produced silica slag has low grade and can leave more iron, and further provides a comprehensive extraction method of lithium ore.
The invention provides a comprehensive extraction method of lithium ore, which comprises the following steps:
1) Mixing lithium ore and silicate, performing 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 an iron-removed solution and iron slag;
3) Mixing the solution after iron removal and carbonate, and then precipitating lithium to obtain a lithium-containing compound;
the lithium ore Dan Xuanzi is at least one of spodumene, lepidolite and lithium porcelain stone.
Preferably, the silicate is selected from at least one of 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 of the step 1) is 500-1200 ℃, and the time is 0.5-3.0h.
Preferably, in the acid leaching step in step 1), the roasted product calcine 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.
Optionally, the adding ratio of the acid solution to the calcine is (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 and controlling the pH value of the lithium-containing filtrate obtained in the step 1) to 0-3, then adding ferrocyanide to remove iron, and filtering to obtain an iron-removed solution and iron slag;
preferably, in the step 2), relative to the content of iron ions in the lithium-containing filtrate, after the pH value of the lithium-containing filtrate is regulated to 0-3, ferrocyanide with an excess coefficient of 1-1.2 is added for iron removal, and the solution and the iron slag after iron removal are obtained through filtration;
preferably, the temperature is kept between 20 and 50 ℃ during the iron removal process, the time is 0.5 to 2.0 hours, and the stirring speed is 200 to 400r/min.
Preferably, the ferrocyanide is at least one selected from the group consisting of 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), and the lithium deposition temperature is 90-100 ℃ and the lithium deposition time is 10-120min;
the carbonate salt comprises 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 addition ratio of the alkali liquor to the 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 ore, which comprises the following steps: 1) Mixing lithium ore and silicate, performing 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 an iron-removed solution and iron slag; 3) Mixing the solution after iron removal and carbonate, and then precipitating lithium to obtain a lithium-containing compound; the lithium ore Dan Xuanzi is at least one of spodumene, lepidolite and lithium porcelain stone.
According to the invention, the lithium ore and the silicate are mixed and then subjected to ball milling to obviously improve the activity of the lithium ore and the silicate, and then roasting is carried out, the addition of the silicate can regulate and control the silicon content in the lithium ore to promote the mineral reconstruction of the lithium ore, lithium atoms in the lithium ore are replaced by cations in the silicate after activation roasting to form free lithium compounds, silicate radicals and Al, mn, zn and Ca in the mineral form high-silicon double salt regenerated mineral phases, so that the phases of lithium combined with the lithium in the lithium ore are reconstructed into lithium silicate phases which are easy to acid leach, and then the lithium silicate phases are separated;
in the acid leaching process, iron is changed into Fe 3+ The form of the silicon slag is dissolved out and separated from the silicon slag to obtain the low-iron silicon slag with improved grade, which is beneficial to comprehensively recovering quartz in the by-products; then, the lithium-containing filtrate is subjected to iron removal treatment and lithium precipitation, so that the grade of the silicon-rich slag is greatly improved while the excellent lithium extraction rate is obtained, and the content of iron in the silicon-rich slag is reduced.
Further, the method comprises the step of reacting the iron slag with the alkali liquor, so that a ferrocyanide solution which can be used as an iron remover is obtained, the iron remover can be regenerated and recycled, and the economical efficiency and the environmental protection performance of the process are improved.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
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 = mole amount of iron in lithium-containing filtrate/mole amount of iron in raw material × 100%;
the removal rate of iron =100% -the molar amount of iron in the solution after iron removal/the molar amount of iron in the lithium-containing filtrate × 100%.
Example 1
The invention provides a comprehensive extraction method of lithium ore, 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 to perform ball milling for 0.2h at the rotating speed of 300r/min for mechanical activation to obtain a mixed material with the particle size of 300 meshes; after ball milling, placing the mixed material in a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain roasted product, soaking the roasted product in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the rotation speed of 300r/min at 75 ℃, and then filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 94.5 percent, the leaching rate of iron reaches 75 percent, the grade of silicon dioxide in the silicon-rich slag reaches 57.3 percent, and the content of iron is 0.33 percent;
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 perform iron removal reaction, keeping the temperature at 25 ℃ in the iron removal process, and stirring at the speed of 300r/min for 0.5h to obtain iron-removed solution and iron slag; wherein, the removal rate of iron in the lithium-containing filtrate 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 to precipitate lithium, 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 deposition is 97 ℃, the reaction time is 0.4h, lithium carbonate is obtained through the reaction, and the yield of the lithium carbonate is 80.12%;
the comprehensive extraction method of the lithium ore further comprises the step of mixing and reacting the iron slag obtained in the step 2) with a sodium hydroxide solution, 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: and 1g, carrying out the reaction at the stirring speed of 300r/min at the reaction temperature of 60 ℃ for 0.5h to obtain a sodium ferrocyanide solution and goethite after the reaction.
Example 2
The invention provides a comprehensive extraction method of lithium ore, 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 to perform ball milling for 0.2h at the rotating speed of 400r/min for mechanical activation to obtain a mixed material with the particle size of 300 meshes; after ball milling, placing the mixed material in a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain roasted product, soaking the roasted product in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the rotation speed of 300r/min at 75 ℃, and then filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 95.5 percent, the leaching rate of iron reaches 68 percent, the grade of silicon dioxide in the silicon-rich slag reaches 60.5 percent, and the content of iron is 0.44 percent;
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 perform iron removal reaction, wherein the temperature is kept at 25 ℃ in the iron removal process, the stirring speed is 300r/min, and the time is 0.5h, so as 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 the 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, lithium carbonate is obtained through the reaction, and the yield of the lithium carbonate is 86.79%;
the comprehensive extraction method of the lithium ore also comprises the step of mixing and reacting the iron slag obtained in the step 2) with a potassium hydroxide solution, 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: and 1g, carrying out the reaction at a stirring speed of 300r/min at a reaction temperature of 80 ℃ for 1h to obtain a potassium ferrocyanide solution and goethite 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 then placing the mixture into a planetary ball mill to perform ball milling for 0.2h at the rotating speed of 400r/min for mechanical activation to obtain a mixed material with the particle size of 300 meshes; after ball milling, placing the mixed material in a high-temperature reaction furnace, roasting for 2 hours at 1000 ℃ to obtain roasted product, soaking the roasted product in hydrochloric acid with the concentration of 2mol/L, stirring for 1 hour at the rotation speed of 300r/min at 75 ℃, and then filtering to obtain lithium-containing filtrate and silicon-rich slag; wherein, the extraction rate of lithium reaches 95.5 percent, the leaching rate of iron reaches 77 percent, the grade of silicon dioxide in the silicon-rich slag reaches 63.3 percent, and the content of iron is 0.32 percent;
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 perform iron removal reaction, wherein the temperature is kept at 20 ℃ in the iron removal process, the stirring speed is 300r/min, and the time is 1.5h, so as to obtain solution and iron slag after iron removal; wherein, the removal rate of iron in the lithium-containing filtrate 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 the 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, lithium carbonate is obtained through the 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 and reacting the iron slag obtained in the step 2) with a sodium hydroxide solution, 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: and 1g, carrying out the reaction at a stirring speed of 300r/min at a reaction temperature of 80 ℃ for 0.5h to obtain a sodium ferrocyanide solution and goethite 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 percent, and the content of iron is 0.67 percent; the yield of lithium carbonate prepared in step 3) was 79.72%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A comprehensive extraction method for lithium ores is characterized by comprising the following steps:
1) Mixing lithium ore and 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 an iron-removed solution and iron slag;
3) Mixing the solution after iron removal and carbonate, and then precipitating lithium to obtain a lithium-containing compound;
the lithium ore Dan Xuanzi is at least one of spodumene, lepidolite and lithium porcelain stone.
2. The method of claim 1, wherein the silicate is at least one selected from the group consisting of sodium silicate, potassium silicate, calcium silicate, magnesium silicate, aluminum silicate, iron silicate, ferrous silicate, zinc silicate, manganese silicate;
the mass ratio of the lithium ore to the silicate is 1 (0.1-1).
3. The comprehensive extraction method of lithium ores according to any one of claims 1 to 2, wherein in the ball milling step of step 1), the ball milling time is 0.1 to 2 hours, the ball milling rotation speed is 150 to 600r/min, and the particle size of the ball-milled material is 200 to 400 meshes.
4. The comprehensive extraction method of lithium ore according to any one of claims 1 to 3, wherein the roasting temperature in the roasting step of step 1) is 500 to 1200 ℃ and the time is 0.5 to 3.0 hours.
5. The integrated lithium ore extraction method according to any one of claims 1 to 4, wherein the roasted product calcine is immersed in an acid solution in the acid immersion step in step 1), wherein the acid solution comprises hydrochloric acid, and the concentration of the acid solution is 0.5 to 5.5mol/L.
6. The comprehensive extraction method of lithium ore according to any one of claims 1 to 5, wherein the impregnation temperature is 50 to 100 ℃, the impregnation time is 0.5 to 2 hours, and the stirring speed is 200 to 400r/min.
7. The comprehensive extraction method of lithium ore according to any one of claims 1 to 6, wherein in step 2): regulating and controlling the pH value of the lithium-containing filtrate obtained in the step 1) to 0-3, then adding ferrocyanide to remove iron, and filtering to obtain an iron-removed solution and iron slag;
preferably, in the step 2), relative to the content of iron ions in the lithium-containing filtrate, after the pH value of the lithium-containing filtrate is regulated to 0-3, ferrocyanide with an excess coefficient of 1-1.2 is added for iron removal, and filtration is carried out to obtain an iron-removed solution and iron slag;
preferably, the temperature is kept between 20 and 50 ℃ during the iron removal process, the time is 0.5 to 2.0 hours, and the stirring speed is 200 to 400r/min.
8. The method for comprehensively extracting lithium ore according to any one of claims 1 to 7, wherein the ferrocyanide is at least one selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide and ammonium ferrocyanide.
9. The method for comprehensively extracting lithium ore according to any one of claims 1 to 8,
the molar ratio of lithium ions to carbonate in the solution after iron removal in the step 3) is 1: (0.5-0.6), the lithium deposition temperature is 90-100 ℃, and the lithium deposition time is 10-120min;
the carbonate salt comprises sodium carbonate.
10. The comprehensive extraction method for lithium ore according to any one of claims 1 to 9, further comprising reacting the iron slag obtained in 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 addition ratio of the alkali liquor to the 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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| CN116786078A (en) * | 2023-05-25 | 2023-09-22 | 苏州博睿特环保科技有限公司 | Lithium iron silicate modified spodumene slag lithium ion sieve, precursor thereof and preparation method thereof |
Citations (20)
| 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 |
| US20170175228A1 (en) * | 2015-12-22 | 2017-06-22 | Richard Hunwick | Recovery of lithium from silicate minerals |
| US20170217796A1 (en) * | 2016-02-01 | 2017-08-03 | Northwestern University | Compounds for lithium extraction via ion exchange |
| 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 |
| 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 |
| US20200399772A1 (en) * | 2019-06-21 | 2020-12-24 | Xerion Advanced Battery Corp. | Methods for extracting lithium from spodumene |
| 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 |
| US20210380429A1 (en) * | 2020-06-09 | 2021-12-09 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| WO2022126053A2 (en) * | 2020-11-04 | 2022-06-16 | Basf Corporation | Methods of obtaining water for downstream processes |
-
2022
- 2022-10-13 CN CN202211253569.XA patent/CN115466854B/en active Active
Patent Citations (21)
| 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 |
| US20170175228A1 (en) * | 2015-12-22 | 2017-06-22 | Richard Hunwick | Recovery of lithium from silicate minerals |
| US20170217796A1 (en) * | 2016-02-01 | 2017-08-03 | Northwestern University | Compounds for lithium extraction via ion exchange |
| 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 |
| US20200399772A1 (en) * | 2019-06-21 | 2020-12-24 | Xerion Advanced Battery Corp. | Methods for extracting lithium from spodumene |
| 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 |
| US20210380429A1 (en) * | 2020-06-09 | 2021-12-09 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| 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 |
|---|
| DMYTRO YELATONTSEV等: "Processing of lithium ores: Industrial technologies and case studies – A review", 《HYDROMETALLURGY》, vol. 201 * |
| 田键等: "典型锂矿石提锂技术研究进展", 《湖北大学学报》, vol. 42, no. 01 * |
| 苏慧等: "矿石资源中锂的提取与回收研究进展", 《化工学报》, vol. 70, no. 01 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116786078A (en) * | 2023-05-25 | 2023-09-22 | 苏州博睿特环保科技有限公司 | Lithium iron silicate modified spodumene slag lithium ion sieve, precursor thereof and preparation method thereof |
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