CN105907943A - A process of extracting lithium from lithium ore through calcination with a chloridizing agent and an inorganic base and dissolving out with an organic solvent - Google Patents
A process of extracting lithium from lithium ore through calcination with a chloridizing agent and an inorganic base and dissolving out with an organic solvent Download PDFInfo
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- CN105907943A CN105907943A CN201610240269.6A CN201610240269A CN105907943A CN 105907943 A CN105907943 A CN 105907943A CN 201610240269 A CN201610240269 A CN 201610240269A CN 105907943 A CN105907943 A CN 105907943A
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- Prior art keywords
- lithium
- acetone
- inorganic base
- roasting
- ore
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 109
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 150000007529 inorganic bases Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 18
- 238000001354 calcination Methods 0.000 title abstract description 5
- 239000003960 organic solvent Substances 0.000 title description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 160
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004568 cement Substances 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 32
- 239000012320 chlorinating reagent Substances 0.000 claims description 29
- 238000005660 chlorination reaction Methods 0.000 claims description 24
- 239000000284 extract Substances 0.000 claims description 19
- 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 description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052642 spodumene Inorganic materials 0.000 claims description 17
- 229910052629 lepidolite Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 229910020489 SiO3 Inorganic materials 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 229910010199 LiAl Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000004035 construction material Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 2
- 230000005494 condensation Effects 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- 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 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- -1 inorganic base sodium hydroxide Chemical class 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- ZSYZSZTWBOHQQK-UHFFFAOYSA-L dilithium;dichloride Chemical compound [Li+].[Li+].[Cl-].[Cl-] ZSYZSZTWBOHQQK-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/1641—Leaching with acyclic or carbocyclic agents of a single type with ketones or aldehydes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process of extracting lithium from lithium ore through calcination with a chloridizing agent and an inorganic base and dissolving out with acetone is disclosed. The process includes (1) a step of material mixing, namely a step of fully mixing the lithium ore with sodium hydroxide or potassium hydroxide, sodium chloride or potassium chloride according to a ratio, (2) a step of calcinating, namely a step of adding the material mixture into a kiln, and calcinating to obtain clinker, (3) a step of extraction with acetone, namely a step of subjecting the clinker cooled to room temperature to selective extraction with the acetone to obtain lithium chloride and performing solid liquid separation to obtain a filtrate and filter residues, (4) a step of distilling, namely a step of heating the filtrate to a temperature higher than the boiling point of the acetone, collecting vapor, condensing to recover the acetone, recycling the acetone, and evaporating thoroughly to obtain pure anhydrous lithium chloride, and (5) a step of residue treating, namely a step of heating the filter residues to a temperature higher than the boiling point of the acetone, collecting vapor, condensing to recover the acetone, and recycling the acetone, wherein the rest residues can be directly used as a raw material for cement production or are adopted as a building material after being treated. The process has advantages of a low material flux, high equipment productivity, low energy consumption, a short process, a high lithium recovery rate, a low production cost, excellent product quality, nearly no generation of 'three wastes', clean and environmental-friendly production, and the like.
Description
Technical field
The present invention relates to extract the industrial process of lithium from lithium Ore, relate to lithium Ore and extract the cleaning of lithium, environment-friendly type
Production technology, belongs to the fields such as lithium ore smelting, chemical industry, chemistry.
Background technology
Lithium belongs to rare non-ferrous metal, is the metal that nature is the lightest, due to physics, the chemical property of its uniqueness, by extensively
General for fields such as military affairs, chemical industry, optics, oils and fats, refrigeration, it is described as " promoting the energy metal of world's progress ", it is expected to become
Important fuel to mankind's long run supply energy.Lithium is the core material of new energy source fuel cell and electrokinetic cell, lithium and change thereof
Compound is widely used in industrial department and new high-tech industry, of many uses in the development of the national economy, occupies critically important
Strategic position.Along with the day by day increase of world's lithium consumption figure, the production of lithium salts product and development directly affect industry new technique
Development, the most also indicate the level of development of a national new high-tech industry.
How to reduce the production cost of lithium, it is achieved clean environment-friendly type and produce, meet the application technology quality to lithium product
Requirement etc. is the task that current lithium industry is extremely urgent.And the extractive technique of lithium falls behind, and production cost is high and " three wastes " discharge
Pollute environment and have become as a big bottleneck of lithium industry development.
Existing lithium smelting process mainly has three kinds: 1, extract from spodumene；2, extract from lepidolite；3, from salt lake
Salt extracts.From spodumene and lepidolite, extract lithium be referred to as lithium Ore and carry lithium, be the main channel in lithium source.Existing skill
Art has from the method for spodumene, lepidolite extraction lithium:
1, limestone calcination method: by spodumene or lepidolite and limestone batch mixing, calcine (spodumene 1050 ~ 11500C；Lithium cloud
Female 880 ~ 10500C.), water extraction, remove impurity, multi-stage evaporation crystallization produces Lithium hydrate.
2, spodumene thermal cracking (1050 ~ 11500C) after becoming β type spodumene: (1) sulfuric acid roasting method: sulfuric acid baking, water
Leaching, causticization, remove impurity, multi-stage evaporation crystallization produces Lithium hydrate.(2) soda autoclaving method: autoclaving leaches, remove impurity, produces lithium carbonate.
3, lepidolite-chlorinating roasting: lepidolite/Calx/sodium chloride=1/0.4/0.3(weight ratio), roasting (920 ~
9600C), water logging, remove impurity, produces lithium carbonate or multi-stage evaporation crystallization produces Lithium hydrate.
It is high to there is energy consumption in prior art, and material circulation is big, lithium metal recovery rate low (η 65 ~ 82%), and the quantity of slag is big, produces stream
Journey is long, and equipment investment is big, and production cost is high.It is additionally, since lithium and there is stronger chemism, and the separation of other metal ion
Extremely difficult, it is very big that product remove impurity purifies difficulty, and product is difficult to reach high-purity standard-required.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of from spodumene, the new work of lepidolite production extraction lithium
Technology, has material circulation little, and equipment capacity is big, and energy consumption is low, and technological process is short, and lithium metal recovery rate is high, production cost
Extremely low, product quality is excellent, produces almost without " three wastes ", cleans the significant superioritys such as environment-friendly type production.
The purpose of the present invention is achieved in that its technique comprises the steps:
1, batch mixing: lithium Ore and inorganic base, chlorinating agent proportioning press lithium Ore: inorganic base: chlorinating agent=1:0.1:0.2 ~ 0.4(is heavily
Amount ratio) mix homogeneously, obtain compound.
Lithium Ore refers to spodumene, lepidolite；Inorganic base refers to sodium hydroxide or potassium hydroxide；Chlorinating agent refers to sodium chloride
Or potassium chloride.Chlorinating agent consumption presses the 110 ~ 130% of theoretical response magnitude, chlorinating agent: inorganic base=1 ~ 10:1(weight ratio).
2, roasting: step 1 compound is entered kiln 650 ~ 10000C roasting 0.5 ~ 3h, obtains grog.
The purpose of roasting is to make the lithium in lithium Ore and chlorination reaction generation lithium chloride, and the effect of inorganic base is to reduce to melt
The fusing point of salt system, fluxes, and suppression alkaline-earth metal is chlorinated.Clinker material loosens, and occasionally has caking.Roasting optimal conditions is: roasting
Burn temperature 650 ~ 7500C, time 1h.Lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + RCl→ LiCl + RAl(SiO3)2
Lepidolite Li2Al2Si3O9(F,OH) + 2 RCl → 2 LiCl + R2 Al2Si3O9(F,OH)
R-Alkali-Metal Na, K.
3, acetone leaching: the coolest grog to room temperature step 2 obtained, adds acetone stirring leaching in airtight container
Taking, make the lithium chloride in grog be completely dissolved out, extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue.
Owing to the valence link in lithium chloride molecule is not typical ionic bond, can be dissolved in a lot of organic solvent, as ethanol,
Acetone etc., utilize this characteristic to be separated with alkali metal by lithium.Practice have shown that acetone has more preferable selectivity, use acetone leaching
Lithium chloride.Optimal conditions: room temperature leaches, and solid-to-liquid ratio is 1:4 ~ 6, time 1 ~ 2h.
4, distillation: the filtrate that step 3 obtains is heated to the boiling point 56.1 of acetone0More than C, making acetone is that gaseous state separates out, and receives
Collection recycling of condensed steam acetone, circulates Reusability.Evaporation prepares pure anhydrous Lithium chloride completely.Pure anhydrous Lithium chloride refers to
In product, non-lithium metal oxide content is trace, i.e. less than 50PPM.
Optimal conditions: vapo(u)rizing temperature 80 ~ 900C。
5, Slag treatment: the filtering residue that step 3 obtains is heated to the boiling point 56.1 of acetone0More than C, making acetone is that gaseous state separates out,
Collect recycling of condensed steam acetone, circulate Reusability.Optimal conditions: vapo(u)rizing temperature 80 ~ 1000C.Recrement can be directly used for water
The raw material that mud produces；Also can reclaim remaining alkali and chlorinating agent through water logging, circulate Reusability, residue can make construction material.
The present invention compared with prior art, has a significant superiority:
(1) lithium Ore sodium chloride or potassium chloride are made chlorinating agent by the present invention, helping of inorganic base sodium hydroxide or potassium hydroxide
The lower roasting of molten and suppression, optionally carries out chlorination and generates lithium chloride lithium Ore, and lithium ore decomposition is complete, and resolution ratio reaches 98%
Above, a difficult problem for lithium ore decomposition is solved.
(2) roasting can either statically or dynamically be carried out, and sintering temperature is low, and energy consumption is low, and industrial realization is easy.
(3) in the commercial production of lithium, use acetone selectivity leaching dissolution lithium chloride initiatively, there is selectivity good,
Raw material is easy to get, and leaching rate is up to more than 98%, not only avoid the pollution to lithium product of other metal ion, decreases substantial amounts of
Remove impurity link, product quality is pure, and thoroughly solves the difficult problem that the lithium response rate is low, and the lithium technique response rate is up to more than 92%.
(4) using acetone selectivity dissolution lithium chloride, not only solid-liquid separation is easy, and the acetone in filtrate, filtering residue holds
Easily reclaim, circulate Reusability, thoroughly solve generation and the emission problem of waste water；Also considerably reduce production cost.
(5) waste residue that lithium ore smelting produces can be used for building materials, thoroughly solves waste sludge discharge problem.
(6) traditional mode of production: lithium Ore → Lithium hydrate or lithium carbonate → lithium chloride → anhydrous Lithium chloride → lithium metal and
Its lithium product, the invention enables lithium Ore → pure anhydrous Lithium chloride → lithium metal and other lithium product to be possibly realized, is lithium smelting
The most great innovation of refining technology.
(7) technological process is brief, and material circulation is little, and equipment capacity is big, and capital expenditure is few.
The boiling point of acetone is generally 56.10C, but along with the change of ambient pressure, the boiling point of acetone will change, this
The boiling point 56.1 of acetone it is heated to described in bright0More than C is heated to more than the boiling point of acetone by becoming, as long as can make acetone is gaseous state
Separate out and just meet the purpose of the present invention.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Embodiment 1
Lithium ore chlorination agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and comprises the steps:
1, batch mixing: lithium Ore and inorganic base, chlorinating agent proportioning are pressed lithium Ore: inorganic base: chlorinating agent=1:0.1:0.4(weight
Than) mix homogeneously, obtain compound.
Spodumene LiAl (SiO3)21000kg mineral chemical composition: Li2O 6.65%, Al2O328.61%, SiO2
61.88%, Fe2O30.83%, Na2O 0.52%, CaO 0.45%, MgO 0.16% powdery
Inorganic base: industrial sodium hydroxide lamellar 100kg；Chlorinating agent: industrial chlorinations sodium 400kg.
Spodumene, industrial sodium hydroxide, industrial chlorinations sodium are ground into the 80 following mix homogeneously of mesh together, obtain compound.
2, roasting: step 1 compound is entered kiln 7500C roasting 1.0h, obtains grog.
Clinker material loosens, and occasionally has caking.Lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + NaCl → LiCl + RAl(SiO3)2
3, acetone leaching: the coolest grog to room temperature step 2 obtained, adds acetone stirring leaching in airtight container, makes
Lithium chloride in grog is completely dissolved out, and extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue.
Industrial acetone 6M3, room temperature leaches, time 2h.
4, distillation: the filtrate that step 3 obtains is heated to 900C, making acetone is that gaseous state separates out, and collects recycling of condensed steam third
Ketone, circulates Reusability.Evaporation prepares pure anhydrous Lithium chloride 176kg completely, and non-lithium metal oxide content is trace, the least
In 50PPM.
5, Slag treatment: the filtering residue that step 3 obtains is heated to 1000C, making acetone is that gaseous state separates out, and collects recycling of condensed steam
Acetone, circulates Reusability.Recrement can be directly used for the raw material of manufacture of cement；Remaining alkali sodium hydroxide can also be reclaimed through water logging
With chlorinating agent sodium chloride, circulating Reusability, residue can make construction material.
Through process above lithium overall recovery: Li2Oη93.41%。
Embodiment 2
Lithium ore chlorination agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and comprises the steps:
1, batch mixing: lithium Ore and inorganic base, chlorinating agent proportioning are pressed lithium Ore: inorganic base: chlorinating agent=1:0.1:0.2(weight
Than) mix homogeneously, obtain compound.
Lepidolite Li2Al2Si3O9(F, OH) 1000kg mineral chemical composition: Li2O 3.95%, Al2O327.48%,
SiO250.38%, Fe2O30.05%, Na2O 0.48%, K2O 8.46%, Rb2O 2.20%, F 5.65% powdery
Inorganic base: industrial sodium hydroxide lamellar 100kg；Chlorinating agent: industrial chlorinations sodium 200kg.
Industrial sodium hydroxide, industrial chlorinations sodium are ground into below 80 mesh and lepidolite mix homogeneously together, obtain compound.
2, roasting: step 1 compound is entered kiln 6500C roasting 1.0h, obtains grog.
Clinker material loosens, and occasionally has caking.Lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
The chemical reaction of roasting:
Lepidolite Li2Al2Si3O9(F,OH) + 2NaCl → 2 LiCl + Na2 Al2Si3O9(F,OH)
3, acetone leaching: the coolest grog to room temperature step 2 obtained, adds acetone stirring leaching in airtight container,
Making the lithium chloride in grog be completely dissolved out, extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue.
Industrial acetone 4M3, room temperature leaches, time 2h.
4, distillation: the filtrate that step 3 obtains is heated to 850C, making acetone is that gaseous state separates out, and collects recycling of condensed steam third
Ketone, circulates Reusability.Evaporation prepares pure anhydrous Lithium chloride 106kg completely, and in product, non-lithium metal oxide content is trace
Amount, respectively less than 50PPM.
5, Slag treatment: the filtering residue that step 3 obtains is heated to 900C, making acetone is that gaseous state separates out, and collects recycling of condensed steam
Acetone, circulates Reusability.Recrement can be directly used for the raw material of manufacture of cement；Remaining alkali sodium hydroxide can also be reclaimed through water logging
With chlorinating agent sodium chloride, circulating Reusability, residue can make construction material.
Through process above lithium overall recovery: Li2Oη94.71%。
Embodiment 3
Lithium ore chlorination agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and comprises the steps:
1, batch mixing: lithium Ore and inorganic base, chlorinating agent proportioning are pressed lithium Ore: inorganic base: chlorinating agent=1:0.1:0.4(weight
Than) mix homogeneously, obtain compound.
Xinjiang, China lithium concentrate: spodumene LiAl (SiO3)21000kg mineral chemical composition: Li2O 6.06%, Al2O3
23.47%, SiO261.93%, Fe2O31.81%, Na2O 1.05%, K2O 0.24%, CaO 1.19%, MgO 0.52%, Mn O2
0.31%, Rb2O 2.2%, P2O5 0.38%, BeO 0.064% powdery
Inorganic base: industrial sodium hydroxide lamellar 100kg；Chlorinating agent: industrial chlorinations sodium 400kg.
Industrial sodium hydroxide, industrial chlorinations sodium are ground into below 80 mesh and lithium concentrate mix homogeneously together, obtain compound.
2, roasting: step 1 compound is entered kiln 7000C roasting 1.0h, obtains grog.
Clinker material loosens, and occasionally has caking.Lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + NaCl → LiCl + RAl(SiO3)2
3, acetone leaching: the coolest grog to room temperature step 2 obtained, adds acetone stirring leaching in airtight container, makes
Lithium chloride in grog is completely dissolved out, and extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue.
Industrial acetone 6M3, room temperature leaches, time 2h.
4, distillation: the filtrate that step 3 obtains is heated to 900C, making acetone is that gaseous state separates out, and collects recycling of condensed steam third
Ketone, circulates Reusability.Evaporation prepares pure anhydrous Lithium chloride 163.3kg completely, and in product, non-lithium metal oxide content is
Trace, respectively less than 50PPM.
5, Slag treatment: the filtering residue that step 3 obtains is heated to 1000C, making acetone is that gaseous state separates out, and collects recycling of condensed steam
Acetone, circulates Reusability.Recrement can be directly used for the raw material of manufacture of cement；Remaining alkali sodium hydroxide can also be reclaimed through water logging
With chlorinating agent sodium chloride, circulating Reusability, residue can make construction material.
Through process above lithium overall recovery: Li2Oη95.11%。
Embodiment 4
Lithium ore chlorination agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and comprises the steps:
1, batch mixing: lithium Ore and inorganic base, chlorinating agent proportioning are pressed lithium Ore: inorganic base: chlorinating agent=1:0.1:0.3(weight
Than) mix homogeneously, obtain compound.
Jiangxi, China lithium concentrate: lepidolite Li2Al2Si3O9(F, OH) 1000kg mineral chemical composition: Li2O 4.39%,
Al2O323.73%, SiO254.33%, Fe2O30.31%, Na2O 1.80%, K2O 8.66%, CaO 0.18%, MgO 0.24%,
Mn O20.25%, Rb2O 1.33%, Cs2O 0.3%, F 5.60%, P2O5 0.38%
Inorganic base: industrial hydrogen potassium oxide bulk 100kg；Chlorinating agent: industrial potassium chloride 300kg.
Industrial hydrogen potassium oxide, industrial potassium chloride are ground into together below 80 mesh and lepidolite mix homogeneously, obtain compound.
2, roasting: step 1 compound is entered kiln 6500C roasting 1h, obtains grog.
Clinker material loosens, and occasionally has caking.Lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
The chemical reaction of roasting:
Lepidolite Li2Al2Si3O9(F,OH) + 2 KCl → 2 LiCl + K2 Al2Si3O9(F,OH)
3, acetone leaching: the coolest grog to room temperature step 2 obtained, adds acetone stirring leaching in airtight container, makes
Lithium chloride in grog is completely dissolved out, and extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue.
Industrial acetone 5M3, room temperature leaches, time 2h.
4, distillation: the filtrate that step 3 obtains is heated to 800C, making acetone is that gaseous state separates out, and collects recycling of condensed steam third
Ketone, circulates Reusability.Evaporation prepares pure anhydrous Lithium chloride 118kg completely, and in product, non-lithium metal oxide content is trace
Amount, respectively less than 50PPM.
5, Slag treatment: the filtering residue that step 3 obtains is heated to 800C, making acetone is that gaseous state separates out, and collects recycling of condensed steam
Acetone, circulates Reusability.Recrement can be directly used for the raw material of manufacture of cement；Remaining alkali potassium hydroxide can also be reclaimed through water logging
With chlorinating agent potassium chloride, circulating Reusability, residue can make construction material.
Through process above lithium overall recovery: Li2Oη94.87%。
Above example is that the foregoing to the present invention is further described, but should this be interpreted as in the present invention
The scope stating theme is only limitted to above-described embodiment, and all methods realized based on foregoing belong to the scope of the present invention.
Claims (9)
1. lithium ore chlorination agent inorganic base roasting acetone leaching extracts lithium technique, and its feature comprises the steps:
(1) batch mixing: by lithium Ore with inorganic base, chlorinating agent by proportioning lithium Ore: inorganic base: chlorinating agent=1:0.1:0.2 ~ 0.4
(weight ratio) mix homogeneously, obtains compound；
(2) roasting: compound is entered kiln 650 ~ 10000C roasting 0.5 ~ 3h, obtains grog, and lithium ore decomposition is complete, and resolution ratio reaches 98%
Above；
(3) acetone leaching: by the coolest grog to room temperature, adds acetone stirring leaching in airtight container, makes in grog
Lithium chloride is completely dissolved out, and extraction rate is more than 98%, and solid-liquid separation obtains filtrate and filtering residue；
(4) distillation: filtrate is heated to more than the boiling point of acetone, making acetone is that gaseous state separates out, and collects recycling of condensed steam acetone,
Circulation Reusability, evaporation prepares pure anhydrous Lithium chloride completely；
(5) Slag treatment: the filtering residue that step (3) obtains is heated to more than the boiling point of acetone, making acetone is that gaseous state separates out, and collects steam
Acetone is reclaimed in condensation, circulates Reusability, and recrement can be directly used for the raw material of manufacture of cement, it is possible to reclaim remaining alkali and chlorine through water logging
Agent, circulates Reusability, and residue can make construction material.
2. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: in step (1), lithium Ore refers to spodumene and/or lepidolite, and inorganic base refers to sodium hydroxide and/or potassium hydroxide, chlorination
Agent refers to sodium chloride and/or potassium chloride, and chlorinating agent consumption presses the 110 ~ 130% of theoretical response magnitude, chlorinating agent: inorganic base=1 ~ 10:1
(weight ratio).
3. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: step (1) lithium Ore and inorganic base, chlorinating agent proportion optimizing are lithium Ore: inorganic base: chlorinating agent=1:0.1:0.2 ~ 0.4
(weight ratio).
4. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
Under: step (2) roasting is the fluxing and suppress alkaline-earth metal to be chlorinated of inorganic base, make the lithium in lithium Ore and chlorination reaction
Generate lithium chloride；
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + RCl →LiCl + RAl(SiO3)2
Lepidolite Li2Al2Si3O9(F,OH) + 2 RCl → 2 LiCl + R2 Al2Si3O9(F,OH)
R-Alkali-Metal Na, K.
5. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: step (2) roasting optimal conditions is: temperature 650 ~ 7500C, time 1h, lithium ore decomposition is complete, and resolution ratio reaches more than 98%.
6. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: the step (3) lithium chloride in acetone selectivity leaching grog.
7. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
Lithium chloride optimal conditions in: step (3) described acetone leaching grog: room temperature leaches, and solid-to-liquid ratio is 1:4 ~ 6, time 1 ~
2h, extraction rate is more than 98%.
8. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: step (4) is described is heated to more than the boiling point of acetone by filtrate, and making acetone is that gaseous state separates out, and evaporation prepares pure nothing completely
Water lithium chloride, pure anhydrous Lithium chloride refers to that in product, non-lithium metal oxide content is trace, i.e. less than 50PPM.
9. the lithium ore chlorination agent inorganic base roasting acetone leaching as described in claims 1 extracts lithium technique, and its feature exists
In: the filtering residue that step (3) obtains is heated to more than the boiling point of acetone by step (5) Slag treatment, and making acetone is that gaseous state separates out, and collects and steams
Acetone is reclaimed in vapour condensation, circulates Reusability, and recrement can directly be applied.
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| CN108285975A (en) * | 2017-12-27 | 2018-07-17 | 中南大学 | A method of using PVC pyrolysis lithium is extracted from lepidolite |
| CN110482576A (en) * | 2019-09-26 | 2019-11-22 | 福州大学 | A kind of method that lepidolite hydro-thermal prepares lithium salts |
| CN110494573A (en) * | 2017-02-28 | 2019-11-22 | Sms集团有限公司 | Method for preparing lithium hydroxide by the ore containing lithium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101172624A (en) * | 2007-08-06 | 2008-05-07 | 青海中信国安科技发展有限公司 | Method of producing high-purity anhydrous lithium chloride |
| CN101775505A (en) * | 2010-02-08 | 2010-07-14 | 中南大学 | Method and device for extracting lithium from lapidolite by chloridizing roasting method |
| CN101974678A (en) * | 2010-11-24 | 2011-02-16 | 中南大学 | Method for extracting lithium and other alkali metal elements from lepidolite mineral |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172624A (en) * | 2007-08-06 | 2008-05-07 | 青海中信国安科技发展有限公司 | Method of producing high-purity anhydrous lithium chloride |
| CN101775505A (en) * | 2010-02-08 | 2010-07-14 | 中南大学 | Method and device for extracting lithium from lapidolite by chloridizing roasting method |
| CN101974678A (en) * | 2010-11-24 | 2011-02-16 | 中南大学 | Method for extracting lithium and other alkali metal elements from lepidolite mineral |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110494573A (en) * | 2017-02-28 | 2019-11-22 | Sms集团有限公司 | Method for preparing lithium hydroxide by the ore containing lithium |
| CN108285975A (en) * | 2017-12-27 | 2018-07-17 | 中南大学 | A method of using PVC pyrolysis lithium is extracted from lepidolite |
| CN110482576A (en) * | 2019-09-26 | 2019-11-22 | 福州大学 | A kind of method that lepidolite hydro-thermal prepares lithium salts |
| CN110482576B (en) * | 2019-09-26 | 2022-05-06 | 福州大学 | Method for preparing lithium salt from lepidolite through hydrothermal method |
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