CN105907943B - Lithium ore chlorinating agent inorganic base roasts organic solvent leaching and extracts lithium technique - Google Patents
Lithium ore chlorinating agent inorganic base roasts organic solvent leaching and extracts lithium technique Download PDFInfo
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- CN105907943B CN105907943B CN201610240269.6A CN201610240269A CN105907943B CN 105907943 B CN105907943 B CN 105907943B CN 201610240269 A CN201610240269 A CN 201610240269A CN 105907943 B CN105907943 B CN 105907943B
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- lithium
- acetone
- inorganic base
- chlorinating agent
- ore
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 106
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000012320 chlorinating reagent Substances 0.000 title claims abstract description 43
- 150000007529 inorganic bases Chemical class 0.000 title claims abstract description 37
- 238000002386 leaching Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000284 extract Substances 0.000 title claims abstract description 10
- 239000003960 organic solvent Substances 0.000 title claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 136
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 9
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004035 construction material Substances 0.000 claims abstract description 7
- 239000004568 cement Substances 0.000 claims abstract description 6
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052629 lepidolite Inorganic materials 0.000 claims description 18
- 229910052642 spodumene Inorganic materials 0.000 claims description 18
- 229910020489 SiO3 Inorganic materials 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 229910010199 LiAl Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 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
- 229910052700 potassium 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
- 239000003795 chemical substances by application Substances 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 claims 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 239000011734 sodium 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
- 229910052708 sodium Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- -1 inorganic base sodium hydroxide Chemical class 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 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
- 241001417490 Sillaginidae Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- JRPMUXPPTDHWAI-UHFFFAOYSA-M lithium propan-2-one chloride Chemical compound CC(=O)C.[Li+].[Cl-] JRPMUXPPTDHWAI-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Lithium ore chlorinating agent inorganic base roasts acetone leaching and extracts lithium technique, comprising: (1) mixing: lithium ore and sodium hydroxide or potassium hydroxide, sodium chloride or potassium chloride are uniformly mixed according to a ratio to obtain mixture.(2) it roasts: mixture being entered into kiln and roasts to obtain clinker.(3) acetone leaches: the cool clinker to room temperature is separated by solid-liquid separation to obtain filtrate and filter residue with acetone selectively leaching lithium chloride.(4) it distills: filtrate being heated to the boiling point of acetone or more, collects recycling of condensed steam acetone, recycles Reusability.Pure anhydrous lithium chloride is made in evaporation completely.(5) Slag treatment: filter residue is heated to the boiling point of acetone or more, collects recycling of condensed steam acetone, recycles Reusability.Recrement can be directly used for manufacture of cement raw material or processing after make construction material.Have material circulation small using the present invention, equipment capacity is big, and low energy consumption, and process flow is short, and the lithium metal rate of recovery is high, and production cost is very low, and product quality is excellent, generates almost without " three wastes ", cleans the significant superiority such as environment-friendly type production.
Description
Technical field
The present invention relates to the industrial processes that lithium is extracted from lithium ore, are related to lithium ore and extract the cleaning of lithium, ring
Guarantor's type production technology belongs to the fields such as lithium ore smelting, chemical industry, chemistry.
Background technique
Lithium belongs to rare non-ferrous metal, is the most light metal of nature, wide due to its unique physics, chemical property
It is general to be used for the fields such as military affairs, chemical industry, optics, grease, refrigeration, it is known as " pushing the energy metal of world's progress ", it is expected to become
To the important fuel of mankind's long run supply energy.Lithium is the core material of new energy source fuel cell and power battery, lithium and its change
Object is closed to be widely used in industrial department and new high-tech industry, it is widely used in the development of the national economy, occupy critically important
Strategic position.With the increasingly increase of world's lithium consumption figure, the production and development of lithium salts product directly affect industrial new technology
Development, also indicate the development level of a national new high-tech industry to a certain extent.
How the production cost of lithium is reduced, and realization cleans environment-friendly type production, meets application technology to the quality of lithium product
It is required that etc. be the extremely urgent task of current lithium industry.And the extractive technique backwardness and high production cost of lithium and " three wastes " discharge
Pollution environment has become a big bottleneck of lithium industry development.
There are mainly three types of existing lithium smelting processes: 1, extracting from spodumene;2, it is extracted from lepidolite;3, from salt lake
It is extracted in brine.Lithium is extracted from spodumene and lepidolite to be referred to as lithium ore and mention lithium, is the main channel in lithium source.Existing skill
Art has from the method that spodumene, lepidolite extract lithium:
1, limestone calcination method: by spodumene or lepidolite and lime stone mixing, (spodumene 1050 ~ 1150 is calcined0C;
Lepidolite 880 ~ 10500C.), water extraction, removal of impurities, multi-stage evaporation crystallization production lithium hydroxide.
2, spodumene thermal cracking (1050 ~ 11500C) after at β type spodumene: (1) sulfuric acid roasting method: sulfuric acid baking, water
Leaching, causticization, removal of impurities, multi-stage evaporation crystallization production lithium hydroxide.(2) soda ash autoclaving method: autoclaving leaching, removal of impurities produce lithium carbonate.
3, lepidolite-chlorinating roasting: lepidolite/lime/sodium chloride=1/0.4/0.3(weight ratio), roasting (920 ~
9600C), water logging, removal of impurities produce lithium carbonate or multi-stage evaporation crystallization production lithium hydroxide.
The prior art is there are energy consumption height, and material circulation is big, and the lithium metal rate of recovery is low (η 65 ~ 82%), and the quantity of slag is big, production stream
Journey is long, and equipment investment is big, high production cost.Moreover, because lithium has the separation of stronger chemical activity and other metal ions
Extremely difficult, product removal of impurities purification is difficult, and product is difficult to reach high-purity standard requirements.
Summary of the invention
The present invention is directed to overcome the deficiencies of the prior art and provide a kind of new work that lithium is extracted from spodumene, lepidolite production
Skill technology has material circulation small, and equipment capacity is big, and low energy consumption, and process flow is short, and the lithium metal rate of recovery is high, production cost
Extremely low, product quality is excellent, generates almost without " three wastes ", cleans the significant superiority such as environment-friendly type production.
It is an object of the present invention to what is be achieved, and technique includes the following steps:
1, mixing: by lithium ore and inorganic base, chlorinating agent proportion by lithium ore: inorganic base: chlorinating agent=1:0.1:0.2 ~
0.4(weight ratio) it is uniformly mixed, obtain mixture.
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 dosage presses the 110 ~ 130% of theoretical reacting dose, chlorinating agent: inorganic base=1 ~ 10:1(weight ratio).
2, it roasts: step 1 mixture is entered into kiln 650 ~ 10000C roasts 0.5 ~ 3h, obtains clinker.
The purpose of roasting is the lithium and chlorination reaction generation lithium chloride made in lithium ore, and the effect of inorganic base is to reduce to melt
The fusing point of salt system, it is fluxing, inhibit alkaline-earth metal to be chlorinated.Clinker material is loose, occasionally there is agglomeration.Roast optimal conditions are as follows: roasting
Burn temperature 650 ~ 7500C, time 1h.Lithium ore is decomposed completely, and resolution ratio is up to 98% or more.
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 leaches: the cool clinker to room temperature that step 2 is obtained, and acetone stirring leaching is added in closed container
It takes, the lithium chloride in clinker is made to be completely dissolved out, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue.
Since the valence link in chlorination lithium dimer is not typical ionic bond, can be dissolved in many organic solvents, as ethyl alcohol,
Acetone etc. is separated lithium with alkali metal using this characteristic.Practice have shown that acetone has better choice, leached using acetone
Lithium chloride.Optimal conditions: room temperature leaching, solid-to-liquid ratio are 1:4 ~ 6,1 ~ 2h of time.
4, it distills: the filtrate that step 3 obtains is heated to the boiling point 56.1 of acetone0Acetone is precipitated in gaseous state in C or more, receives
Collect recycling of condensed steam acetone, recycles Reusability.Pure anhydrous lithium chloride is made in evaporation completely.Pure anhydrous lithium chloride refers to
Non- lithium metal oxide content is trace in product, that is, is less than 50PPM.
Optimal conditions: vapo(u)rizing temperature 80 ~ 900C。
5, the filter residue that step 3 obtains Slag treatment: is heated to the boiling point 56.1 of acetone0Acetone is precipitated in gaseous state in C or more,
Recycling of condensed steam acetone is collected, Reusability is recycled.Optimal conditions: vapo(u)rizing temperature 80 ~ 1000C.Recrement can be directly used for water
The raw material of mud production;Remaining alkali and chlorinating agent can also be recycled through water logging, recycle Reusability, residue can make construction material.
Compared with prior art, the present invention having significant superiority:
(1) lithium ore sodium chloride or potassium chloride are made chlorinating agent by the present invention, in inorganic base sodium hydroxide or potassium hydroxide
It is fluxing and inhibit lower roasting, chlorination selectively is carried out to lithium ore and generates lithium chloride, lithium ore is decomposed completely, and resolution ratio reaches
98% or more, solve the problems, such as lithium ore decomposition.
(2) roasting can be carried out either statically or dynamically, and maturing temperature is low, and low energy consumption, and industrial realization is easy.
(3) initiatively in the industrial production of lithium using acetone selectively leaching dissolution lithium chloride, have selectivity good,
Raw material is easy to get, and leaching rate is up to 98% or more, not only avoids pollution of other metal ions to lithium product, reduces a large amount of
Clean link, and product quality is pure, and thoroughly solves the problems, such as that the lithium rate of recovery is low, and the lithium technique rate of recovery is up to 92% or more.
(4) it using acetone selectively dissolution lithium chloride, is not only separated by solid-liquid separation and is easy, but also the acetone in filtrate, filter residue holds
Easily recycling recycles Reusability, thoroughly solves generation and the emission problem of waste water;Also considerably reduce production cost.
(5) lithium ore, which smelts the waste residue generated, can be used for building materials, thoroughly solve the problems, such as waste sludge discharge.
(6) traditional mode of production: lithium ore → lithium hydroxide or lithium carbonate → lithium chloride → anhydrous lithium chloride → lithium metal and its
Its lithium product, the invention enables lithium ore → pure anhydrous lithium chloride → lithium metals and other lithium products to be possibly realized, and is lithium smelting
The primary great innovation of refining technology.
(7) process flow is brief, and material circulation is small, and equipment capacity is big, and capital expenditure is few.
The boiling point of acetone is generally 56.10C, but with the variation of ambient pressure, the boiling point of acetone will change, this hair
The bright boiling point 56.1 for being heated to acetone0C or more will become to be heated to the boiling point of acetone or more, as long as acetone can be made in gaseous state
Precipitation just meets the purpose of the present invention.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
Lithium ore chlorinating agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and includes the following steps:
1, lithium ore and inorganic base, chlorinating agent proportion mixing: are pressed into lithium ore: inorganic base: chlorinating agent=1:0.1:0.4(weight
Measure ratio) it is uniformly mixed, obtain mixture.
Spodumene LiAl (SiO3)21000kg mineral chemical composition: Li2O 6.65%, Al2O328.61%, SiO2
61.88%, Fe2O30.83%, Na20.16% powdery of O 0.52%, CaO 0.45%, MgO
Inorganic base: industrial sodium hydroxide sheet 100kg;Chlorinating agent: industrial chlorinations sodium 400kg.
Spodumene, industrial sodium hydroxide, industrial chlorinations sodium are ground into 80 mesh or less to be uniformly mixed together, obtain mixture.
2, it roasts: step 1 mixture is entered into kiln 7500C roasts 1.0h, obtains clinker.
Clinker material is loose, occasionally there is agglomeration.Lithium ore is decomposed completely, and resolution ratio is up to 98% or more.
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + NaCl → LiCl + RAl(SiO3)2
3, acetone leaches: the cool clinker to room temperature that step 2 is obtained, and acetone stirring leaching is added in closed container
It takes, the lithium chloride in clinker is made to be completely dissolved out, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue.
Industrial acetone 6M3, room temperature leaching, time 2h.
4, it distills: the filtrate that step 3 obtains is heated to 900Acetone is precipitated in gaseous state in C, collects recycling of condensed steam third
Ketone recycles Reusability.Pure anhydrous lithium chloride 176kg is made in evaporation completely, and non-lithium metal oxide content is trace, small
In 50PPM.
5, the filter residue that step 3 obtains Slag treatment: is heated to 1000Acetone is precipitated in gaseous state in C, collects recycling of condensed steam
Acetone recycles Reusability.Recrement can be directly used for the raw material of manufacture of cement;Remaining alkali sodium hydroxide can also be recycled by water logging
With chlorinating agent sodium chloride, Reusability is recycled, residue can make construction material.
Through process above lithium overall recovery: Li2Oη93.41%。
Embodiment 2
Lithium ore chlorinating agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and includes the following steps:
1, lithium ore and inorganic base, chlorinating agent proportion mixing: are pressed into lithium ore: inorganic base: chlorinating agent=1:0.1:0.2(weight
Measure ratio) it is uniformly mixed, obtain mixture.
Lepidolite Li2Al2Si3O9(F, OH) 1000kg mineral chemical composition: Li2O 3.95%, Al2O327.48%,
SiO250.38%, Fe2O30.05%, Na2O 0.48%, K2O 8.46%, Rb25.65% powdery of O 2.20%, F
Inorganic base: industrial sodium hydroxide sheet 100kg;Chlorinating agent: industrial chlorinations sodium 200kg.
Industrial sodium hydroxide, industrial chlorinations sodium are ground into 80 mesh or less together and lepidolite is uniformly mixed, obtains mixture.
2, it roasts: step 1 mixture is entered into kiln 6500C roasts 1.0h, obtains clinker.
Clinker material is loose, occasionally there is agglomeration.Lithium ore is decomposed completely, and resolution ratio is up to 98% or more.
The chemical reaction of roasting:
Lepidolite Li2Al2Si3O9(F,OH) + 2NaCl → 2 LiCl + Na2 Al2Si3O9(F,OH)
3, acetone leaches: the cool clinker to room temperature that step 2 is obtained, and acetone stirring leaching is added in closed container
It takes, the lithium chloride in clinker is made to be completely dissolved out, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue.
Industrial acetone 4M3, room temperature leaching, time 2h.
4, it distills: the filtrate that step 3 obtains is heated to 850Acetone is precipitated in gaseous state in C, collects recycling of condensed steam third
Ketone recycles Reusability.Pure anhydrous lithium chloride 106kg is made in evaporation completely, and non-lithium metal oxide content is trace in product
Amount, respectively less than 50PPM.
5, the filter residue that step 3 obtains Slag treatment: is heated to 900Acetone is precipitated in gaseous state in C, collects recycling of condensed steam
Acetone recycles Reusability.Recrement can be directly used for the raw material of manufacture of cement;Remaining alkali sodium hydroxide can also be recycled by water logging
With chlorinating agent sodium chloride, Reusability is recycled, residue can make construction material.
Through process above lithium overall recovery: Li2Oη94.71%。
Embodiment 3
Lithium ore chlorinating agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and includes the following steps:
1, lithium ore and inorganic base, chlorinating agent proportion mixing: are pressed into lithium ore: inorganic base: chlorinating agent=1:0.1:0.4(weight
Measure ratio) it is uniformly mixed, obtain mixture.
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 0.064% powdery of 0.38%, BeO
Inorganic base: industrial sodium hydroxide sheet 100kg;Chlorinating agent: industrial chlorinations sodium 400kg.
Industrial sodium hydroxide, industrial chlorinations sodium are ground into 80 mesh or less together and lithium concentrate is uniformly mixed, obtains mixture.
2, it roasts: step 1 mixture is entered into kiln 7000C roasts 1.0h, obtains clinker.
Clinker material is loose, occasionally there is agglomeration.Lithium ore is decomposed completely, and resolution ratio is up to 98% or more.
The chemical reaction of roasting:
Spodumene LiAl (SiO3)2 + NaCl → LiCl + RAl(SiO3)2
3, acetone leaches: the cool clinker to room temperature that step 2 is obtained, and acetone stirring leaching is added in closed container
It takes, the lithium chloride in clinker is made to be completely dissolved out, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue.
Industrial acetone 6M3, room temperature leaching, time 2h.
4, it distills: the filtrate that step 3 obtains is heated to 900Acetone is precipitated in gaseous state in C, collects recycling of condensed steam third
Ketone recycles Reusability.Pure anhydrous lithium chloride 163.3kg is made in evaporation completely, and non-lithium metal oxide content is in product
Trace, respectively less than 50PPM.
5, the filter residue that step 3 obtains Slag treatment: is heated to 1000Acetone is precipitated in gaseous state in C, collects recycling of condensed steam
Acetone recycles Reusability.Recrement can be directly used for the raw material of manufacture of cement;Remaining alkali sodium hydroxide can also be recycled by water logging
With chlorinating agent sodium chloride, Reusability is recycled, residue can make construction material.
Through process above lithium overall recovery: Li2Oη95.11%。
Embodiment 4
Lithium ore chlorinating agent inorganic base roasting acetone leaching of the present invention extracts lithium technique and includes the following steps:
1, lithium ore and inorganic base, chlorinating agent proportion mixing: are pressed into lithium ore: inorganic base: chlorinating agent=1:0.1:0.3(weight
Measure ratio) it is uniformly mixed, obtain mixture.
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 potassium hydroxide bulk 100kg;Chlorinating agent: industrial potassium chloride 300kg.
Industrial potassium hydroxide, industrial potassium chloride are ground into 80 mesh or less together and lepidolite is uniformly mixed, obtains mixture.
2, it roasts: step 1 mixture is entered into kiln 6500C roasts 1h, obtains clinker.
Clinker material is loose, occasionally there is agglomeration.Lithium ore is decomposed completely, and resolution ratio is up to 98% or more.
The chemical reaction of roasting:
Lepidolite Li2Al2Si3O9(F,OH) + 2 KCl → 2 LiCl + K2 Al2Si3O9(F,OH)
3, acetone leaches: the cool clinker to room temperature that step 2 is obtained, and acetone stirring leaching is added in closed container
It takes, the lithium chloride in clinker is made to be completely dissolved out, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue.
Industrial acetone 5M3, room temperature leaching, time 2h.
4, it distills: the filtrate that step 3 obtains is heated to 800Acetone is precipitated in gaseous state in C, collects recycling of condensed steam third
Ketone recycles Reusability.Pure anhydrous lithium chloride 118kg is made in evaporation completely, and non-lithium metal oxide content is trace in product
Amount, respectively less than 50PPM.
5, the filter residue that step 3 obtains Slag treatment: is heated to 800Acetone is precipitated in gaseous state in C, collects recycling of condensed steam
Acetone recycles Reusability.Recrement can be directly used for the raw material of manufacture of cement;Remaining alkali potassium hydroxide can also be recycled by water logging
With chlorinating agent potassium chloride, Reusability is recycled, residue can make construction material.
Through process above lithium overall recovery: Li2Oη94.87%。
Above embodiments are to be further described to above content of the invention, but this should not be interpreted as in the present invention
The range for stating theme is only limitted to above-described embodiment, all to belong to the scope of the present invention based on the method that above content is realized.
Claims (8)
1. lithium ore chlorinating agent inorganic base roasts organic solvent leaching and extracts lithium technique, feature includes the following steps:
(1) mixing: by lithium ore and inorganic base, chlorinating agent quality proportioning by lithium ore: inorganic base: chlorinating agent=1:0.1:0.2 ~
0.4 is uniformly mixed, and obtains mixture, lithium ore refers to spodumene and/or lepidolite;Inorganic base refers to sodium hydroxide and/or hydrogen-oxygen
Change potassium;Chlorinating agent refers to sodium chloride and/or potassium chloride;
(2) it roasts: step (1) mixture is entered into kiln 650 ~ 10000C roasts 0.5 ~ 3h, obtains clinker, and lithium ore is decomposed sufficiently, decomposed
Rate is up to 98% or more;
(3) acetone leaches: the cool clinker to room temperature that step (2) are obtained, and acetone stirring leaching is added in closed container
It takes, is dissolved out the lithium chloride in clinker sufficiently, extraction rate is greater than 98%, is separated by solid-liquid separation to obtain filtrate and filter residue;
(4) it distills: the filtrate that step (3) obtain being heated to the boiling point of acetone or more, acetone is precipitated in gaseous state, it is cold to collect steam
Solidifying recycling acetone, recycles Reusability, and pure anhydrous lithium chloride is made in evaporation completely;
(5) Slag treatment: the filter residue that step (3) obtain is heated to the boiling point of acetone or more, acetone is precipitated in gaseous state, collects steam
Condensing recovery acetone recycles Reusability;Recrement can be directly used for the raw material of manufacture of cement;Remaining alkali and chlorine can also be recycled through water logging
Agent, recycles Reusability, and residue can make construction material.
2. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: lithium ore refers to spodumene and/or lepidolite in step (1);Inorganic base refers to sodium hydroxide and/or potassium hydroxide;
Chlorinating agent refers to sodium chloride and/or potassium chloride, and chlorinating agent dosage presses the 110 ~ 130% of theoretical reacting dose.
3. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: step (2) roasting makes the lithium and chlorination in lithium ore in the fluxing of inorganic base and under inhibiting alkaline-earth metal to be chlorinated
Agent reaction generates 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.
4. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: step (2) roasts optimal conditions are as follows: temperature 650 ~ 7500C, time 1h, lithium ore are decomposed sufficiently, and resolution ratio is up to 98%
More than.
5. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: lithium chloride of the step (3) in acetone selectively leaching clinker.
6. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: step (3) the lithium chloride optimal conditions in acetone leaching clinker: room temperature leaches, and solid-to-liquid ratio is 1:4 ~ 6, when
Between 1 ~ 2h, extraction rate be greater than 98%.
7. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: the filtrate is heated to the boiling point of acetone or more by step (4), and acetone is precipitated in gaseous state, and evaporation is made pure completely
Net anhydrous lithium chloride, pure anhydrous lithium chloride refer to that non-lithium metal oxide content is trace in product, that is, is less than 50PPM.
8. lithium technique is extracted by the roasting organic solvent leaching of lithium ore chlorinating agent inorganic base described in claims 1, it is special
Sign is: the filter residue that step (3) obtain is heated to the boiling point of acetone or more by step (5) Slag treatment, and acetone is precipitated in gaseous state, is received
Collect recycling of condensed steam acetone, recycle Reusability, recrement can be applied directly.
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