CN111187924B - Continuous lithium smelting device and method for lithium-containing material - Google Patents
Continuous lithium smelting device and method for lithium-containing material Download PDFInfo
- Publication number
- CN111187924B CN111187924B CN202010151000.7A CN202010151000A CN111187924B CN 111187924 B CN111187924 B CN 111187924B CN 202010151000 A CN202010151000 A CN 202010151000A CN 111187924 B CN111187924 B CN 111187924B
- Authority
- CN
- China
- Prior art keywords
- lithium
- isolation valve
- chamber
- aluminum
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 205
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000003723 Smelting Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000010439 graphite Substances 0.000 claims abstract description 67
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 67
- 230000006698 induction Effects 0.000 claims abstract description 52
- 238000007599 discharging Methods 0.000 claims abstract description 46
- 238000002955 isolation Methods 0.000 claims description 154
- 238000006722 reduction reaction Methods 0.000 claims description 115
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 54
- -1 aluminum-silicon-calcium Chemical compound 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000003638 chemical reducing agent Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000292 calcium oxide Substances 0.000 claims description 37
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 37
- 229910000676 Si alloy Inorganic materials 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 34
- 239000008188 pellet Substances 0.000 claims description 33
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical group [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000605 extraction Methods 0.000 claims description 28
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 25
- 239000012752 auxiliary agent Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 23
- 238000007670 refining Methods 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 21
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000002802 bituminous coal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000002006 petroleum coke Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 13
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 13
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005292 vacuum distillation Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 8
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 6
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000005674 electromagnetic induction Effects 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 20
- 238000010924 continuous production Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052642 spodumene Inorganic materials 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization 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
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
Abstract
The invention provides a continuous lithium smelting device and method for lithium-containing materials, and belongs to the field of resource utilization. The invention has the following technical effects: the induction heating device and the graphite crucible are heated, so that the heating is rapid and uniform, the reduction time is controlled to be 2 hours after each charging, and the time is saved; the vertical reduction chamber is always in a molten state and is not bonded with the reduction slag, slag is discharged rapidly, the slag discharging problem of the shaft furnace is solved, and the feeding and discharging are carried out from the lower end, so that the process is more convenient; in the whole working process, the reduction chamber is not cooled and vacuum is not broken, continuous production can be realized, the labor efficiency is improved, energy conservation and environmental protection are realized, the production efficiency is improved, continuous production is realized, the service life of equipment can be prolonged, meanwhile, the vacuum degree is kept, the purity of lithium is high, compared with the existing lithium smelting technology, the current efficiency is 90%, the recovery rate of lithium is more than 90%, and the purity of lithium is as high as 99.9%.
Description
Technical Field
The invention relates to the technical field of resource utilization, in particular to a continuous lithium smelting device and method for lithium-containing materials.
Background
At present, consumer electronic products represented by batteries, notebook computers and mobile phones have vigorous demands for lithium batteries, and are main power for pulling the growth of lithium metal demands. Along with the progress and development of science and technology, people have increasingly high requirements on environmental protection, and the development of electric locomotives, electric bicycles and new energy automobiles is promoted, and the lead-acid batteries are heavy and inconvenient and are easy to cause traffic accidents, so that the pace of replacing the lead-acid batteries with the future lithium batteries is further accelerated, and especially the popularization of the new energy automobiles greatly stimulates the requirements of the lithium batteries.
Lithium exists in nature mainly in two types, one in the form of lithium-containing ores such as spodumene, lepidolite, petalite and the like, and the other in the form of lithium ions in salt lake brine, underground brine and seawater. At present, the main current technology for industrially producing lithium metal is a molten salt electrolysis method and a vacuum reduction method for smelting lithium, wherein the molten salt electrolysis method takes lithium chloride (LiCl) as a raw material and potassium chloride as an electrolyte, so that the effects of stabilization, cooling and electric conduction are achieved, and the electrolysis temperature is about 450-500 ℃. The method has the defects that firstly, lithium in spodumene is extracted into lithium carbonate and then is converted into lithium chloride, the production cost is high, and 5 tons of chlorine gas is generated when 1 ton of lithium is produced, so that the air is seriously polluted; the vacuum reduction method is also used for refining lithium by taking lithium carbonate or lithium hydroxide monohydrate as raw materials, but the existing vacuum reduction method lithium refining equipment has the problems of incapability of continuous production and low labor efficiency.
Disclosure of Invention
In view of the above, the present invention is directed to a device and a method for continuously smelting lithium from a lithium-containing material. The device provided by the invention can be used for continuous production, so that the labor efficiency is improved, and the service life of equipment is prolonged.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a continuous lithium smelting device for lithium-containing materials, which comprises: the device comprises a reduction chamber (1), a graphite crucible (11), an electrical appliance control system (4), a vacuum unit (14), a hydraulic system (12) and a water cooling system (13);
the bottom of the reduction chamber (1) is provided with an induction heating device (2), the induction heating device (2) is connected with a heating power supply (3), a crucible lifting device (8) is arranged below the induction heating device (2), an isolation valve 1 (16) is arranged between the induction heating device (2) and the crucible lifting device (8), the reduction chamber (1) is connected with a vacuum unit (14) through an isolation valve 5 (18), the reduction chamber (1) is communicated with a crystallizer (17), the crystallizer (17) is connected with a metal lithium tank (21) through an isolation valve 6 (19), and the crystallizer (17) is connected with the vacuum unit (14) through an isolation valve 7 (20);
the two sides of the crucible lifting device (8) are respectively provided with a feeding chamber (5) and a discharging chamber (10), an isolation valve 4 (7) is arranged between the crucible lifting device (8) and the feeding chamber (5), and an isolation valve 3 (9) is arranged between the crucible lifting device (8) and the discharging chamber (10); the vacuum unit (14) is communicated with the discharge chamber (10) through the isolation valve 2 (15);
The graphite crucible (11) moves among the feeding chamber (5), the crucible lifting device (8) and the discharging chamber (10) through the moving device (6);
the electric appliance control system (4) is respectively connected with the reduction chamber (1), the feeding chamber (5), the discharging chamber (10), the crystallizer (17), the isolation valve 1 (16), the isolation valve 2 (15), the isolation valve 3 (9), the isolation valve 4 (7), the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20), and the electric appliance control system (4) comprises a temperature measuring device and a vacuum detecting device, and displays the temperature and the vacuum degree;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the crucible lifting device (8) to lift;
the water cooling system (13) is respectively connected with the reduction chamber (1), the induction heating device (2), the vacuum unit (14) and the crystallizer (17).
Preferably, the reduction chamber (1) is of a double-layer water-cooling structure.
Preferably, the lithium metal tank (21) contains liquid paraffin.
Preferably, a graphite filter is arranged in the crystallization chamber (17).
Preferably, the induction heating device (2) is an electromagnetic induction heating device.
The invention also provides a continuous lithium smelting method for the lithium-containing material, which adopts the technical scheme, and comprises the following steps:
Manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve 4 (7) through an electrical control system 4, and moving the graphite crucible 11 to a crucible lifting device 8 through a moving device 6; opening an isolation valve 1 (16), and lifting the graphite crucible 11 into the induction heating device 2 through a crucible lifting device 8; opening a vacuum unit (14) through an electrical control system (4), opening an isolation valve 2 (15) and an isolation valve 3 (9), and vacuumizing a discharge chamber (10) and a feed chamber (5); opening the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20) to vacuumize the reduction chamber (1), the crystallizer (17) and the lithium metal tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, collecting lithium in a liquid state in a crystallization chamber (17), and flowing into a metal lithium tank (21);
after the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) and the isolation valve 4 (7) are closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum;
The hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8).
Preferably, the temperature of the crystallization chamber (17) is 200-300 ℃.
Preferably, when the lithium-containing material is lithium carbonate or lithium hydroxide monohydrate, the auxiliary agent is a mixture of aluminum oxide and calcium oxide, and the reducing agent is aluminum-silicon alloy.
Preferably, when the lithium-containing material is a lithium-containing mineral, the auxiliary agent comprises a metal oxide and the reducing agent comprises one or more of aluminum, magnesium, silicon, calcium, a calcium-silicon alloy, an aluminum-magnesium alloy, an aluminum-silicon alloy, and a silicon-magnesium alloy.
Preferably, the reduction reaction further comprises the following steps:
mixing lithium extraction tailings of the lithium-containing material obtained in the discharging chamber (10), a reducing agent, a binder and water, and agglomerating to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for preparing metal lithium from lithium-containing materials and extracting lithium tailings;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain the metal calcium and aluminum-silicon alloy.
The invention provides a continuous lithium smelting device for lithium-containing materials, which comprises: the device comprises a reduction chamber (1), a graphite crucible (11), an electrical appliance control system (4), a vacuum unit (14), a hydraulic system (12) and a water cooling system (13);
the bottom of the reduction chamber (1) is provided with an induction heating device (2), the induction heating device (2) is connected with a heating power supply (3), a crucible lifting device (8) is arranged below the induction heating device (2), an isolation valve 1 (16) is arranged between the induction heating device (2) and the crucible lifting device (8), the reduction chamber (1) is connected with a vacuum unit (14) through an isolation valve 5 (18), the reduction chamber (1) is communicated with a crystallizer (17), the crystallizer (17) is connected with a metal lithium tank (21) through an isolation valve 6 (19), and the crystallizer (17) is connected with the vacuum unit (14) through an isolation valve 7 (20);
the two sides of the crucible lifting device (8) are respectively provided with a feeding chamber (5) and a discharging chamber (10), an isolation valve 4 (7) is arranged between the crucible lifting device (8) and the feeding chamber (5), and an isolation valve 3 (9) is arranged between the crucible lifting device (8) and the discharging chamber (10); the vacuum unit (14) is communicated with the discharge chamber (10) through the isolation valve 2 (15);
the graphite crucible (11) moves among the feeding chamber (5), the crucible lifting device (8) and the discharging chamber (10) through the moving device (6);
The electric appliance control system (4) is respectively connected with the reduction chamber (1), the feeding chamber (5), the discharging chamber (10), the crystallizer (17), the isolation valve 1 (16), the isolation valve 2 (15), the isolation valve 3 (9), the isolation valve 4 (7), the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20), and the electric appliance control system (4) comprises a temperature measuring device and a vacuum detecting device, and displays the temperature and the vacuum degree;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the crucible lifting device (8) to lift;
the water cooling system (13) is respectively connected with the reduction chamber (1), the induction heating device (2), the vacuum unit (14) and the crystallizer (17).
The invention has the following technical effects:
(1) The induction heating device and the graphite crucible are heated, heating is rapid and uniform, the reduction time after each feeding is controlled to be 2 hours, and time is saved.
(2) And the material feeding and discharging are smooth. Firstly, the reduction chamber is vertical and is always in a molten state and is not bonded with the reduction slag in a reaction way, secondly, slag is discharged rapidly, and the slag discharging problem of the shaft furnace is solved; thirdly, the material is fed and discharged from the lower end, which is more convenient.
(3) In the whole working process, the reduction chamber is not cooled and vacuum is not broken, continuous production can be realized, the labor efficiency is improved, energy conservation and environmental protection are realized, the production efficiency is improved, continuous production is realized, the service life of equipment can be prolonged, meanwhile, the vacuum degree is kept, the purity of lithium is high, compared with the existing lithium smelting technology, the current efficiency is 90%, the recovery rate of lithium is more than 90%, and the purity of lithium is as high as 99.9%.
Further, the crystallizer is provided with a graphite filter and a metal lithium tank, the metal lithium is in a liquid state, the temperature in the crystallizer is controlled to be 200-300 ℃, and the purity of the lithium is high.
The invention also provides a continuous lithium smelting method for the lithium-containing material, which realizes continuous lithium smelting without solid waste discharge.
Drawings
FIG. 1 is a schematic diagram of a continuous lithium-smelting device for lithium-containing materials, wherein a 1-reduction chamber, a 2-induction heating device, a 3-heating power supply, a 4-electric control system, a 5-feeding chamber, a 6-moving device, a 7-isolation valve 4, an 8-crucible lifting device, a 9-isolation valve 3, a 10-discharging chamber, an 11-graphite crucible, a 12-hydraulic system, a 13-water cooling system, a 14-vacuum unit, a 15-isolation valve 2, a 16-isolation valve 1, a 17-crystallizer, an 18-isolation valve 5, a 19-isolation valve 6, a 20-isolation valve 7, and a 21-metallic lithium tank are arranged;
fig. 2 is a flow chart of a method for continuous lithium-smelting without solid waste by using spodumene as lithium-containing material in example 1.
Detailed Description
The invention provides a continuous lithium smelting device for lithium-containing materials, which comprises: the device comprises a reduction chamber (1), a graphite crucible (11), an electrical appliance control system (4), a vacuum unit (14), a hydraulic system (12) and a water cooling system (13);
the bottom of the reduction chamber (1) is provided with an induction heating device (2), the induction heating device (2) is connected with a heating power supply (3), a crucible lifting device (8) is arranged below the induction heating device (2), an isolation valve 1 (16) is arranged between the induction heating device (2) and the crucible lifting device (8), the reduction chamber (1) is connected with a vacuum unit (14) through an isolation valve 5 (18), the reduction chamber (1) is communicated with a crystallizer (17), the crystallizer (17) is connected with a metal lithium tank (21) through an isolation valve 6 (19), and the crystallizer (17) is connected with the vacuum unit (14) through an isolation valve 7 (20);
The two sides of the crucible lifting device (8) are respectively provided with a feeding chamber (5) and a discharging chamber (10), an isolation valve 4 (7) is arranged between the crucible lifting device (8) and the feeding chamber (5), and an isolation valve 3 (9) is arranged between the crucible lifting device (8) and the discharging chamber (10); the vacuum unit (14) is communicated with the discharge chamber (10) through the isolation valve 2 (15);
the graphite crucible (11) moves among the feeding chamber (5), the crucible lifting device (8) and the discharging chamber (10) through the moving device (6);
the electric appliance control system (4) is respectively connected with the reduction chamber (1), the feeding chamber (5), the discharging chamber (10), the crystallizer (17), the isolation valve 1 (16), the isolation valve 2 (15), the isolation valve 3 (9), the isolation valve 4 (7), the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20), and the electric appliance control system (4) comprises a temperature measuring device and a vacuum detecting device, and displays the temperature and the vacuum degree;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the crucible lifting device (8) to lift;
the water cooling system (13) is respectively connected with the reduction chamber (1), the induction heating device (2), the vacuum unit (14) and the crystallizer (17).
FIG. 1 is a schematic diagram of a continuous lithium-smelting device for lithium-containing materials, wherein a 1-reduction chamber, a 2-induction heating device, a 3-heating power supply, a 4-electric control system, a 5-feeding chamber, a 6-moving device, a 7-isolation valve 4, an 8-crucible lifting device, a 9-isolation valve 3, a 10-discharging chamber, an 11-graphite crucible, a 12-hydraulic system, a 13-water cooling system, a 14-vacuum unit, a 15-isolation valve 2, a 16-isolation valve 1, a 17-crystallizer, an 18-isolation valve 5, a 19-isolation valve 6, a 20-isolation valve 7 and a 21-metallic lithium tank are arranged.
In the invention, the reduction chamber (1) is preferably a double-layer water-cooling structure.
In the invention, the metal lithium tank (21) contains liquid paraffin, the metal lithium tank (21) is preferably removed from the crystallization chamber (17) periodically, connected to a glove box filled with high-purity argon, and then a valve of the metal lithium tank is opened to obtain a lithium ingot.
In the invention, a graphite filter is preferably arranged in the crystallization chamber (17), which can filter dust and also acts as a temperature diffusion prevention.
In the present invention, the induction heating device (2) is preferably an electromagnetic induction heating device.
The invention also provides a continuous lithium smelting method for the lithium-containing material, which adopts the technical scheme, and comprises the following steps:
manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve 4 (7) through an electrical control system 4, and moving the graphite crucible 11 to a crucible lifting device 8 through a moving device 6; opening an isolation valve 1 (16), and lifting the graphite crucible 11 into the induction heating device 2 through a crucible lifting device 8; opening a vacuum unit (14) through an electrical control system (4), opening an isolation valve 2 (15) and an isolation valve 3 (9), and vacuumizing a discharge chamber (10) and a feed chamber (5); opening the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20) to vacuumize the reduction chamber (1), the crystallizer (17) and the lithium metal tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, collecting lithium in a liquid state in a crystallization chamber (17), and flowing into a metal lithium tank (21);
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) and the isolation valve 4 (7) are closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8).
In the present invention, when the lithium-containing material is preferably lithium carbonate or lithium hydroxide monohydrate, the auxiliary agent is preferably a mixture of aluminum oxide and calcium oxide, and the reducing agent is preferably an aluminum-silicon alloy.
In the present invention, the purity of both the lithium carbonate and the lithium hydroxide monohydrate is preferably 98% or more, and the purity of both the aluminum oxide and the calcium oxide is preferably more than 98%. In the present invention, the lithium carbonate or lithium hydroxide monohydrate: alumina: the mass ratio of the calcium oxide is preferably 2-3:1-1.5:1-1.5.
In the present invention, it is preferable that the lithium carbonate or lithium hydroxide monohydrate and the auxiliary agent are mixed and then calcined and ground in this order, and the obtained mixture, the reducing agent and the catalyst are mixed and then pressed into pellets and placed in a graphite crucible (11). In the present invention, the baking temperature is preferably 750 to 850℃and the time is preferably 60 to 100 minutes. In the present invention, the grinding is preferably to 60 mesh. In the invention, the aluminum-silicon alloy is preferably added in the form of aluminum-silicon alloy powder, the granularity of the aluminum-silicon alloy powder is preferably 60 meshes, and the adding amount is preferably 5-10% of the total mass of the mixture of lithium carbonate or lithium hydroxide monohydrate and the auxiliary agent after roasting.
In the present invention, the catalyst is preferably CaF 2 CaF in the graphite crucible (11) 2 The mass fraction of (2) is preferably 2 to 5%, more preferably 3 to 4%.
In the present invention, the temperature of the reduction reaction is preferably 1100 to 1200 ℃, the vacuum degree is preferably 5 to 10Pa, and the time is preferably 1 to 2 hours.
Lithium obtained by the reduction reaction is collected in a liquid form in a crystallizer (17). In the present invention, the temperature of the crystallizer (17) is preferably 200 to 300 ℃.
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) and the isolation valve 4 (7) are closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum. In the invention, the lithium extraction tailings obtained by the reduction reaction preferably comprise CaO.7Al 2 O 3 (s) (slag), 2CaO.SiO 2 (s)，CaO(s)·SiO 2 (s) and Al 2 O 3 ·2SiO 2 The chemical components are preferably: 40-50 wt% of calcium oxide, 40-60 wt% of aluminum oxide, 15-30 wt% of silicon oxide and the balance of other oxides.
In the present invention, when the lithium-containing material is preferably a lithium-containing mineral, the auxiliary agent preferably includes a metal oxide, and the preferred reducing agent includes one or more of aluminum, magnesium, silicon, calcium, a calcium-silicon alloy, an aluminum-magnesium alloy, an aluminum-silicon alloy, and a silicon-magnesium alloy.
In the present invention, it is preferable to further include a catalyst CaF 2 Put into a graphite crucible (11) for reduction reaction. In the invention, the catalyst CaF in the graphite crucible (11) 2 The mass fraction of (2) is preferably 2 to 5%, more preferably 3 to 4%.
In the invention, the metal oxide active lime preferably comprises the following components in percentage by weight of CaO more than or equal to 95 percent by weight and SiO 2 ≤1.0wt％，P≤0.03wt％，S≤0.03wt％。
In the present invention, the lithium-containing mineral is preferably spodumene.
In the invention, the mass ratio of the lithium-containing mineral, the auxiliary agent and the reducing agent is preferably (45-50): (40-45): (5-10).
In the present invention, the reduction reaction preferably includes a first reduction and a second reduction in sequence,
the temperature of the first reduction is preferably 500-700 ℃, more preferably 550-650 ℃, the vacuum degree of the first reduction is preferably 1-50 Pa, more preferably 20-45 Pa, the heating rate of the first reduction to the temperature of the first reduction is preferably 5-15 ℃/min, more preferably 8-14 ℃/min, and the heat preservation time of the first reduction is preferably 30-60 min, more preferably 40-50 min;
the temperature of the second reduction is preferably 1100-1300 ℃, more preferably 1150-1250 ℃, the vacuum degree of the second reduction is preferably 1000-1200 Pa, more preferably 1050-1150 Pa, the heating rate of the second reduction to the second reduction is preferably 5-15 ℃/min, more preferably 9-12 ℃/min, and the heat preservation time of the second reduction is preferably 2.5-3 h. In the present invention, the incubation time of the second reduction can ensure that no lithium vapor is generated any more.
In the invention, spodumene is taken as an example, a catalyst is added, an auxiliary agent is metal oxide such as calcium oxide, and a reducing agent is aluminum-silicon alloy, and the process of the reduction reaction is as follows:
7[Li 2 O·Al 2 O 3 ·4SiO 2 ](spodumene) +43CaO (auxiliary agent) +2[ AlSi)](reducing agent) =cao.7al 2 O 3 (s) (slag) +14[ 2CaO.SiO 2 (s)]+14[Li](g) (metallic lithium) +14[ CaO(s) & SiO 2 (s)](slag) + [ Al 2 O 3 ·2SiO 2 ](slag)
Lithium obtained by the reduction reaction is collected in a liquid form in a crystallizer (17) for crystallization. In the present invention, the temperature of the crystallizer (17) is preferably 200 to 300 ℃.
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) and the isolation valve 4 (7) are closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum. In the invention, the lithium extraction tailings obtained by the reduction reaction preferably comprise CaO.7Al 2 O 3 (s) (slag), 2CaO.SiO 2 (s)，CaO(s)·SiO 2 (s) and Al 2 O 3 ·2SiO 2 The chemical components preferably include: 30-50 wt% of calcium oxide, 15-30 wt% of aluminum oxide, 30-50 wt% of silicon oxide, the balance of ferric oxide and the like.
After the reduction reaction is finished, preferably mixing the lithium-containing material extracted from the discharge chamber (10), a reducing agent, a binder and water, and agglomerating to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
Carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for preparing raw materials of lithium metal and lithium extraction tailings from lithium-containing materials;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain the metal calcium and aluminum-silicon alloy.
According to the invention, the lithium-containing material obtained in the discharging chamber (10) is subjected to lithium extraction tailings, a reducing agent, a binder and water, and then is subjected to agglomeration to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke.
In the present invention, the pellets preferably comprise the following components in weight percent: 50-65% of lithium extraction tailings of lithium-containing materials, 20-40% of reducing agents, 5-8% of binders and 4-6% of water, wherein the sum of the mass percentages of the components is 100%. The kind of the binder is not particularly limited, and the kind of the binder known to those skilled in the art may be used.
In the invention, the lithium extraction slag and the reducing agent of the lithium-containing material are preferably independently ground into powder with the granularity smaller than 1mm and then used.
In the invention, the mass ratio of the bituminous coal to the petroleum coke is preferably 8:2 to 6:4.
In the present invention, the fixed carbon content of the bituminous coal is preferably 40 to 60%, and the fixed carbon content of the petroleum coke is preferably 80 to 90%. In the present invention, the sum of the fixed carbon contents in the bituminous coal and the petroleum coke is preferably 93 to 95% of the theoretical requirement that the reduction reaction be completely performed.
In the present invention, the pellets are preferably produced in a pelletizer, and the pressure of the pellets is preferably 20 to 30MPa.
In the invention, the agglomeration preferably further comprises drying, and the drying is preferably carried out at 100-200 ℃ until the mass percentage of water in the pellets is not more than 1%.
After the pellets are obtained, the pellets are subjected to a reduction reaction to obtain aluminum-silicon-calcium alloy liquid and scum, and the scum is used for preparing a metal lithium auxiliary agent from lithium extraction tailings of lithium-containing materials.
In the present invention, the temperature of the reduction reaction is preferably 1600 to 1900 ℃, more preferably 1550 to 1600 ℃, and the time is preferably 2 to 3 hours. The invention uses the lithium extraction tailings of the lithium-containing material, and the lithium extraction tailings of the lithium-containing material contain a large amount of calcium oxide, so the temperature of the reduction reaction is low. In the present invention, the reduction reaction is preferably performed in an ac or dc ore-smelting electric arc furnace.
In the present invention, the yield of the dross is preferably 2 to 5%, and the main components of the dross include 30 to 50% by weight of calcium oxide, 15 to 30% by weight of aluminum oxide, 30 to 50% by weight of silicon oxide, and the balance of other oxides.
After the reduction reaction is completed, the aluminum-silicon-calcium alloy liquid is preferably discharged from an aluminum outlet ladle at regular intervals. In the present invention, the regular intervals are preferably 2 to 3 hours.
After the aluminum-silicon-calcium alloy liquid is obtained, the aluminum-silicon-calcium alloy liquid is mixed with a refining agent for refining, so that the aluminum-silicon-calcium alloy is obtained. In the invention, because the aluminum-silicon-calcium alloy liquid contains a certain amount of nonmetallic impurities, a refining agent is added into a ladle to remove slag. The type and amount of the refining agent are not particularly limited, and those skilled in the art can use conventional techniques.
In the invention, the refining preferably comprises vacuum filtration to remove slag, mixing and diluting, and then casting ingot to obtain the aluminum-silicon-calcium alloy. In the present invention, the aluminum-silicon-calcium alloy preferably comprises the following components: 30-45 wt% of aluminum, 20-40 wt% of silicon, 20-45 wt% of calcium and the balance of other elements contained in raw materials entering the aluminum-silicon-calcium alloy through refining.
After the aluminum-silicon-calcium alloy is obtained, the aluminum-silicon-calcium alloy is subjected to vacuum distillation to obtain the metal calcium and aluminum-silicon alloy. In the present invention, the vacuum degree of the vacuum distillation is preferably 0.5 to 20Pa, the temperature is preferably 1000 to 1300 ℃, and the time is preferably 2 to 5 hours. In the present invention, it is preferable that the aluminum-silicon-calcium alloy is crushed into pieces having a particle size of 10cm or less, and then placed in a vacuum distillation tank for vacuum distillation. In the invention, after the vacuum distillation is completed, calcium is distilled out and condensed into solid metal calcium, and the rest material is aluminum-silicon alloy. In the present invention, the aluminum-silicon alloy preferably comprises the following components: 35 to 50 weight percent of Al, 40 to 60 weight percent of Si, 0.001 to 0.005 weight percent of Ca and the balance of other elements contained in the raw materials entering the aluminum-silicon-calcium alloy through refining. In the invention, the aluminum-silicon alloy is preferably recycled as a lithium extracting reducing agent for lithium-containing materials.
For further explanation of the present invention, the apparatus and method for continuous lithium-making of lithium-containing materials provided in the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The examples of the present invention were all carried out in a continuous lithium-making plant for lithium-containing materials as shown in fig. 1.
Example 1
Fig. 2 is a flow chart of a method for continuously smelting lithium without solid waste by taking spodumene as a lithium-containing material in example 1, crushing and grinding the lithium-containing material, mixing the crushed material with an auxiliary agent and a reducing agent, pressing balls, carrying out reduction reaction in a continuous lithium-smelting device for the lithium-containing material shown in fig. 1 to obtain metal lithium and lithium extraction tailings, carrying out reduction reaction on the lithium extraction tailings, the reducing agent and a binder mixed pressed balls to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for preparing the metal lithium from the lithium-containing material, refining the aluminum-silicon-calcium alloy liquid to obtain aluminum-silicon-calcium alloy, carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy, and using the aluminum-silicon alloy as the reducing agent for extracting lithium from the lithium-containing material.
The first furnace starts: according to the weight ratio of the dry spodumene to the lithium-containing material (crushed and ground), calcium oxide and aluminum-silicon alloy of 45:45:5 ingredients, and CaF is added 2 Forming a mixed raw material, forming the mixed raw material, and pressing the mixed raw material into pellets under 50 Mpa; the pellet size of the pressed mixed raw material is about 40mm. The adopted silicon-calcium alloy is in powder shape, the fineness is 120 meshes, and the chemical components are silicon: 60wt%, aluminum: 40wt%.
Manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve 4 (7) through an electrical control system 4, and moving the graphite crucible 11 to a crucible lifting device 8 through a moving device 6; opening an isolation valve 1 (16), and lifting the graphite crucible 11 into the induction heating device 2 through a crucible lifting device 8; opening a vacuum unit (14) through an electrical control system (4), opening an isolation valve 2 (15) and an isolation valve 3 (9), and vacuumizing a discharge chamber (10) and a feed chamber (5); opening the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20) to vacuumize the reduction chamber (1), the crystallizer (17) and the lithium metal tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, heating the induction heating device (2) to 550 ℃ at a heating rate of 14 ℃/min, keeping the temperature for 50min, and keeping the vacuum degree at 1Pa; continuously heating, heating to 1150 ℃ at a heating rate of 14 ℃/min, controlling the vacuum degree of a vacuum reactor to 1050Pa, keeping the vacuum reactor at a constant temperature for about 3 hours until no lithium steam is generated, collecting lithium in a liquid form in a crystallizer (17), connecting a crystallization chamber (17) with a metal lithium tank (21), meanwhile, arranging a graphite filter, containing liquid paraffin in the metal lithium tank (20), periodically taking down the metal lithium tank (21) from the crystallization chamber (17), connecting the metal lithium tank to a glove box filled with high-purity argon, and then opening a valve of the metal lithium tank to obtain a lithium ingot with purity of 99.9%, recovery rate of 92% and current efficiency of 90%;
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 4 (7) is closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8);
the water cooling system (13) is respectively connected with the vacuum unit (14), the reduction chamber (1), the induction heating device (2) and the crystallization chamber (17).
The second furnace starts: closing the isolation valve 4 (7), manually opening the feeding chamber (5), filling the graphite crucible (11) with materials, closing the door of the feeding chamber (5), vacuumizing the feeding chamber (5) to the process requirement vacuum degree, opening the isolation valve 4 (7), moving the graphite crucible (11) to the crucible lifting device (8) through the moving device (6), opening the isolation valve 1 (16), lifting the graphite crucible (11) into the induction heating device (2) through the crucible lifting device (8), wherein the vacuum degree and the temperature of the reduction chamber (1) meet the process requirement of the reduction reaction, and the reduction reaction starts, so that lithium is collected in the crystallizer (17) in a liquid state and flows into the metal lithium tank (21). After the reaction is completed, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 3 (9) is opened, the mobile device (6) enters the discharge chamber (10), the isolation valve 3 (9) is closed, the discharge chamber (10) is subjected to vacuum breaking, the graphite crucible (11) is taken out, the residues of the graphite crucible (11) are cleaned, the door of the discharge chamber (10) is closed, and the discharge chamber (10) is vacuumized to the process requirement vacuum degree, and the process is sequentially circulated.
The lithium extraction tailings obtained in the discharge chamber (10) preferably comprise CaO.7Al 2 O 3 (s) (slag), 2CaO.SiO 2 (s)，CaO(s)·SiO 2 (s) and Al 2 O 3 ·2SiO 2 Chemical components: 50wt% of calcium oxide, 15wt% of aluminum oxide, 30wt% of silicon oxide, the balance of ferric oxide and the like.
Grinding lithium extraction tailings obtained in a discharge chamber (10) to obtain powder with the granularity of 100-120 meshes, mixing the lithium extraction tailings powder, a reducing agent, a binder and water, agglomerating at 30MPa, and dehydrating at 200 ℃ until the mass percentage of water in the pellets is not more than 1%, wherein the pellets comprise the following components in percentage by weight: 50% of lithium-containing material lithium extraction tailings powder, 40% of a reducing agent, 5% of a binder and 5% of water, wherein the reducing agent comprises bituminous coal and petroleum coke (the mass ratio is 8:2), the fixed carbon content of the bituminous coal is 40%, the fixed carbon content of the petroleum coke is 80%, the sum of the fixed carbon contents in the bituminous coal and the petroleum coke is 93% of the theoretical requirement of the complete reduction reaction, the pellets undergo reduction reaction at 1900 ℃ for 2 hours to obtain aluminum-silicon-calcium alloy liquid and scum, the aluminum-silicon-calcium alloy liquid is regularly lifted from an aluminum outlet at intervals of 2 hours, the scum is used for preparing a metal lithium auxiliary agent from the lithium-containing material lithium extraction tailings, the yield of the scum is 2%, the main components of the scum comprise 50wt% of calcium oxide, 15wt% of aluminum oxide, 30wt% of silicon oxide and the balance of other oxides; mixing the aluminum-silicon-calcium alloy liquid with a refining agent, performing vacuum filtration to remove slag, mixing and diluting, and then casting ingot to obtain the aluminum-silicon-calcium alloy, wherein the aluminum-silicon-calcium alloy comprises the following components: 30wt% of aluminum, 40wt% of silicon and 20wt% of calcium, and the balance of other elements contained in raw materials entering the aluminum-silicon-calcium alloy through refining, wherein the aluminum-silicon-calcium alloy is subjected to vacuum distillation (the vacuum degree is 0.5Pa, the temperature is 1000 ℃ and the time is 2 h) to obtain metal calcium and aluminum-silicon alloy, and the aluminum-silicon alloy comprises the following components: 40wt% of Al, 58wt% of Si, 0.005wt% of Ca and the balance of other elements contained in the raw materials which are refined into the aluminum-silicon-calcium alloy, wherein the aluminum-silicon alloy is preferably recycled as a lithium extracting reducing agent for lithium-containing materials.
Example 2
Continuous lithium smelting by using lithium carbonate as raw material
The first furnace starts: the lithium carbonate is used as raw material, the mixture of alumina and calcium oxide is used as auxiliary agent, and the aluminium-silicon alloy is used as reducer. Wherein the purity of the lithium carbonate is more than 98 percent. The purity of the alumina and the calcium oxide is more than 98 percent. The proportion (mass ratio): lithium carbonate: alumina: calcium oxide=2:1:1, and the mixture is uniformly mixed, baked at 750 ℃ for 100 minutes. Grinding to 60 mesh after the mixture is burnt, adding aluminum-silicon alloy powder with granularity of 60 mesh and adding CaF accounting for 2% of the mixture after the mixture of lithium carbonate, aluminum oxide and calcium oxide is roasted to 8% of the mixture 2 The mixed raw materials are obtained and pressed into pellets.
Manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve 4 (7) through an electrical control system 4, and moving the graphite crucible 11 to a crucible lifting device 8 through a moving device 6; opening an isolation valve 1 (16), and lifting the graphite crucible 11 into the induction heating device 2 through a crucible lifting device 8; opening a vacuum unit (14) through an electrical control system (4), opening an isolation valve 2 (15) and an isolation valve 3 (9), and vacuumizing a discharge chamber (10) and a feed chamber (5); opening the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20) to vacuumize the reduction chamber (1), the crystallizer (17) and the lithium metal tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, heating the induction heating device (2) to 550 ℃ at a heating rate of 14 ℃/min, keeping the temperature for 50min, and keeping the vacuum degree at 1Pa; continuously heating, heating to 1150 ℃ at a heating rate of 14 ℃/min, controlling the vacuum degree of a vacuum reactor to 1050Pa, keeping the vacuum reactor at a constant temperature for about 3 hours until no lithium steam is generated, collecting lithium in a liquid form in a crystallizer (17), connecting a crystallization chamber (17) with a metal lithium tank (21), meanwhile, arranging a graphite filter, containing liquid paraffin in the metal lithium tank (20), periodically taking down the metal lithium tank (21) from the crystallization chamber (17), connecting the metal lithium tank to a glove box filled with high-purity argon, and then opening a valve of the metal lithium tank to obtain a lithium ingot with purity of 99.9%, recovery rate of 92% and current efficiency of 90%;
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 4 (7) is closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8);
the water cooling system (13) is respectively connected with the vacuum unit (14), the reduction chamber (1), the induction heating device (2) and the crystallization chamber (17).
The second furnace starts: closing the isolation valve 4 (7), manually opening the feeding chamber (5), filling the graphite crucible (11) with materials, vacuumizing the feeding chamber (5) to the process requirement vacuum degree, opening the isolation valve 4 (7), moving the graphite crucible (11) to the crucible lifting device (8) through the moving device (6), opening the isolation valve 1 (16), lifting the graphite crucible (11) into the induction heating device (2) through the crucible lifting device (8), wherein the vacuum degree and the temperature of the reduction chamber (1) meet the process requirement of the reduction reaction, the reduction reaction starts, and lithium is collected in the crystallizer (17) in a liquid state and flows into the metal lithium tank (21). After the reaction is completed, the graphite crucible (11) is descended through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 3 (9) is opened, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, the discharging chamber (10) is opened for breaking vacuum, the graphite crucible (11) is taken out, the residues of the graphite crucible (11) are cleaned, the discharging chamber (10) is closed, and the discharging chamber (10) is vacuumized to the process requirement vacuum degree, and the process is sequentially circulated.
The lithium extraction tailings obtained in the discharge chamber (10) comprise CaO.7Al 2 O 3 (s) (slag), 2CaO.SiO 2 (s)，CaO(s)·SiO 2 (s) and Al 2 O 3 ·2SiO 2 The chemical components are as follows: 30wt% of calcium oxide, 30wt% of aluminum oxide, 30wt% of silicon oxide and the balance of other oxides.
Grinding lithium extraction tailings obtained in a discharge chamber (10) to obtain powder with the granularity of 100-120 meshes, mixing the lithium extraction tailings powder, a reducing agent, a binder and water, agglomerating at 30MPa, and dehydrating at 100 ℃ until the mass percentage of water in the pellets is not more than 1%, wherein the pellets comprise the following components in percentage by weight: 65% of lithium-containing material lithium extraction tailings powder, 25% of a reducing agent, 6% of a binder and 4% of water, wherein the reducing agent comprises bituminous coal and petroleum coke (the mass ratio is 6:4), the fixed carbon content of the bituminous coal is 60%, the fixed carbon content of the petroleum coke is 90%, the sum of the fixed carbon contents in the bituminous coal and the petroleum coke is 95% of the theoretical requirement amount for complete reduction reaction, the pellets undergo reduction reaction for 3 hours at 1600 ℃ to obtain aluminum-silicon-calcium alloy liquid and scum, the aluminum-silicon-calcium alloy liquid is regularly discharged from an aluminum outlet ladle at intervals of 3 hours, the scum is used for preparing a metal lithium auxiliary agent from the lithium-containing material lithium extraction tailings, the yield of the scum is 3%, the main components of the scum comprise 30wt% of calcium oxide, 30wt% of aluminum oxide, 38wt% of silicon oxide and the balance of other oxides; mixing the aluminum-silicon-calcium alloy liquid with a refining agent, performing vacuum filtration to remove slag, mixing and diluting, and then casting ingot to obtain the aluminum-silicon-calcium alloy, wherein the aluminum-silicon-calcium alloy comprises the following components: 45wt% of aluminum, 24wt% of silicon, 30wt% of calcium and the balance of other elements contained in raw materials entering the aluminum-silicon-calcium alloy through refining, and performing vacuum distillation (the vacuum degree is 20Pa, the temperature is 1300 ℃ and the time is 5 h) on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy, wherein the aluminum-silicon alloy comprises the following components: 50wt% of Al, 48wt% of Si, 0.001wt% of Ca and the balance of other elements contained in the raw materials which are refined into the aluminum-silicon-calcium alloy, wherein the aluminum-silicon alloy is preferably recycled as a lithium extracting reducing agent for lithium-containing materials.
Example 3
Continuous lithium smelting by taking lithium hydroxide monohydrate as raw material
The first furnace starts: the lithium hydroxide monohydrate sold in the market is used as a raw material, a mixture of aluminum oxide and calcium oxide is matched as an auxiliary agent, and aluminum-silicon alloy is used as a reducing agent. Wherein the purity of the lithium hydroxide monohydrate is more than 98 percent. The purity of the alumina and the calcium oxide is more than 98 percent. The proportion (mass ratio): lithium hydroxide monohydrate: alumina: calcium oxide=3:1.5:1.5, and the mixture is uniformly mixed, and baked at 850 ℃ for 60 minutes. Grinding to fine powder after the mixture is burnt out60 meshes, adding aluminum-silicon alloy powder with granularity of 60 meshes and adding CaF accounting for 2% of the mixture, wherein the adding amount accounts for 10% of the total mass of the mixture of lithium hydroxide monohydrate, aluminum oxide and calcium oxide after roasting 2 The mixed raw materials are obtained and pressed into pellets.
Manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve 4 (7) through an electrical control system 4, and moving the graphite crucible 11 to a crucible lifting device 8 through a moving device 6; opening an isolation valve 1 (16), and lifting the graphite crucible 11 into the induction heating device 2 through a crucible lifting device 8; opening a vacuum unit (14) through an electrical control system (4), opening an isolation valve 2 (15) and an isolation valve 3 (9), and vacuumizing a discharge chamber (10) and a feed chamber (5); opening the isolation valve 5 (18), the isolation valve 6 (19) and the isolation valve 7 (20) to vacuumize the reduction chamber (1), the crystallizer (17) and the lithium metal tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, heating the induction heating device (2) to 550 ℃ at a heating rate of 14 ℃/min, keeping the temperature for 50min, and keeping the vacuum degree at 1Pa; continuously heating, heating to 1150 ℃ at a heating rate of 14 ℃/min, controlling the vacuum degree of a vacuum reactor to 1050Pa, keeping the vacuum reactor at a constant temperature for about 3 hours until no lithium steam is generated, collecting lithium in a liquid form in a crystallizer (17), connecting a crystallization chamber (17) with a metal lithium tank (21), meanwhile, arranging a graphite filter, containing liquid paraffin in the metal lithium tank (20), periodically taking down the metal lithium tank (21) from the crystallization chamber (17), connecting the metal lithium tank to a glove box filled with high-purity argon, and then opening a valve of the metal lithium tank to obtain a lithium ingot with purity of 99.9%, recovery rate of 96% and current efficiency of 94%;
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 4 (7) is closed, the mobile device (6) enters the discharging chamber (10), the isolation valve 3 (9) is closed, and the discharging chamber (10) is opened to break vacuum;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8);
the water cooling system (13) is respectively connected with the vacuum unit (14), the reduction chamber (1), the induction heating device (2) and the crystallization chamber (17).
The second furnace starts: closing the isolation valve 4 (7), manually opening the feeding chamber (5), filling the graphite crucible (11) with materials, closing the door of the feeding chamber (5), vacuumizing the feeding chamber (5) to the process requirement vacuum degree, opening the isolation valve 4 (7), moving the graphite crucible (11) to the crucible lifting device (8) through the moving device (6), opening the isolation valve 1 (16), lifting the graphite crucible (11) into the induction heating device (2) through the crucible lifting device (8), wherein the vacuum degree and the temperature of the reduction chamber (1) meet the process requirement of the reduction reaction, and the reduction reaction starts, so that lithium is collected in the crystallizer (17) in a liquid state and flows into the metal lithium tank (21). After the reaction is completed, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve 1 (16) is closed, the isolation valve 3 (9) is opened, the mobile device (6) enters the discharge chamber (10), the isolation valve 3 (9) is closed, the door of the discharge chamber (10) is opened, the graphite crucible (11) is taken out, the residues of the graphite crucible (11) are cleaned, the door of the discharge chamber (10) is closed, and the discharge chamber (10) is vacuumized to the process requirement vacuum degree and sequentially circulated.
The lithium extraction tailings obtained in the discharge chamber (10) comprise CaO.7Al 2 O 3 (s) (slag), 2CaO.SiO 2 (s)，CaO(s)·SiO 2 (s) and Al 2 O 3 ·2SiO 2 The chemical components are as follows: 50wt% of calcium oxide, 15wt% of aluminum oxide, 30wt% of silicon oxide and the balance of other oxides.
Grinding lithium extraction tailings obtained in a discharge chamber (10) to obtain powder with the granularity of 100-120 meshes, mixing the lithium extraction tailings powder, a reducing agent, a binder and water, agglomerating at 30MPa, and dehydrating at 100 ℃ until the mass percentage of water in the pellets is not more than 1%, wherein the pellets comprise the following components in percentage by weight: 55% of lithium extraction tailings powder of lithium-containing materials, 35% of reducing agent, 6% of binder and 4% of water, wherein the reducing agent comprises bituminous coal and petroleum coke (the mass ratio is 6:4), the fixed carbon content of the bituminous coal is 60%, the fixed carbon content of the petroleum coke is 90%, the sum of the fixed carbon contents in the bituminous coal and the petroleum coke is 95% of the theoretical requirement for complete reduction reaction, the pellets undergo reduction reaction at 1650 ℃ for 2.5 hours to obtain aluminum-silicon-calcium alloy liquid and scum, the aluminum-silicon-calcium alloy liquid is periodically ladle-discharged from an aluminum outlet at intervals of 3 hours, the scum is used for preparing a metal lithium auxiliary agent from the lithium-containing materials lithium extraction tailings, the yield of the scum is 5%, the main components of the scum comprise 40wt% of calcium oxide, 25wt% of aluminum oxide, 34wt% of silicon oxide and the balance of other oxides; mixing the aluminum-silicon-calcium alloy liquid with a refining agent, performing vacuum filtration to remove slag, mixing and diluting, and then casting ingot to obtain the aluminum-silicon-calcium alloy, wherein the aluminum-silicon-calcium alloy comprises the following components: 40wt% of aluminum, 30wt% of silicon and 28wt% of calcium, and the balance of other elements contained in raw materials entering the aluminum-silicon-calcium alloy through refining, wherein the aluminum-silicon-calcium alloy is subjected to vacuum distillation (the vacuum degree is 10Pa, the temperature is 1200 ℃ and the time is 4 h), so as to obtain metal calcium and aluminum-silicon alloy, and the aluminum-silicon alloy comprises the following components: 50wt% of Al, 49wt% of Si, 0.001wt% of Ca and the balance of other elements contained in the raw materials which are refined into the aluminum-silicon-calcium alloy, wherein the aluminum-silicon alloy is preferably recycled as a lithium extracting reducing agent for lithium-containing materials.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A continuous lithium-smelting method for lithium-containing materials is characterized by utilizing a continuous lithium-smelting device for lithium-containing materials, and comprises the following steps:
manually opening a door of a feeding chamber (5), putting pellets made of lithium-containing materials, auxiliary agents and reducing agents into a graphite crucible (11), and closing the door of the feeding chamber (5); opening an isolation valve D (7) through an electrical control system (4), and moving the graphite crucible (11) to a crucible lifting device (8) through a moving device (6); opening an isolation valve A (16), and lifting the graphite crucible (11) into the induction heating device (2) through the crucible lifting device (8); opening a vacuum unit (14) through an electric appliance control system (4), opening an isolation valve B (15) and an isolation valve C (9), and vacuumizing a discharging chamber (10) and a feeding chamber (5); opening an isolation valve E (18), an isolation valve F (19) and an isolation valve G (20) to vacuumize a reduction chamber (1), a crystallizer (17) and a metal lithium tank (21); starting a water cooling system (13) to cool the vacuum unit (14), the reduction chamber (1), the crystallizer (17) and the induction heating device (2) by water; starting a heating power supply (3) to heat the induction heating device (2), displaying vacuum degree and temperature in an electric appliance control system (4), performing reduction reaction, collecting lithium in a liquid state in a crystallizer (17), and flowing into a metal lithium tank (21);
After the reduction reaction is finished, the graphite crucible (11) is lowered through the crucible lifting device (8), the isolation valve A (16) and the isolation valve D (7) are closed, the mobile device (6) enters the discharging chamber (10), the isolation valve C (9) is closed, and the discharging chamber (10) is opened to break vacuum; the hydraulic system (12) is connected with the crucible lifting device (8) and controls the lifting of the crucible lifting device (8);
the continuous lithium smelting device for lithium-containing materials comprises: the device comprises a reduction chamber (1), a graphite crucible (11), an electrical appliance control system (4), a vacuum unit (14), a hydraulic system (12) and a water cooling system (13);
the bottom of the reduction chamber (1) is provided with an induction heating device (2), the induction heating device (2) is connected with a heating power supply (3), a crucible lifting device (8) is arranged below the induction heating device (2), an isolation valve A (16) is arranged between the induction heating device (2) and the crucible lifting device (8), the reduction chamber (1) is connected with a vacuum unit (14) through an isolation valve E (18), the reduction chamber (1) is communicated with a crystallizer (17), the crystallizer (17) is connected with a metal lithium tank (21) through an isolation valve F (19), and the crystallizer (17) is connected with the vacuum unit (14) through an isolation valve G (20);
the two sides of the crucible lifting device (8) are respectively provided with a feeding chamber (5) and a discharging chamber (10), an isolation valve D (7) is arranged between the crucible lifting device (8) and the feeding chamber (5), and an isolation valve C (9) is arranged between the crucible lifting device (8) and the discharging chamber (10); the vacuum unit (14) is communicated with the discharge chamber (10) through an isolation valve B (15);
The graphite crucible (11) moves among the feeding chamber (5), the crucible lifting device (8) and the discharging chamber (10) through the moving device (6);
the electric appliance control system (4) is respectively connected with the reduction chamber (1), the feeding chamber (5), the discharging chamber (10), the crystallizer (17), the isolation valve A (16), the isolation valve B (15), the isolation valve C (9), the isolation valve D (7), the isolation valve E (18), the isolation valve F (19) and the isolation valve G (20), and the electric appliance control system (4) comprises a temperature measuring device and a vacuum detecting device, and displays the temperature and the vacuum degree;
the hydraulic system (12) is connected with the crucible lifting device (8) and controls the crucible lifting device (8) to lift;
the water cooling system (13) is respectively connected with the reduction chamber (1), the induction heating device (2), the vacuum unit (14) and the crystallizer (17).
2. The method according to claim 1, characterized in that the temperature of the crystallizer (17) is 200-300 ℃.
3. The method of claim 1, wherein when the lithium-containing material is lithium carbonate or lithium hydroxide monohydrate, the auxiliary agent is a mixture of aluminum oxide and calcium oxide, and the reducing agent is an aluminum-silicon alloy.
4. The method of claim 1, wherein when the lithium-containing material is a lithium-containing mineral, the promoter comprises a metal oxide and the reducing agent comprises one or more of aluminum, magnesium, silicon, calcium, a calcium-silicon alloy, an aluminum-magnesium alloy, an aluminum-silicon alloy, and a silicon-magnesium alloy.
5. The method according to claim 1, further comprising the following steps after the reduction reaction:
mixing lithium extraction tailings of the lithium-containing material obtained in the discharging chamber (10), a reducing agent, a binder and water, and agglomerating to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for preparing metal lithium from lithium-containing materials and extracting lithium tailings;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain the metal calcium and aluminum-silicon alloy.
6. The method according to claim 1, characterized in that the reduction chamber (1) is of a double-layer water-passing cooling structure.
7. The method according to claim 1, characterized in that the metallic lithium tank (21) contains liquid paraffin.
8. A method according to claim 1, characterized in that a graphite filter is provided in the crystallizer (17).
9. The method according to claim 1, characterized in that the induction heating device (2) is an electromagnetic induction heating device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010151000.7A CN111187924B (en) | 2020-03-06 | 2020-03-06 | Continuous lithium smelting device and method for lithium-containing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010151000.7A CN111187924B (en) | 2020-03-06 | 2020-03-06 | Continuous lithium smelting device and method for lithium-containing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111187924A CN111187924A (en) | 2020-05-22 |
| CN111187924B true CN111187924B (en) | 2024-04-12 |
Family
ID=70706924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010151000.7A Active CN111187924B (en) | 2020-03-06 | 2020-03-06 | Continuous lithium smelting device and method for lithium-containing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111187924B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528859A (en) * | 2020-11-30 | 2021-10-22 | 深圳市研一新材料有限责任公司 | Preparation method and preparation equipment of ultrathin metal lithium foil |
| CN112322913A (en) * | 2020-12-10 | 2021-02-05 | 中国核电工程有限公司 | Refining device and refining method |
| CN112410580A (en) * | 2020-12-10 | 2021-02-26 | 中国核电工程有限公司 | Refining device and refining method with stable work |
| CN113526474B (en) * | 2020-12-31 | 2023-03-31 | 深圳市研一新材料有限责任公司 | Lithium nitride particles, and method and apparatus for producing same |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149911C1 (en) * | 1999-07-29 | 2000-05-27 | Спасенников Сергей Владимирович | Method of lithium production and device for its embodiment |
| CN201942729U (en) * | 2010-12-13 | 2011-08-24 | 昆明理工大学 | Semi-continuous vacuum induction heating magnesium reduction furnace |
| CN102560148A (en) * | 2012-01-19 | 2012-07-11 | 东北大学 | Method for smelting lithium by vacuum aluminothermic reduction |
| CN103193233A (en) * | 2013-04-01 | 2013-07-10 | 北京博大格林高科技有限公司 | Device and method for preparing solar-grade polycrystalline silicon by reducing silicon tetrafluoride with sodium |
| CN107858544A (en) * | 2017-11-17 | 2018-03-30 | 山东重山光电材料股份有限公司 | The preparation method and reactor of a kind of lithium boron alloy |
| CN108165768A (en) * | 2018-01-15 | 2018-06-15 | 东北大学 | The apparatus and method of lithium are produced in a kind of vacuum metal thermal reduction |
| CN109722551A (en) * | 2019-03-20 | 2019-05-07 | 北京欧菲金太科技有限责任公司 | The continuous producing apparatus and continuous producing method of magnesium metal |
| CN109811145A (en) * | 2019-04-09 | 2019-05-28 | 北京欧菲金太科技有限责任公司 | A method of lithium metal is prepared containing lithium minerals |
| CN110129587A (en) * | 2019-05-27 | 2019-08-16 | 昆明理工大学 | A kind of method that spodumene vacuum metling extracts lithium metal and prepares alusil alloy |
| CN211897068U (en) * | 2020-03-06 | 2020-11-10 | 北京欧菲金太科技有限责任公司 | Lithium-containing material continuous lithium smelting device |
-
2020
- 2020-03-06 CN CN202010151000.7A patent/CN111187924B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149911C1 (en) * | 1999-07-29 | 2000-05-27 | Спасенников Сергей Владимирович | Method of lithium production and device for its embodiment |
| CN201942729U (en) * | 2010-12-13 | 2011-08-24 | 昆明理工大学 | Semi-continuous vacuum induction heating magnesium reduction furnace |
| CN102560148A (en) * | 2012-01-19 | 2012-07-11 | 东北大学 | Method for smelting lithium by vacuum aluminothermic reduction |
| CN103193233A (en) * | 2013-04-01 | 2013-07-10 | 北京博大格林高科技有限公司 | Device and method for preparing solar-grade polycrystalline silicon by reducing silicon tetrafluoride with sodium |
| CN107858544A (en) * | 2017-11-17 | 2018-03-30 | 山东重山光电材料股份有限公司 | The preparation method and reactor of a kind of lithium boron alloy |
| CN108165768A (en) * | 2018-01-15 | 2018-06-15 | 东北大学 | The apparatus and method of lithium are produced in a kind of vacuum metal thermal reduction |
| CN109722551A (en) * | 2019-03-20 | 2019-05-07 | 北京欧菲金太科技有限责任公司 | The continuous producing apparatus and continuous producing method of magnesium metal |
| CN109811145A (en) * | 2019-04-09 | 2019-05-28 | 北京欧菲金太科技有限责任公司 | A method of lithium metal is prepared containing lithium minerals |
| CN110129587A (en) * | 2019-05-27 | 2019-08-16 | 昆明理工大学 | A kind of method that spodumene vacuum metling extracts lithium metal and prepares alusil alloy |
| CN211897068U (en) * | 2020-03-06 | 2020-11-10 | 北京欧菲金太科技有限责任公司 | Lithium-containing material continuous lithium smelting device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111187924A (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111187924B (en) | Continuous lithium smelting device and method for lithium-containing material | |
| AU2020101985A4 (en) | A continuous lithium refining device and method for lithium containing materials | |
| CN106077040B (en) | A kind of method of ultrasonic wave auxiliary alkali leaching process aluminum electrolytic waste and old cathode carbon block | |
| CN102912140A (en) | Method for recycling waste aluminum ring-pull cans in green circular relegation way | |
| WO2017031798A1 (en) | Apparatus for treating and recycling aluminum electrolysis solid waste | |
| CN112111660B (en) | Method for enriching lithium from lithium ore and preparing ferro-silicon alloy and recycling aluminum oxide | |
| GB2588364A (en) | Method for recycling zinc by comprehensively utilizing steelmaking dust | |
| CN109750155A (en) | A method of the Call Provision from waste lithium ion cell anode material | |
| CN109811145B (en) | Method for preparing metallic lithium from lithium-containing mineral | |
| CN111471817A (en) | Gas quenching method for improving stability of steel slag and recovering physical heat of molten steel slag | |
| CN107090551A (en) | A kind of method of the direct vanadium extraction of vanadium titano-magnetite | |
| CN108754170A (en) | A kind of full constituent method of comprehensive utilization of copper ashes | |
| CN108754143A (en) | A method of producing Antaciron using metallurgical white residue | |
| WO2017190393A1 (en) | Method for extracting iron and titanium with ferrotitanium complex ore as raw material and filtering device | |
| CN112941324A (en) | Novel process for comprehensively utilizing resources containing heavy metal hazardous wastes | |
| CN108588316A (en) | A method of recycling sintering machine head end electro-precipitating dust | |
| EP4338858A1 (en) | Impurity removal method for silicate solid waste and use thereof | |
| CN110819822A (en) | Electric heating aluminum smelting device | |
| CN105239097B (en) | A kind of water quenching of aluminium electrolysis anode breeze and sorting processing method | |
| CN211897068U (en) | Lithium-containing material continuous lithium smelting device | |
| CN101476047B (en) | Method for preparing metal aluminum from aluminum-containing raw material | |
| CN211311551U (en) | Electric heating aluminum smelting device | |
| CN106756060A (en) | A kind of recovery method of indium metal | |
| CN114231743B (en) | Method for preparing indium tin alloy by reducing ITO waste target at high temperature | |
| CN109609776A (en) | A method of copper cobalt in copper vessel slag is extracted using waste cathode of aluminum electrolytic cell carbon block |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |