CN116479258A - Lithium extraction method and equipment - Google Patents
Lithium extraction method and equipment Download PDFInfo
- Publication number
- CN116479258A CN116479258A CN202310339384.9A CN202310339384A CN116479258A CN 116479258 A CN116479258 A CN 116479258A CN 202310339384 A CN202310339384 A CN 202310339384A CN 116479258 A CN116479258 A CN 116479258A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid phase
- sulfate
- lithium sulfate
- gasified
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 167
- 238000000605 extraction Methods 0.000 title claims abstract description 71
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 181
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000007790 solid phase Substances 0.000 claims abstract description 158
- 150000001875 compounds Chemical class 0.000 claims abstract description 66
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000001180 sulfating effect Effects 0.000 claims abstract description 7
- 230000008016 vaporization Effects 0.000 claims abstract description 7
- 238000009834 vaporization Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 149
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 93
- 239000003546 flue gas Substances 0.000 claims description 93
- 238000005670 sulfation reaction Methods 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 41
- 229910052629 lepidolite Inorganic materials 0.000 claims description 32
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 32
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- 238000002309 gasification Methods 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 10
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical group [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical group [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052642 spodumene Inorganic materials 0.000 claims description 4
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 3
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000002535 acidifier Substances 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 239000002918 waste heat Substances 0.000 description 26
- 239000000428 dust Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 14
- 230000023556 desulfurization Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- 230000019635 sulfation Effects 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000003517 fume Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 2
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- -1 sulfate radical ions Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
The invention discloses a lithium extraction method and equipment, which are used for solving the technical problems of long technological process and great environmental pollution of a sulfuric acid method. Comprising the following steps: converting a first solid phase containing a lithium-based compound into a second solid phase containing lithium sulfate by dry sulfating reaction by mixing the first solid phase with a sulfate-ion-based acidulant, the lithium sulfate being obtained from the lithium-based compound by the dry sulfating reaction; vaporizing lithium sulfate in the second solid phase by heating the second solid phase to volatilize the lithium sulfate from the second solid phase, wherein the solid phase remaining after the vaporization and volatilization of the lithium sulfate in the second solid phase is a third solid phase; and recovering gasified lithium sulfate, wherein the mass percentage of lithium sulfate in the solid lithium sulfate is more than or equal to 95% when the gasified lithium sulfate is cooled to the solid lithium sulfate.
Description
Technical Field
The embodiment of the application relates to the technical field of lithium metallurgy, in particular to a lithium ore pretreatment device, a lithium extraction method, lithium extraction equipment and a lithium source preparation method.
Background
The most common lithium-containing minerals are lithium ores (spodumene and lepidolite) and brine, and based on these two raw materials, the lithium source preparation process can be further divided into a lithium source preparation method of lithium ores and a lithium source preparation method of brine.
The "lithium source" is typically lithium carbonate (Li 2 CO 3 ) And lithium hydroxide (LiOH. H) 2 O) can be classified into industrial grade lithium sources and battery grade lithium sources according to purity requirements. For example, the mass percent of lithium carbonate in the industrial grade lithium carbonate is 98% -99%, and the mass percent of lithium carbonate in the battery grade lithium carbonate is more than or equal to 99.5%.
At present, a sulfuric acid method is mainly adopted in a lithium source preparation method of lithium ores. The sulfuric acid process belongs to wet metallurgy, and the method aims at the lithium sulfate solution leached by the wet process, and the refined lithium sulfate solution can be obtained only by carrying out multi-step impurity removal procedures, so that the whole process flow is long and the environmental pollution is large.
Disclosure of Invention
The aim of some embodiments of the present application is to provide a lithium extraction method and a device, so as to solve the technical problems of long technological process and large environmental pollution of the sulfuric acid method.
The object of some embodiments of the present application is to provide a method for preparing a lithium source, which can be used as a subsequent step of the above-mentioned lithium extraction method to obtain a battery-level lithium source in a simpler manner.
The aim of some embodiments of the present application is to provide a lithium ore pretreatment device and a lithium extraction apparatus, which can provide a lithium ore pretreatment scheme for the lithium extraction method and apparatus, reduce environmental pollution of lithium ore pretreatment and realize waste heat utilization.
In a first aspect, there is provided a lithium extraction method comprising: converting a first solid phase containing a lithium-based compound into a second solid phase containing lithium sulfate by dry sulfating reaction by mixing the first solid phase with a sulfate-ion-based acidulant, the lithium sulfate being obtained from the lithium-based compound by the dry sulfating reaction; vaporizing lithium sulfate in the second solid phase by heating the second solid phase to volatilize the lithium sulfate from the second solid phase, wherein the solid phase remaining after the vaporization and volatilization of the lithium sulfate in the second solid phase is a third solid phase; and recovering gasified lithium sulfate, wherein the mass percentage of lithium sulfate in the solid lithium sulfate is more than or equal to 95% when the gasified lithium sulfate is cooled to the solid lithium sulfate.
In the lithium extraction method according to the first aspect, optionally, the first solid phase material is mainly composed of at least one of a first class of compounds, a second class of compounds, and a third class of compounds, except for the lithium-based compound; the first type of compound is a metal compound and is converted into first type of metal sulfate through the dry sulfation reaction, and the first type of metal sulfate is converted into first type of metal oxide through the heating and is decomposed into sulfur dioxide gas; the second class of compounds are metal compounds and are converted into second class of metal sulfates by the dry sulfation reaction, the second class of metal sulfates not being converted by the heating; the third class of compounds are nonmetallic compounds and are not converted by both the dry sulfation reaction and the heating.
Optionally, in the lithium extraction method of the first aspect, the first solid phase is from lithium ore; if the first solid phase substance contains the first type of compound, the first type of compound is mainly composed of at least one metal oxide; if the first solid phase contains the second class of compounds, the second class of compounds is mainly composed of at least one metal oxide; if the first solid phase contains the third class of compounds, the third class of compounds mainly consists of at least one nonmetallic oxide.
Optionally, in the lithium extraction method of the first aspect, the first compound includes at least one of aluminum oxide, iron oxide, calcium oxide, magnesium oxide, and manganese oxide; the second class of compounds comprises at least one of sodium oxide, potassium oxide, rubidium oxide and cesium oxide; the third class of compounds comprises silicon oxide. Optionally, in the method for extracting lithium according to the first aspect, the lithium ore is spodumene or lepidolite.
The lithium extraction method of the first aspect is optionally that the first solid phase is obtained by pretreating a lithium ore, the pretreatment comprising loosening the structure of the lithium ore (e.g. converting the spodumene form from α to β form) by roasting the lithium ore and defluorinating the lithium ore when fluorine is contained in the lithium ore, and refining the lithium ore to form particles.
In the lithium extraction method according to the first aspect, optionally, the dry sulfation reaction is performed by mixing the first solid phase with a sulfate ion-based acidulant thoroughly while keeping the whole of the first solid phase in a solid state.
In the lithium extraction method of the first aspect, optionally, the dry sulfation reaction is performed by thoroughly mixing the first solid phase material with the sulfate ion-based acidulant in a molar ratio of 1 to 1.3 of sulfate ions in the sulfate ion-based acidulant to total reactants in the first solid phase material.
In the lithium extraction method according to the first aspect, the sulfate ion group acidulant is specifically concentrated sulfuric acid.
The lithium extraction method of the first aspect may be further characterized by, after or simultaneously with the conversion of the first solid phase into a second solid phase containing lithium sulfate by dry sulfation by mixing the first solid phase with a sulfate ion-based acidulant, fully differentiating the dry sulfation by baking the second solid phase and removing the incompletely reacted sulfate ion-based acidulant, and then volatilizing lithium sulfate in the second solid phase from the second solid phase by heating the second solid phase.
Optionally, in the lithium extraction method according to the first aspect, the heating is specifically heating the second solid phase to 1350 ℃ under a condition of lower than one atmosphere.
In the lithium extraction method according to the first aspect, the first solid phase and the sulfate ion-based acidulant are mixed with each other in the form of particles.
In the lithium extraction method of the first aspect, optionally, the recovering gasified lithium sulfate includes recovering heat from the gasified lithium sulfate by flue gas cooling and heat exchanging, and outputting cooled flue gas containing solid lithium sulfate converted from the gasified lithium sulfate, and performing gas-solid separation on the cooled flue gas by flue gas filtration, and discharging a first filtered solid phase and a first filtered gas phase respectively, wherein the first filtered solid phase is mainly solid lithium sulfate, and the mass percentage of the lithium sulfate in the first filtered solid phase is more than or equal to 95%.
Optionally, in the lithium extraction method of the first aspect, the recovering gasified lithium sulfate comprises mixing gasified lithium sulfate with a sodium carbonate solution or a sodium hydroxide solution to react the lithium sulfate with sodium carbonate or sodium hydroxide to produce lithium carbonate or lithium hydroxide.
According to the lithium extraction method in the first aspect, high-purity lithium sulfate can be obtained without complex and cumbersome wet process, the liquid treatment capacity after subsequent water dissolution is greatly reduced, the subsequent impurity removal and purification production scale is greatly reduced, and the flow is greatly shortened. The process slag is dry slag, which is favorable for storage, utilization and environmental protection.
In a second aspect, a lithium extraction apparatus is provided that can be used to implement the lithium extraction method of the first aspect described above. Comprising the following steps: a mixing reactor for mixing a first solid phase substance with a sulfate radical ion group acidulant to carry out dry sulfation reaction so as to convert the first solid phase substance into a second solid phase substance containing lithium sulfate, wherein the first solid phase substance contains a lithium-based compound, and the lithium sulfate is obtained by the dry sulfation reaction of the lithium-based compound; a heating gasification furnace for heating the second solid phase material to gasify lithium sulfate in the second solid phase material and volatilize the gasified lithium sulfate from the second solid phase material, wherein the solid phase material remaining after the gasified and volatilized lithium sulfate in the second solid phase material is a third solid phase material; and the gasified lithium sulfate recovery device is used for recovering the gasified lithium sulfate, and the mass percentage of the lithium sulfate in the solid lithium sulfate is more than or equal to 95% when the gasified lithium sulfate is cooled to the solid lithium sulfate.
Optionally, in the lithium extraction apparatus of the second aspect, the gasified lithium sulfate recovery device includes: the flue gas cooling heat exchanger is used for recovering heat of high-temperature flue gas discharged by the heating gasification furnace and outputting cooled flue gas containing solid lithium sulfate converted from gasified lithium sulfate; the first flue gas filter is used for carrying out gas-solid separation on the cooled flue gas and respectively discharging a first filtered solid phase object and a first filtered gas phase object, and the first filtered solid phase object is mainly solid lithium sulfate.
The lithium extraction device of the second aspect may further include: and a roasting kiln arranged between the mixing reactor and the heating gasification furnace and used for carrying out dry sulfation reaction on a first solid phase substance and a sulfate radical ion group acidulant to convert the first solid phase substance into a second solid phase substance containing lithium sulfate, roasting the second solid phase substance to fully differentiate the dry sulfation reaction and remove the incompletely reacted sulfate radical ion group acidulant, and then heating the second solid phase substance to gasify the lithium sulfate in the second solid phase substance and volatilize the lithium sulfate from the second solid phase substance.
In a third aspect, there is provided a lithium extraction method comprising: converting a first material containing a lithium-based compound into a second material containing lithium sulfate by mixing the first material with a sulfate-ion-based acidulant, the lithium sulfate being obtained from the lithium-based compound by the sulfation; after or simultaneously with converting a first material into a second material containing lithium sulfate by mixing the first material with a sulfate-ion-based acidulant for sulfation, fully differentiating the sulfation by roasting the second material and removing incompletely reacted sulfate-based acidulant; the second material is heated to gasify lithium sulfate in the second material and volatilize the gasified lithium sulfate from the second solid phase material, and the solid phase material remained after the gasified and volatilized lithium sulfate in the second material is a third material; and recovering the gasified lithium sulfate.
In the above-mentioned lithium extraction method according to the third aspect, optionally, the first material is a first solid phase, and the first solid phase mainly includes at least one of a first class of compound, a second class of compound, and a third class of compound, except for the lithium-based compound; the first type of compounds are metal compounds and are converted into first type of metal sulfates through the sulfation reaction, and the first type of metal sulfates are converted into first type of metal oxides through the heating and decompose sulfur dioxide gas; the second class of compounds are metal compounds and are converted into second class of metal sulfates by the sulfation reaction, the second class of metal sulfates not being converted by the heating; the third class of compounds are nonmetallic compounds and are not converted by both the sulfation reaction and the heating.
Optionally, in the lithium extraction method of the third aspect, the first solid phase is from lithium ore; if the first solid phase substance contains the first type of compound, the first type of compound is mainly composed of at least one metal oxide; if the first solid phase contains the second class of compounds, the second class of compounds is mainly composed of at least one metal oxide; if the first solid phase contains the third class of compounds, the third class of compounds mainly consists of at least one nonmetallic oxide.
Optionally, in the lithium extraction method of the third aspect, the first compound includes at least one of aluminum oxide, iron oxide, calcium oxide, magnesium oxide, and manganese oxide; the first class of compounds comprise at least one of sodium oxide, potassium oxide, rubidium oxide and cesium oxide; the third class of compounds comprises silicon oxide. Optionally, in the method for extracting lithium according to the third aspect, the lithium ore is spodumene or lepidolite.
In the lithium extraction method according to the third aspect, the first solid phase is obtained by pretreating a lithium ore, the pretreatment comprising loosening the structure of the lithium ore by roasting the lithium ore and defluorinating the lithium ore when fluorine is contained in the lithium ore, and refining the lithium ore to form particles of the lithium ore.
In the lithium extraction method according to the third aspect, the sulfation reaction is that the first material and the sulfate ion group acidulant are fully mixed and reacted under the condition that the whole material in the first material is kept in a solid state or a mud state.
In the lithium extraction method of the third aspect, optionally, the sulfating reaction is performed by fully mixing the first material and the sulfate ion-based acidulant according to a molar ratio of sulfate ions in the sulfate ion-based acidulant to total reactants in the first material of 1-1.3.
In the lithium extraction method according to the third aspect, the sulfate ion group acidulant is specifically concentrated sulfuric acid.
Optionally, in the lithium extraction method according to the third aspect, the heating is specifically heating the second solid phase to 1350 ℃ under a condition of lower than one atmosphere. In the lithium extraction method according to the third aspect, the roasting temperature is 180-300 ℃.
In the lithium extraction method according to the third aspect, the first material and the sulfate ion-based acidulant are mixed with each other in the form of particles.
In the lithium extraction method of the third aspect, optionally, the recovering gasified lithium sulfate includes recovering heat from the gasified lithium sulfate by flue gas cooling and heat exchanging, and outputting cooled flue gas containing solid lithium sulfate converted from the gasified lithium sulfate, and performing gas-solid separation on the cooled flue gas by flue gas filtration, and discharging a first filtered solid phase and a first filtered gas phase respectively, wherein the first filtered solid phase is mainly solid lithium sulfate, and the mass percentage of the lithium sulfate in the first filtered solid phase is not less than 95%.
Optionally, in the lithium extraction method of the third aspect, the recovering gasified lithium sulfate comprises mixing gasified lithium sulfate with sodium carbonate solution or sodium hydroxide solution to react the lithium sulfate with sodium carbonate or sodium hydroxide to prepare lithium carbonate or lithium hydroxide.
According to the lithium extraction method in the third aspect, high-purity lithium sulfate can be obtained without complex and cumbersome wet process, the liquid treatment capacity after subsequent water dissolution is greatly reduced, the subsequent impurity removal and purification production scale is greatly reduced, and the flow is greatly shortened. The process slag is dry slag, which is favorable for storage, utilization and environmental protection.
In the lithium extraction method according to the third aspect, the sulfation reaction of the lithium extraction method according to the third aspect may allow the first material and the sulfate ion-based acidulant to be sufficiently mixed and reacted while keeping the entirety of the material in the first material in a mud state, as compared with the lithium extraction method according to the third aspect.
In a fourth aspect, a lithium extraction apparatus is provided that can be used to implement the lithium extraction method of the second aspect described above. Comprising the following steps: the mixing reactor is used for mixing a first material with a sulfate radical ion group acidulant to carry out a sulfation reaction so as to convert the first material into a second material containing lithium sulfate, wherein the first material contains a lithium-based compound, and the lithium sulfate is obtained by the sulfation reaction of the lithium-based compound; a roasting kiln for roasting a second material containing lithium sulfate after or while mixing the first material with a sulfate ion-based acidulant to perform a sulfation reaction to convert the first material into the second material, to fully differentiate the sulfation reaction and remove the incompletely reacted sulfate ion-based acidulant; the heating gasification furnace is used for heating the second material to gasify lithium sulfate in the second material and volatilize the lithium sulfate from the second material, and the solid phase material remained after the gasification and volatilization of the lithium sulfate in the second material is a third material; and a gasified lithium sulfate recovery device for recovering the gasified lithium sulfate.
Optionally, in the lithium extraction apparatus of the fourth aspect, the gasified lithium sulfate recovery device includes: the flue gas cooling heat exchanger is used for recovering heat of high-temperature flue gas discharged by the heating gasification furnace and outputting cooled flue gas containing solid lithium sulfate converted from gasified lithium sulfate; the first flue gas filter is used for carrying out gas-solid separation on the cooled flue gas and respectively discharging a first filtered solid phase object and a first filtered gas phase object, and the first filtered solid phase object is mainly solid lithium sulfate.
The lithium extraction device of the fourth aspect is optional, wherein the roasting kiln is connected with a roasting flue gas treatment system; the roasting fume treatment system comprises: the second flue gas filter is used for carrying out gas-solid separation on the roasting flue gas discharged by the roasting kiln and respectively discharging a second filtered solid phase object and a second filtered gas phase object; the flue gas desulfurization equipment is used for receiving the second filtered gas-phase object, desulfurizing the second filtered gas-phase object and discharging desulfurized tail gas; and the material conveying equipment is used for receiving the second filtered solid phase material and returning the filtered solid phase material to the first material or the second material.
Optionally in the lithium extraction apparatus of the fourth aspect, the flue gas desulfurization apparatus outputs the recovered sulfur to a sulfate-ion-based acidulant supply system in the form of the sulfate-ion-based acidulant or in the form of a raw material of the sulfate-ion-based acidulant.
In the lithium extraction device of the fourth aspect, optionally, the flue gas desulfurization device adopts a catalytic flue gas desulfurization device, the catalytic flue gas desulfurization device adsorbs sulfur dioxide, water and oxygen contained in the filtered gas phase substance on a catalyst and reacts under the catalysis of active components to generate sulfuric acid, when the sulfuric acid attached on the catalyst reaches a certain degree, dilute sulfuric acid and/or water is used as a regeneration liquid to spray the catalyst, so that the attached sulfuric acid is removed on the catalyst and the active site of the catalyst is released, and the used regeneration liquid is used as sulfuric acid to prepare the sulfate radical ion acidulant.
In the lithium extraction device of the fourth aspect, optionally, the first filtered gas phase material discharged from the first flue gas filter is subjected to desulfurization treatment by the flue gas desulfurization device.
In a fifth aspect, a method for preparing a lithium source is provided, wherein the lithium source is lithium carbonate or lithium hydroxide, and specifically, the method uses solid lithium sulfate (which can be obtained by the lithium extraction method in the first aspect or the lithium extraction method in the third aspect) with the mass percent of lithium sulfate more than or equal to 95% obtained by cooling gasified lithium sulfate as a raw material, and the raw material is dissolved in water, and then is mixed with sodium carbonate or sodium hydroxide for reaction after impurity removal, so as to prepare the battery-level lithium carbonate or lithium hydroxide.
In the method for preparing a lithium source according to the fifth aspect, if the battery grade lithium carbonate is to be prepared, after the raw materials are dissolved in water, the raw materials may be first alkalized and decontaminated to obtain a refined solution of lithium sulfate, and then the refined solution of lithium sulfate is mixed with sodium carbonate to react, thereby preparing the battery grade lithium carbonate.
Because the high-purity lithium sulfate is used as the raw material, the liquid treatment capacity after water dissolution is greatly reduced, and the subsequent impurity removal and purification production scale is greatly reduced, and the flow is greatly shortened.
In a sixth aspect, a lithium ore pretreatment device is provided, which can provide a lithium ore pretreatment scheme for the lithium extraction method and the lithium extraction device in the above aspects. Comprising the following steps: a pretreatment roasting kiln for roasting a lithium ore to loosen a structure of the lithium ore and defluorinating when fluorine is contained in the lithium ore; the roasting flue gas purification system is used for purifying flue gas discharged by the pretreatment roasting kiln and recovering dust in the flue gas; the roasting material waste heat utilization system is used for cooling and utilizing waste heat of the roasted material discharged from the pretreatment roasting kiln; and the crushing processing device is used for refining the waste heat utilized material discharged by the roasting material waste heat utilization system to enable the lithium ore to be particles.
In the above lithium ore pretreatment device according to the sixth aspect, the pretreatment roasting kiln is a rotary kiln, an input end of the roasting flue gas purification system is connected to a kiln tail of the rotary kiln, and an input end of the roasting material waste heat utilization system is connected to a kiln head of the rotary kiln.
Optionally, in the lithium ore pretreatment device of the sixth aspect, the roasting flue gas purification system includes a first flue gas dust remover, and the first flue gas dust remover physically intercepts dust in flue gas discharged from the pretreatment roasting kiln through a filter element.
In an optional lithium ore pretreatment device according to the sixth aspect, the roasting material waste heat utilization system comprises a grate cooler and a second flue gas dust remover connected to an exhaust end of the grate cooler, and the second flue gas dust remover is used for physically intercepting dust in flue gas discharged by the grate cooler through a filter element.
In a seventh aspect, there is provided a lithium extraction apparatus comprising: a lithium ore pretreatment device according to the sixth aspect; a mixing reactor for mixing the first solid phase of the particulate matter with a sulfate ion group acidulant to perform a dry sulfation reaction so as to convert the first solid phase into a second solid phase containing lithium sulfate; a heating gasification furnace for heating the second solid phase material to gasify lithium sulfate in the second solid phase material and volatilize the gasified lithium sulfate from the second solid phase material, wherein the solid phase material remaining after the gasified and volatilized lithium sulfate in the second solid phase material is a third solid phase material; and a gasified lithium sulfate recovery device for recovering the gasified lithium sulfate.
In an eighth aspect, there is provided a lithium extraction apparatus comprising: a lithium ore pretreatment device according to the sixth aspect; a mixing reactor for mixing a first material using the particulate matter with a sulfate ion group acidulant to perform a sulfation reaction so as to convert the first material into a second material containing lithium sulfate; a roasting kiln for roasting a second material containing lithium sulfate after or while mixing the first material with a sulfate ion-based acidulant to perform a sulfation reaction to convert the first material into the second material, to fully differentiate the sulfation reaction and remove the incompletely reacted sulfate ion-based acidulant; the heating gasification furnace is used for heating the second material to gasify lithium sulfate in the second material and volatilize the second material, and the solid phase of the second material which is left after the gasification and volatilization of the lithium sulfate is a third material; and a gasified lithium sulfate recovery device for recovering the gasified lithium sulfate.
The present application is further described below with reference to the drawings and detailed description. Additional aspects and advantages provided by the application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice.
Drawings
The accompanying drawings, which form a part hereof, are included to provide an understanding of the present application, and in which are shown by way of illustration, and not limitation, specific examples of which are given herein. In the drawings:
fig. 1 is a schematic overall flow chart of a process for producing lithium carbonate from lepidolite according to example 1 of the present application.
Fig. 2 is a specific process flow diagram of the pretreatment process of lithium ores of fig. 1.
FIG. 3 is a specific process flow diagram of the acidification gasification process of FIG. 1.
Fig. 4 is a specific process flow diagram of the lithium source production process of fig. 1.
Fig. 5 is a schematic diagram of the mass conversion in the process of producing lithium carbonate from lepidolite shown in fig. 1.
Detailed Description
The embodiments of the present application will now be described more fully hereinafter with reference to the accompanying drawings. Those of ordinary skill in the art will be able to implement embodiments of the present application based on these descriptions. Before describing embodiments of the present application with reference to the accompanying drawings, it should be noted in particular that:
The technical solutions and technical features provided in the respective sections including the following description may be combined with each other without conflict. Furthermore, the described embodiments, features, and combinations of features can be combined as desired and claimed in any given application.
The embodiments of the present application to which reference is made in the following description are typically only a few, but not all, embodiments, based on which all other embodiments that a person of ordinary skill in the art would obtain without undue effort are within the scope of patent protection.
The terms "comprising," "including," "having," and any variations thereof, in this specification and the corresponding claims and related parts, are intended to cover a non-exclusive inclusion. Other related terms and units may be reasonably construed based on the description provided herein.
Fig. 1 is a schematic overall flow chart of a process for producing lithium carbonate from lepidolite according to example 1 of the present application. The composition of lepidolite is shown in Table 1.
TABLE 1
Note that: the mineral sample had a water content of 9.63wt% and after drying to constant weight at 270 ℃ the physical properties of the various oxides shown in table 1 were tested and shown in table 2.
TABLE 2
The physical properties of the sulfates of the various metal elements shown in table 1 are shown in table 3.
TABLE 3 Table 3
Thus, based on the contents shown in tables 1, 2 and 3, as shown in fig. 1, the process for producing lithium carbonate from lepidolite of example 1 will take the technical idea that: firstly, entering a lithium ore pretreatment process S1, and pretreating lepidolite. The pretreatment includes loosening the lepidolite structure by firing the lepidolite and defluorinating, and refining the lepidolite to form particles (first material). Wherein, the lepidolite structure is loosened by roasting the lepidolite, and the crystal form of the lepidolite ore is changed, for example, the crystal form of lithium oxide is changed from alpha to beta, so that the structure of the lepidolite ore is changed from compact to loose, and fluorine and other organic matters are removed from the ore in the process. Then, the process goes to the acidification and gasification step S2. In the acidification and gasification step S2, the first material is first mixed with a sulfate ion group acidulant to perform a sulfation reaction (acidification for short), so that various oxides (except silica) in the first material are converted into sulfate to form a second material, and lithium oxide is also converted into lithium sulfate. And then, heating the second material to gasify lithium sulfate in the second material so as to volatilize (short for gasification) the second material, wherein other oxides in the second material are converted into metal oxides through heating and decompose sulfur dioxide gas, or are not converted, so that the gas generated by gasification basically consists of gasified lithium sulfate and sulfur dioxide, and the solid phase matters remained after the gasified and volatilized lithium sulfate in the second material are third materials (dry materials). Then, the gasified lithium sulfate is recovered through heat recovery, namely, the gasified lithium sulfate is subjected to heat exchange through flue gas cooling, cooled flue gas containing solid lithium sulfate converted from the gasified lithium sulfate is output, the cooled flue gas is subjected to gas-solid separation through flue gas filtration, and a first filtered solid phase substance and a first filtered gas phase substance are respectively discharged, wherein the first filtered solid phase substance is mainly solid lithium sulfate, and the mass percentage of the lithium sulfate in the first filtered solid phase substance is more than or equal to 95 percent (usually more than or equal to 97 percent), namely, the high-purity lithium sulfate. Finally, the lithium source production process S3 is carried out, the first filtered solid phase substance is taken as a raw material, the raw material is dissolved by water, and then the raw material is mixed with sodium carbonate or sodium hydroxide for reaction after impurity removal, so that the battery-grade lithium carbonate or lithium hydroxide is prepared.
Fig. 5 is a schematic diagram of the mass conversion in the process of producing lithium carbonate from lepidolite shown in fig. 1. As shown in fig. 5, after acidification, all the various oxides (except silica) in the first material are converted to sulfates, where the first material consists essentially of lithium sulfate, aluminum sulfate, iron sulfate, calcium sulfate, magnesium sulfate, manganese sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, and silicon oxide. During gasification, aluminum sulfate, ferric sulfate, calcium sulfate, magnesium sulfate and manganese sulfate are respectively converted into aluminum oxide, ferric oxide, calcium oxide, magnesium oxide and manganese oxide due to the fact that the decomposition temperature is far lower than that of lithium sulfate, sulfur dioxide gas is released, and sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate and silicon oxide are not gasified or decomposed due to the fact that the boiling point is far higher than that of lithium sulfate. Therefore, the gas generated by controllable gasification basically consists of gasified lithium sulfate and sulfur dioxide, and just between the gasified lithium sulfate and the sulfur dioxide, the gasified lithium sulfate can be converted into solid lithium sulfate by cooling to realize separation.
The process for producing lithium carbonate by lepidolite in the embodiment 1 can obtain high-purity lithium sulfate without complex and complicated wet process, greatly reduces the liquid treatment capacity after subsequent water dissolution, and can greatly reduce the scale and the flow of subsequent impurity removal and purification production. The process slag is dry slag, which is favorable for storage, utilization and environmental protection.
Fig. 2 is a specific process flow diagram of the pretreatment process of lithium ores of fig. 1. FIG. 3 is a specific process flow diagram of the acidification gasification process of FIG. 1. Fig. 4 is a specific process flow diagram of the lithium source production process of fig. 1. The process of producing lithium carbonate from this lepidolite is further described below with reference to fig. 2-4.
As shown in fig. 2, a lithium ore pretreatment apparatus includes: a pretreatment roasting kiln 11, a roasting flue gas purification system 12, a roasting material waste heat utilization system 13 and a crushing processing device 14. Wherein the pretreatment roasting kiln 11 is used for roasting lithium ores to loosen the structures of the lithium ores and defluorinating the lithium ores when fluorine is contained in the lithium ores; the roasting flue gas purification system 12 is used for purifying flue gas discharged by the pretreatment roasting kiln 11 and recovering dust in the flue gas; the roasting material waste heat utilization system 13 is used for cooling and utilizing waste heat of the roasted material discharged from the pretreatment roasting kiln 11; the crushing processing device 14 is used for refining the material which is discharged by the roasting material waste heat utilization system and is subjected to waste heat utilization, so that lithium ore becomes particles. Due to the adoption of the roasting flue gas purification system 12 and the roasting material waste heat utilization system 13, the environmental pollution of the pretreatment of the lithium ore can be reduced and the waste heat utilization can be realized.
In a specific embodiment, the pretreatment roasting kiln 11 may adopt a rotary kiln, an input end of the roasting flue gas purification system 12 is connected with a kiln tail of the rotary kiln, and an input end of the roasting material waste heat utilization system 13 is connected with a kiln head of the rotary kiln. When the device works, the flue gas discharged from the kiln tail of the rotary kiln enters a roasting flue gas purification system 12, and the flue gas discharged from the pretreatment roasting kiln 11 is purified by the roasting flue gas purification system 12 and dust in the flue gas is recovered; the roasted material discharged from the kiln head of the rotary kiln enters a roasted material waste heat utilization system 13, and the roasted material discharged from the pretreatment roasting kiln 11 is cooled and subjected to waste heat utilization by the roasted material waste heat utilization system 13.
In a specific embodiment, the roasting fume cleaning system 12 includes a first fume dust remover 121, and the first fume dust remover 121 physically intercepts dust in fume discharged from the pre-treatment roasting kiln 11 through a filter element. The filter element in the first flue gas dust separator 121 may be a metal filter element or a ceramic filter element in order to achieve filtration at higher temperatures. In addition, the flue gas cleaning system 12 may further comprise a waste heat recovery device 122 and an exhaust gas cleaning device 123. The waste heat recovery device 122 may employ a waste heat boiler, so as to perform waste heat recovery on the dedusted flue gas output from the first flue gas dust remover 121. The tail gas purifying device 123 is used for further purifying the flue gas output by the waste heat recovering device 122, such as denitration, defluorination, etc., and specifically sets corresponding purifying measures according to the pollutant components and the content of the flue gas output by the waste heat recovering device 122.
In a specific embodiment, the roasting material waste heat utilization system 13 includes a grate cooler 131 and a second flue gas dust remover 132 connected to an exhaust end of the grate cooler 131, where the second flue gas dust remover 132 includes a filter element for physically intercepting dust in flue gas discharged from the grate cooler 131. Likewise, the filter element in the second flue gas dust collector 132 may be a metal filter element or a ceramic filter element. The grate cooler 131 is an existing cooling device for cooling high-temperature solid materials by using air, and the high-temperature air flow generated by cooling the grate cooler 131 is filtered and dedusted by the second flue gas dust remover 132.
The crushing plant 14 may employ various existing equipment or combinations of equipment so that particles of a corresponding size will be obtained. In one embodiment, the crushing processing device 14 mainly comprises a coarse crusher, a fine crusher and a particle classification system which are arranged in sequence,
in the process for producing lithium carbonate from lepidolite in example 1, lepidolite is fed into a pretreatment firing kiln 11 to be fired to loosen the lepidolite structure and to be defluorinated, and specific firing conditions can be referred to the existing sulfuric acid method. The calcined lepidolite is sent to a calcined material waste heat utilization system 13, cooled, and sent to a crushing processing device 14 for refining processing, so that the lepidolite becomes particles (first material).
As shown in fig. 3, a lithium extraction apparatus includes: a mixing reactor 21, a roasting kiln 22, a heating gasification furnace 23 and a gasification lithium sulfate recovery device 24. The mixing reactor 21 is used for mixing a first material with a sulfate ion group acidulant to carry out sulfation reaction so as to convert the first material into a second material containing lithium sulfate; the roasting kiln 22 is used for roasting the second material after or simultaneously with mixing the first material with the sulfate ion group acidulant to carry out the sulfation reaction so as to convert the first material into the second material containing lithium sulfate, so that the sulfation reaction is fully differentiated and the sulfate ion group acidulant which is not completely reacted is removed; the heating gasification furnace 23 is configured to heat the second material to gasify lithium sulfate in the second material and volatilize the gasified lithium sulfate from the second material, wherein a solid phase remaining after the gasified and volatilized lithium sulfate in the second solid phase is a third material; the gasified lithium sulfate recovery device 24 is used for recovering gasified lithium sulfate.
The mixing reactor 21 may be configured to mix the first material in a number of ways, where the sulfate ion-based acidulant (in the case of concentrated sulfuric acid in particular) is sprayed onto the first material by means of an atomizer head with stirring (e.g., blade stirring or fluidized stirring) the first material. The kiln 22 may be a rotary kiln or a tunnel kiln. The heating gasification furnace 23 may be a converter or a tunnel kiln.
In one embodiment, the gasified lithium sulfate recovery apparatus 24 comprises: a flue gas cooling heat exchanger 241 for recovering heat from the high-temperature flue gas discharged from the heating gasification furnace 23 and outputting cooled flue gas containing solid lithium sulfate converted from gasified lithium sulfate; the first flue gas filter 242 is configured to perform gas-solid separation on the cooled flue gas and discharge a first filtered solid phase object and a first filtered gas phase object respectively, where the first filtered solid phase object is mainly solid lithium sulfate. The filter element in the first smoke filter 242 may be a metal filter element or a ceramic filter element.
In one embodiment, the kiln 22 is coupled to a flue gas treatment system 25; the roasting fume treatment system 25 comprises: a second flue gas filter 251, configured to perform gas-solid separation on the roasting flue gas discharged from the roasting kiln 22, and discharge a second filtered solid phase material and a second filtered gas phase material respectively; a flue gas desulfurization device 252, configured to receive the second filtered gas phase object, perform desulfurization treatment on the second filtered gas phase object, and discharge the desulfurized tail gas; and the material conveying equipment is used for receiving the second filtered solid phase material and returning the filtered solid phase material to the first material or the second material. The filter element in the second smoke filter 251 may be a metal filter element or a ceramic filter element.
In one embodiment, the flue gas desulfurization apparatus 252 outputs the recovered sulfur to a sulfate-ion-based acidulant supply system in the form of the sulfate-ion-based acidulant or in the form of a feedstock for the sulfate-ion-based acidulant. For example, the flue gas desulfurization apparatus 252 may employ a catalytic flue gas desulfurization apparatus that adsorbs sulfur dioxide, water, and oxygen contained in a filtered gas phase on a catalyst and reacts under the catalysis of an active component to generate sulfuric acid, and when the sulfuric acid adhering to the catalyst reaches a certain level, dilute sulfuric acid and/or water is used as a regeneration liquid to spray the catalyst so as to remove the adhering sulfuric acid on the catalyst and release the active site of the catalyst, and the used regeneration liquid is used as sulfuric acid to prepare the sulfate ion group acidulant. The flue gas desulfurization device by the catalytic method is the prior art and is not described in detail herein.
In one embodiment, the first filtered gaseous effluent exiting the first flue gas filter 242 is desulfurized by the flue gas desulfurization apparatus 252.
In the process for producing lithium carbonate from lepidolite according to embodiment 1, the sulfation reaction is carried out by thoroughly mixing the first material with concentrated sulfuric acid while keeping the whole of the first material in a solid state, wherein a sulfate ion-based acidulant is specifically concentrated sulfuric acid (specifically, a sulfuric acid solution with a mass fraction of 98%), and the sulfate ion-based acidulant is reacted with the concentrated sulfuric acid in such a manner that the molar ratio of the sulfate ion in the sulfate ion-based acidulant to the total reactant in the first material is 1.1, whereby various oxides (excluding silica) in the first material are converted into sulfate to form a second material. After the first material is converted into a second material containing lithium sulfate by mixing the first material with a sulfate ion-based acidulant for sulfation, the second material is baked by a baking kiln 22 at a temperature of 180-300 ℃ to fully differentiate the sulfation and remove the incompletely reacted sulfate ion-based acidulant. Thereafter, the second solid phase is heated by the heating gasifier 23, specifically, the second solid phase is heated to 1350 ℃ under the condition of lower than one atmosphere, at this time, lithium sulfate in the second phase is gasified and volatilized (gasified for short) from the second phase, aluminum sulfate, ferric sulfate, calcium sulfate, magnesium sulfate and manganese sulfate in the second phase are converted into metal oxides by the heating and decompose sulfur dioxide gas, and the rest of oxides in the second phase are not converted, so that the gas generated by the gasification is basically composed of gasified lithium sulfate and sulfur dioxide, and the solid phase remained after the lithium sulfate in the second phase is gasified and volatilized is a third material (dry material). Then, the gasified lithium sulfate is recovered by recovering heat of the gasified lithium sulfate through a flue gas cooling heat exchanger 241, and cooled flue gas containing solid lithium sulfate converted from the gasified lithium sulfate is output, and then the cooled flue gas is subjected to gas-solid separation through a first flue gas filter 242, and the first filtered solid phase and the first filtered gas phase are respectively discharged, wherein the first filtered solid phase is mainly solid lithium sulfate, and the mass percentage of the lithium sulfate in the first filtered solid phase is more than or equal to 95% (usually more than or equal to 97%).
As shown in fig. 4, the first solid phase to be filtered is mixed with water by a mixer 31, so that the first solid phase to be filtered is dissolved by water, then the lithium sulfate solution is alkalized and decontaminated by a decontaminating device 32 to obtain a lithium sulfate refined solution, then sodium carbonate is added into the lithium sulfate refined solution by a lithium precipitation device 33, lithium carbonate is generated by reaction, and lithium carbonate is dried by a drying device 44 to obtain battery grade lithium carbonate. Wherein, the alkalization, impurity removal, lithium precipitation and drying are all the prior art.
The process for producing lithium carbonate by lepidolite according to embodiment 2 of the present application is improved on the basis of the process for producing lithium carbonate by lepidolite according to embodiment 1, and the mixing reactor 21 and the roasting kiln 22 in the lithium extraction device are integrated, namely, a rotary kiln is directly adopted. Meanwhile, the first material and the concentrated sulfuric acid are fully mixed and reacted under the condition that the whole substances in the first material are kept in a mud state during the sulfation reaction, wherein the sulfate radical ion group acidulant specifically adopts the concentrated sulfuric acid (specifically a sulfuric acid solution with the mass fraction of 70 percent), and the first material and the concentrated sulfuric acid are fully mixed and reacted according to the mol ratio of sulfate radical ions in the sulfate radical ion group acidulant to the total reactants in the first material of 1.3, so that various oxides (except silicon dioxide) in the first material are converted into sulfate to form a second material.
The process for producing lithium carbonate by lepidolite in the embodiment 3 is improved on the basis of the process for producing lithium carbonate by lepidolite in the embodiment 1, a roasting kiln 22 is omitted, and acidification is directly realized through a mixing reactor 21. In the mixing reactor 21, the first material is sprayed out in the form of particles, and at the same time, the concentrated sulfuric acid as the sulfate-ion-based acidulant is also in the form of particles, so that the first material and the sulfate-ion-based acidulant are prepared in the form of particles to be mixed and reacted with each other.
The process for producing lithium carbonate by lepidolite according to example 4 of the present application is improved on the basis of the process for producing lithium carbonate by lepidolite according to example 1, and the process for producing lithium carbonate or lithium hydroxide by directly mixing gasified lithium sulfate with a sodium carbonate solution or a sodium hydroxide solution to thereby react the lithium sulfate with sodium carbonate or sodium hydroxide is adopted in the recovery of gasified lithium sulfate.
The content of the present application is described above. Those of ordinary skill in the art will be able to implement the present application based on these descriptions. Based on the foregoing specification, all other embodiments that may be obtained by one of ordinary skill in the art without making any inventive effort are intended to be within the scope of this application.
Claims (16)
1. A method of extracting lithium, comprising:
converting a first solid phase containing a lithium-based compound into a second solid phase containing lithium sulfate by dry sulfating reaction by mixing the first solid phase with a sulfate-ion-based acidulant, the lithium sulfate being obtained from the lithium-based compound by the dry sulfating reaction;
vaporizing lithium sulfate in the second solid phase by heating the second solid phase to volatilize the lithium sulfate from the second solid phase, wherein the solid phase remaining after the vaporization and volatilization of the lithium sulfate in the second solid phase is a third solid phase; and
and recycling gasified lithium sulfate, wherein the mass percentage of lithium sulfate in the solid lithium sulfate is more than or equal to 95% when the gasified lithium sulfate is cooled to be solid lithium sulfate.
2. The lithium extraction method according to claim 1, wherein: the first solid phase compound mainly comprises at least one of a first class of compounds, a second class of compounds and a third class of compounds except the lithium-based compounds;
the first type of compound is a metal compound and is converted into first type of metal sulfate through the dry sulfation reaction, and the first type of metal sulfate is converted into first type of metal oxide through the heating and is decomposed into sulfur dioxide gas;
The second class of compounds are metal compounds and are converted into second class of metal sulfates by the dry sulfation reaction, the second class of metal sulfates not being converted by the heating;
the third class of compounds are nonmetallic compounds and are not converted by both the dry sulfation reaction and the heating.
3. The lithium extraction method according to claim 2, wherein: the first solid phase is from lithium ore; if the first solid phase substance contains the first type of compound, the first type of compound is mainly composed of at least one metal oxide; if the first solid phase contains the second class of compounds, the second class of compounds is mainly composed of at least one metal oxide; if the first solid phase contains the third class of compounds, the third class of compounds mainly consists of at least one nonmetallic oxide.
4. A method of extracting lithium as claimed in claim 3, wherein: the first class of compounds comprises at least one of aluminum oxide, iron oxide, calcium oxide, magnesium oxide and manganese oxide; the second class of compounds comprises at least one of sodium oxide, potassium oxide, rubidium oxide and cesium oxide; the third class of compounds comprises silicon oxide.
5. A method of extracting lithium as claimed in claim 3, wherein: the lithium ore is spodumene or lepidolite.
6. A method of extracting lithium as claimed in claim 3, wherein: the first solid phase is obtained by pretreating a lithium ore, the pretreatment comprising loosening the structure of the lithium ore by roasting the lithium ore and defluorinating when fluorine is contained in the lithium ore, and refining the lithium ore to form particles of the lithium ore.
7. The lithium extraction method according to claim 1, wherein: the dry sulfation reaction is to fully mix the first solid phase substance and the sulfate radical acidulant under the condition that the whole substance in the first solid phase substance is kept in a solid state.
8. The lithium extraction method according to claim 7, wherein: and during the dry sulfation reaction, the sulfate ion acidifier and the first solid phase substance are fully mixed and reacted according to the mol ratio of the sulfate ion in the sulfate ion acidifier to the total reactant in the first solid phase substance of 1-1.3.
9. The lithium extraction method according to claim 7, wherein: the sulfate radical ion radical acidulant is concentrated sulfuric acid.
10. The lithium extraction method according to claim 7, wherein: and further comprising, after or simultaneously with the conversion of the first solid phase into a second solid phase containing lithium sulfate by dry sulfation reaction by mixing the first solid phase with sulfate ion-based acidulant, fully differentiating the dry sulfation reaction by roasting the second solid phase and removing the incompletely reacted sulfate ion-based acidulant, and then vaporizing lithium sulfate in the second solid phase by heating the second solid phase to volatilize from the second solid phase.
11. The lithium extraction method according to claim 1, wherein: the heating is specifically heating the second solid phase up to 1350 ℃ under conditions of less than one atmosphere.
12. The lithium extraction method according to claim 1, wherein: the first solid phase and the sulfate-based acidulant are prepared in the form of particles and are mixed with each other.
13. The lithium extraction method according to claim 1, wherein: the method comprises the steps of recycling gasified lithium sulfate, namely, carrying out heat recovery on the gasified lithium sulfate through flue gas cooling heat exchange, outputting cooled flue gas containing solid lithium sulfate converted from the gasified lithium sulfate, carrying out gas-solid separation on the cooled flue gas through flue gas filtration, and respectively discharging a first filtered solid phase substance and a first filtered gas phase substance, wherein the first filtered solid phase substance is mainly solid lithium sulfate, and the mass percentage of the lithium sulfate in the first filtered solid phase substance is more than or equal to 95%;
Alternatively, the recovering the vaporized lithium sulfate comprises mixing the vaporized lithium sulfate with a sodium carbonate solution or sodium hydroxide solution to react the lithium sulfate with sodium carbonate or sodium hydroxide to produce lithium carbonate or lithium hydroxide.
14. A lithium extraction apparatus, comprising:
a mixing reactor for mixing a first solid phase substance with a sulfate radical ion group acidulant to carry out dry sulfation reaction so as to convert the first solid phase substance into a second solid phase substance containing lithium sulfate, wherein the first solid phase substance contains a lithium-based compound, and the lithium sulfate is obtained by the dry sulfation reaction of the lithium-based compound;
a heating gasification furnace for heating the second solid phase material to gasify lithium sulfate in the second solid phase material and volatilize the gasified lithium sulfate from the second solid phase material, wherein the solid phase material remaining after the gasified and volatilized lithium sulfate in the second solid phase material is a third solid phase material; and
the gasified lithium sulfate recovery device is used for recovering gasified lithium sulfate.
15. The lithium extraction apparatus of claim 14, wherein the gasified lithium sulfate recovery device comprises:
the flue gas cooling heat exchanger is used for recovering heat of high-temperature flue gas discharged by the heating gasification furnace and outputting cooled flue gas containing solid lithium sulfate converted from gasified lithium sulfate;
The first flue gas filter is used for carrying out gas-solid separation on the cooled flue gas and respectively discharging a first filtered solid phase object and a first filtered gas phase object, and the first filtered solid phase object is mainly solid lithium sulfate.
16. The lithium extraction apparatus of claim 14, further comprising: and a roasting kiln arranged between the mixing reactor and the heating gasification furnace and used for carrying out dry sulfation reaction on a first solid phase substance and a sulfate radical ion group acidulant to convert the first solid phase substance into a second solid phase substance containing lithium sulfate, roasting the second solid phase substance to fully differentiate the dry sulfation reaction and remove the incompletely reacted sulfate radical ion group acidulant, and then heating the second solid phase substance to gasify the lithium sulfate in the second solid phase substance and volatilize the lithium sulfate from the second solid phase substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310339384.9A CN116479258A (en) | 2023-03-31 | 2023-03-31 | Lithium extraction method and equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310339384.9A CN116479258A (en) | 2023-03-31 | 2023-03-31 | Lithium extraction method and equipment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116479258A true CN116479258A (en) | 2023-07-25 |
Family
ID=87226000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310339384.9A Pending CN116479258A (en) | 2023-03-31 | 2023-03-31 | Lithium extraction method and equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116479258A (en) |
-
2023
- 2023-03-31 CN CN202310339384.9A patent/CN116479258A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7258093B2 (en) | Recovery of lithium from silicate minerals | |
| CN109047285B (en) | Method and system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of aluminum electrolytic cell | |
| JP7354507B2 (en) | Desulfurized ash resource recovery method and resource recovery system | |
| CN107475542B (en) | Method for treating rare earth concentrate | |
| CN108754125B (en) | Clean process for extracting vanadium from vanadium-containing material through sodium salt roasting | |
| CN109809456B (en) | System and method for co-producing calcium oxide and sulfur by coal gasification and gypsum calcination | |
| CN111498811B (en) | Process and device for gypsum calcination and CO coupling carbon thermal reduction | |
| CN109928415B (en) | System and method for recovering calcium carbonate and sulfur by calcining gypsum | |
| CN109573955B (en) | Device and process for preparing sulfur and recovering desulfurizer through sulfate carbon thermal reduction | |
| CN107324288B (en) | Comprehensive treatment and recycling process for acidic waste gypsum | |
| CN109108050B (en) | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis overhaul residues | |
| CN109108048B (en) | Mechanochemical conversion and recovery method of sodium-containing compound and fluorine-containing compound in aluminum electrolysis anode carbon slag | |
| CN102755829A (en) | Desulfurizer and application thereof | |
| US8623319B2 (en) | Process for directly producing sulfur trioxide and sulfuric acid using gypsum as raw material | |
| CN104555947B (en) | Method for recovering electrolytic manganese slag | |
| CN100453450C (en) | Coproducing cement technological method of producing acid using phosphogypsum and sulfur | |
| WO2020124655A1 (en) | Process for preparing sulfur by means of sulfate/nitrate iron-carbon reduction and recovering desulfurization/denitrification agent | |
| CN109127657B (en) | Mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in aluminum electrolysis overhaul residues | |
| CN107267784B (en) | System for handle rare earth concentrate | |
| CN111233020B (en) | System and method for preparing calcium oxide and sulfur by using industrial byproduct gypsum | |
| CN220012758U (en) | Lithium ore preprocessing device and lithium extraction equipment | |
| CN103301744B (en) | Desulfurization device and method for preparing sulfur particles by removing SO2 from flue gas | |
| CN109351150B (en) | Device and method for gradient utilization of energy in carbon thermal reduction process | |
| CN116479258A (en) | Lithium extraction method and equipment | |
| CN116463510A (en) | Lithium extraction method and equipment |
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 |