CN116770098A - Method for extracting lithium from clay-type lithium ore - Google Patents
Method for extracting lithium from clay-type lithium ore Download PDFInfo
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- CN116770098A CN116770098A CN202310797059.7A CN202310797059A CN116770098A CN 116770098 A CN116770098 A CN 116770098A CN 202310797059 A CN202310797059 A CN 202310797059A CN 116770098 A CN116770098 A CN 116770098A
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- Prior art keywords
- lithium
- leaching
- clay
- iron
- slag
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002386 leaching Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 52
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 49
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 49
- 239000002893 slag Substances 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 43
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000004927 clay Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 230000023556 desulfurization Effects 0.000 claims abstract description 8
- 238000001723 curing Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000012054 meals Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001166 ammonium sulphate Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 39
- 229910052742 iron Inorganic materials 0.000 abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000605 extraction Methods 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 63
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- 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 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229960004887 ferric hydroxide Drugs 0.000 description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011552 falling film Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical group O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- -1 phospholithium-aluminum Chemical compound 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 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 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000001238 wet grinding 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
-
- 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
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps: mixing clay type lithium ores with acid liquor for slurry mixing reaction, and carrying out solid-liquid separation to obtain ferric salt leaching liquid and iron-removing clay type lithium slag; mixing the iron-removing clay-type lithium slag with ammonium sulfate to obtain a raw material; curing the raw materials to obtain clinker; leaching the clinker to obtain a lithium aluminum leaching solution and high-silicon slag; adding ammonia gas and/or ammonia water into the lithium aluminum leaching solution, and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution; and carrying out desulfurization treatment on the lithium-containing aluminum hydroxide, and roasting and leaching to obtain lithium-rich liquid and aluminum oxide. The method overcomes the defects in the clay type lithium ore lithium extraction technology, has short flow and low energy consumption, and achieves the purposes of separating and extracting lithium, aluminum, iron and silicon under the system.
Description
Technical Field
The invention belongs to the field of lithium production, and relates to a method for extracting lithium from clay-type lithium ores.
Background
Lithium is currently widely used as an important energy strategic metal in the fields of new energy, nuclear energy, medical treatment, ceramics and the like, and is known as white petroleum. At present, the lithium extraction raw materials are divided into three types, one type is hard rock such as spodumene, lepidolite and phospholithium-aluminum stone; the other is brine type of salt lake such as salt lake brine, mineral spring and well brine; the last one is of the clay type. The clay type lithium ores are not developed and utilized on a large scale due to the fact that the clay type lithium ores are found to be late and the lithium occurrence state is complex, and along with the continuous increase of the demand of lithium resources, the development and the utilization of the clay type lithium ores are important points in the future.
The current methods for extracting lithium from clay-type lithium ores studied at home and abroad are roughly divided into an auxiliary agent roasting method, an acid method and an alkali method. The auxiliary agent roasting is to mix and roast clay type lithium ore with sulfate such as calcium sulfate, calcium fluoride, sodium sulfate and the like, the leaching effect of lithium is considerable, but elements such as fluorine, calcium potassium and the like are introduced into the solution, the cost of later purification is increased, the corrosiveness of furnace gas is higher, and the requirement on equipment is high. The alkaline method adopts lime and sodium hydroxide for roasting, and has large slag quantity and high equipment maintenance cost. The acid method directly uses sulfuric acid for low-temperature curing, the leaching rate is over 90 percent, but the sulfuric acid is large in dosage, and a large amount of sulfur oxides can be generated by roasting, so that the equipment is severely corroded, and the flue gas treatment cost is high.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for extracting lithium from clay-type lithium ores, which overcomes the defects in the technology for extracting lithium from clay-type lithium ores, has short flow and low energy consumption, and achieves the purposes of separating and extracting lithium, aluminum, iron and silicon under the system.
In order to achieve the technical effects, the invention adopts the following technical scheme:
the invention provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps:
(1) Mixing clay type lithium ores with acid liquor for slurry mixing reaction to obtain ferric salt leaching solution and iron-removing clay type lithium slag;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate to obtain a raw material; curing the raw materials to obtain clinker;
(3) Leaching the clinker in the step (2) to obtain a lithium aluminum leaching solution and high-silicon slag;
(4) Adding ammonia gas and/or ammonia water into the lithium aluminum leaching solution obtained in the step (3), and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
(5) And (3) desulfurizing the lithium-containing aluminum hydroxide in the step (4), and roasting and leaching to obtain lithium-rich liquid and aluminum oxide.
In the invention, ammonium sulfate is used as an additive for sulfate roasting, so that the method has the advantages of low roasting temperature, no introduction of impurity ions in the roasting process, and the like, and no sulfide gas is generated theoretically. And compared with sulfuric acid, the ammonium sulfate has higher safety, the pH of the ammonium sulfate aqueous solution is about 5.5, the ammonium sulfate aqueous solution is almost non-corrosive, and the requirement on equipment is lower than that of sulfuric acid.
In the invention, the clay type lithium ore is subjected to iron removal before raw material preparation, so that iron element is prevented from forming iron hydroxide in the subsequent steps, the iron hydroxide can adsorb lithium, and the extraction rate of lithium is reduced. The purpose of desulfurization is to increase the purity of aluminum hydroxide, and alumina containing sulfur impurities has no economic value.
As a preferred technical scheme of the invention, the acid liquor in the step (1) comprises sulfuric acid.
In a preferred embodiment of the present invention, the time of the slurry mixing reaction in the step (1) is 1 to 3 hours, such as 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours or 3 hours, but the present invention is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the temperature of the slurry mixing reaction in the step (1) is 70 to 100 ℃, such as 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like, but the method is not limited to the listed values, and other non-listed values within the range are applicable.
As a preferred technical scheme of the invention, the mass ratio of the ammonium sulfate to the iron-removing clay-type lithium slag in the step (2) is 3-7:1, such as 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1 or 7:1, etc., but not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
In a preferred embodiment of the present invention, the curing temperature in the step (2) is 300 to 600 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, but the curing temperature is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the curing time in step (2) is 1 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the ammonium sulfate solution in the step (4) is returned to the step (2) for preparing the raw material.
As a preferable technical scheme of the invention, the lithium-containing aluminum hydroxide in the step (5) is mixed with alkali for desulfurization treatment.
Preferably, the base comprises any one or a combination of at least two of ammonia, sodium hydroxide and sodium carbonate.
In a preferred embodiment of the present invention, the baking temperature in the step (5) is 500 to 1100 ℃, such as 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
In a preferred embodiment of the present invention, the leaching temperature in the step (5) is 70 to 100 ℃, such as 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
Preferably, the leaching time in step (5) is 0.5-3 hours, such as 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the method for extracting lithium from the clay-type lithium ore comprises the following steps:
(1) Mixing clay type lithium ores with sulfuric acid for a slurry mixing reaction, wherein the temperature of the slurry mixing reaction is 70-100 ℃ and the time is 1-3 hours, and carrying out solid-liquid separation to obtain ferric salt leaching liquid and iron-removing clay type lithium slag;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate according to a mass ratio of 1:3-7 to obtain a raw material; curing the raw materials to obtain clinker, wherein the curing temperature is 300-600 ℃ and the curing time is 1-5 h;
(3) Leaching the clinker in the step (2) to obtain a lithium aluminum leaching solution and high-silicon slag;
(4) Adding ammonia gas or ammonia water into the lithium aluminum leaching solution obtained in the step (3), and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
(5) And (3) mixing the lithium-containing aluminum hydroxide and alkali in the step (4) for desulfurization treatment, roasting at 500-1100 ℃, and leaching at 70-100 ℃ for 0.5-3 h to obtain lithium-rich liquid and aluminum oxide.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The method does not add any auxiliary agent capable of introducing new impurities, can effectively extract lithium, aluminum and iron in clay type lithium ores, has dissolution rates of more than 90%, 70% and 95% of lithium, aluminum and iron respectively, adopts a process of removing iron firstly and then curing and dissolving out, adopts an advanced aluminum hydroxide desulfurization technology, ensures that sulfur trioxide is not generated in the aluminum hydroxide roasting process, and reduces the flue gas treatment difficulty and the material requirement of a roasting furnace;
(2) The invention uses the adsorptivity of aluminum hydroxide, uses a neutralizer to adjust the pH of leaching liquid to enable the aluminum in the leaching liquid to be precipitated in the form of aluminum hydroxide, simultaneously adsorbs and precipitates lithium ions in the solution, the adsorption capacity reaches 99.5%, then the desulfurized lithium-containing aluminum hydroxide is roasted, the roasted alumina is soaked in water, the lithium enrichment rate in the solution can be improved by more than 2 times, the deintercalation rate is up to more than 95%, the metallurgical grade alumina which is favorable for realizing resource utilization and the lithium-rich liquid with the impurity ion concentration of iron, aluminum, manganese, magnesium, calcium and the like lower than 200mg/L are obtained, and the lithium carbonate, the lithium phosphate, the lithium hydroxide and the like can be prepared by the impurity removal procedure of the lithium-rich liquid.
Drawings
Fig. 1 is a schematic flow chart of a method for extracting lithium from clay-type lithium ores according to an embodiment of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
the specific embodiment of the invention provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps:
(1) Mixing clay type lithium ores with acid liquor for slurry mixing reaction, and carrying out solid-liquid separation to obtain ferric salt leaching liquid and iron-removing clay type lithium slag;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate to obtain a raw material; curing the raw materials to obtain clinker;
(3) Leaching the clinker in the step (2) to obtain a lithium aluminum leaching solution and high-silicon slag;
(4) Adding alkali into the lithium aluminum leaching solution obtained in the step (3), and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
(5) And (3) desulfurizing the lithium-containing aluminum hydroxide in the step (4), and roasting and leaching to obtain lithium-rich liquid and aluminum oxide.
In one specific embodiment of the present invention, the clay-type lithium ore is subjected to a fine grinding treatment before the slurry mixing reaction in the step (1), and the fine grinding treatment may be wet grinding or dry grinding.
In one specific embodiment of the invention, in the step (1), the iron element of the clay-type lithium ore reacts with the acid solution to generate soluble ferric salt (such as ferric sulfate) which enters the liquid phase, so that the soluble ferric salt is separated from other valuable elements in the clay-type lithium ore.
In one embodiment of the present invention, the amount of the acid solution and the concentration of the acid solution in the slurry mixing reaction in the step (1) may be specifically selected according to the content of the iron element and the content of other elements in the clay-type lithium ore, which is not specifically limited herein.
In one embodiment of the invention, the iron-free clay-type lithium slag is washed, preferably in multistage countercurrent washing, to remove excess acid solution and residual soluble iron salts prior to step (2) of preparing the raw meal.
In one embodiment of the invention, a neutralizing agent (such as ammonia water) is added into a solution containing soluble ferric salt (such as ferric sulfate), and the solution is subjected to solid-liquid separation to obtain an ammonium sulfate solution and iron-containing slag, wherein the ammonium sulfate solution can be used for preparing the raw material in the step (2) after evaporation and crystallization. In another embodiment of the invention, the dissolution solution containing soluble ferric salt (such as ferric sulfate) and the multi-stage countercurrent washing solution of the iron-removing clay-type lithium slag are combined, and then a neutralizing agent (such as ammonia water) is added. The conditions of the multistage countercurrent washing may be specifically selected according to the pH of the liquid after washing and the content of elemental iron, and are not particularly limited herein.
In one embodiment of the present invention, the mode of mixing the iron-removing clay-type lithium slag and the ammonium sulfate in the step (2) may be grinding and mixing.
In one specific embodiment of the invention, clinker and a dissolution solvent (such as water) in the step (3) are dissolved in a stirred normal pressure reaction tank, lithium and aluminum enter the solution in the form of sulfate, and silicon remains in the residue to form high silicon slag; and (3) solid-liquid separation and multistage countercurrent washing are carried out on the high-silicon slag, so that lithium and aluminum in the clinker are fully dissolved out, and the lithium-containing aluminum sulfate solution and the high-silicon slag are obtained. The conditions of the elution and the multistage countercurrent washing may be specifically selected according to the content of lithium and aluminum elements in the elution solution and the post-washing solution, and are not particularly limited herein.
In one embodiment of the present invention, the specific amount of ammonia gas or ammonia water in step (4) may be specifically selected according to the content of lithium and aluminum elements in the lithium-aluminum leachate, and is not specifically limited herein.
In a specific embodiment of the present invention, the amount of the alkali used for desulfurizing the lithium-containing aluminum hydroxide in the step (5) may be specifically selected according to the content of the sulfur element in the lithium-containing aluminum hydroxide, and is not particularly limited herein. The conditions for desulfurizing the lithium-containing aluminum hydroxide can be that the lithium-containing aluminum hydroxide is dissolved by adopting liquid alkali, and sodium hydroxide solution is added at 70 ℃ until the pH value is more than 12, so as to prepare purer sodium aluminate solution, and Al (OH) is added into the solution 3 Seed crystal, sulfur-free lithium-containing aluminum hydroxide precipitate is prepared by adopting a seed decomposition method
In one specific embodiment of the invention, the main component of the prepared high silicon slag is silicon dioxide, and the prepared high silicon slag is used for preparing high silicon filler; the main component of the ferric hydroxide slag is ferric hydroxide, and is used for preparing polymeric ferric sulfate; the lithium-rich liquid can be used for preparing lithium carbonate, lithium phosphate, lithium hydroxide and the like by impurity removal.
Example 1
The embodiment provides a method for extracting lithium from clay-type lithium ores, the flow of which is shown in fig. 1, the method comprises the following steps:
(1) Mixing 1000g of clay type lithium ore (the main elements comprise (dry basis) aluminum oxide 61.09%, lithium oxide 0.38%, silicon dioxide 18.53% and ferric oxide 1.87%) with 15wt% sulfuric acid according to a solid-to-liquid ratio of 5:1 for a slurry mixing reaction, wherein the temperature of the slurry mixing reaction is 70 ℃, the time is 3 hours, the secondary countercurrent leaching is carried out, and the solid-liquid separation is carried out to obtain ferric sulfate leaching solution and iron-removing clay type lithium slag;
adding ammonia water (from the curing treatment of the step (2)) into the ferric sulfate leaching solution, precipitating iron element in the form of ferric hydroxide, performing pressurized solid-liquid separation and washing to obtain ferric hydroxide slag and ammonium sulfate solution, performing falling film evaporation on the ammonium sulfate solution, performing pressurized separation to obtain ammonium sulfate, and returning the ammonium sulfate to the step (2) for raw material preparation and recycling;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate according to a mass ratio of 1:3 to obtain a raw material; curing the raw material to obtain clinker and ammonia gas (the ammonia gas is used for preparing ammonia water), wherein the curing temperature is 400 ℃ and the curing time is 2 hours;
(3) Dissolving the clinker in the step (2) in hot water by using a reaction tank with stirring and normal pressure for 2 hours, and carrying out pressurized separation for three-stage countercurrent to obtain lithium aluminum leaching solution and high silicon slag; the main components of the high silicon slag are as follows: al (Al) 2 O 3 ：23.89％、Li 2 O：0.07％、SiO 2 ：53.61％、Fe 2 O 3 ：0.04％；
(4) Adding ammonia water (from the curing treatment of the step (2)) into the lithium aluminum leaching solution in the step (3), and carrying out vacuum solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
the ammonium sulfate is subjected to falling film evaporation, and then the pressurized separation is carried out to obtain the ammonium sulfate, and the ammonium sulfate is returned to the step (2) for raw material preparation and recycling;
(5) Dissolving the lithium-containing aluminum hydroxide in the step (4) by adopting liquid alkali, adding a sodium hydroxide solution at 70 ℃ until the pH value is more than 12, and preparing a purer sodium aluminate solution, wherein Al (OH) is added into the solution 3 Seed crystal, adopt seed decomposition method to prepare and obtain sulfur-free lithium-containing aluminum hydroxide precipitate; roasting the sulfur-free lithium-containing aluminum hydroxide in a rotary kiln at 500 ℃ to obtain lithium-containing aluminum oxide; and leaching the lithium-containing alumina in hot water at 90 ℃ for 2 hours by using a reaction tank with stirring and normal pressure to obtain lithium-rich liquid and alumina. The main components of the lithium-rich liquid are Li:1267ppm, al:28pm, fe:20ppm, mn, 9ppm, ca:11ppm, mg:12ppm, K:14ppm, na:2157ppm, S:5ppm of alumina component Al 2 O 3 ：98.5％、Fe 2 O 3 ：0.01％、Na 2 O：0.63％、SiO 2 ：0.0％、SO 3 ：0.02％。
Example 2
The embodiment provides a method for extracting lithium from clay-type lithium ores, the flow of which is shown in fig. 1, the method comprises the following steps:
(1) Mixing 1000g of clay type lithium ore (the main elements are (dry basis) aluminum oxide 68.39%, lithium oxide 0.53%, silicon dioxide 16.53% and ferric oxide 7.89%) with sulfuric acid with concentration of 10wt% according to a solid-to-liquid ratio of 4:1 for a slurry mixing reaction, wherein the temperature of the slurry mixing reaction is 100 ℃, the time is 1h, single-stage countercurrent leaching is carried out, and pressure solid-liquid separation and washing are carried out to obtain ferric sulfate leaching solution and iron-removing clay type lithium slag;
adding ammonia water (from the curing treatment of the step (2)) into the ferric sulfate leaching solution, precipitating the iron element in the form of ferric hydroxide, carrying out pressurized solid-liquid separation and washing to obtain ferric hydroxide slag and ammonium sulfate solution, adopting forced circulation evaporation of the ammonium sulfate solution, and carrying out centrifugal separation to obtain ammonium sulfate, and returning the ammonium sulfate to the step (2) for raw material preparation and recycling;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate according to a mass ratio of 1:4 to obtain a raw material; curing the raw material to obtain clinker and ammonia gas (the ammonia gas is used for preparing ammonia water), wherein the curing temperature is 600 ℃ and the curing time is 1h;
(3) Dissolving the clinker in the step (2) in hot water for 1h by using a one-stage mill, and carrying out pressurized separation on four-stage countercurrent to obtain lithium aluminum leaching solution and high-silicon slag; the main components of the high silicon slag are as follows: al (Al) 2 O 3 ：26.17％、Li 2 O：0.06％、SiO 2 ：48.9％、Fe 2 O 3 ：0.01％；
(4) Adding ammonia water (from the curing treatment of the step (2)) into the lithium aluminum leaching solution in the step (3), and carrying out vacuum solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
the ammonium sulfate is subjected to forced circulation evaporation, and the ammonium sulfate obtained after centrifugal separation is returned to the step (2) for raw material preparation and recycling;
(5) Dissolving the lithium-containing aluminum hydroxide in the step (4) by adopting liquid alkali, adding a sodium hydroxide solution at 70 ℃ until the pH value is more than 12, and preparing a purer sodium aluminate solution, wherein Al (OH) is added into the solution 3 Seed crystal, adopt seed decomposition method to prepare and obtain sulfur-free lithium-containing aluminum hydroxide precipitate; thereafter said is free ofRoasting sulfur lithium-containing aluminum hydroxide in a rotary kiln at 1200 ℃ to obtain lithium-containing aluminum oxide; and leaching the lithium-containing alumina in hot water at 70 ℃ for 1h by using a reaction tank with stirring and normal pressure to obtain lithium-rich liquid and alumina. The main components of the lithium-rich liquid are Li:1538ppm, al:13pm, fe:0ppm, mn, 5ppm, ca:24ppm, mg:12ppm, K:36ppm, na:4117ppm, S:23ppm of alumina component Al 2 O 3 ：98.6％、Fe 2 O 3 ：0.00％、Na 2 O：0.65％、SiO 2 ：0.0％、SO 3 ：0.02％。
Example 3
The embodiment provides a method for extracting lithium from clay-type lithium ores, the flow of which is shown in fig. 1, the method comprises the following steps:
(1) Mixing 1000g of clay type lithium ore (the main elements comprise (dry basis) aluminum oxide 58.73%, lithium oxide 0.63%, silicon dioxide 21.78% and ferric oxide 6.24%) with 15wt% sulfuric acid according to a solid-to-liquid ratio of 4:1 for a slurry mixing reaction, wherein the temperature of the slurry mixing reaction is 80 ℃, the time is 2 hours, three-stage countercurrent leaching is carried out, and pressure solid-liquid separation and washing are carried out to obtain ferric sulfate leaching solution and iron-removing clay type lithium slag;
adding ammonia water (from the curing treatment of the step (2)) into the ferric sulfate leaching solution, precipitating iron element in the form of ferric hydroxide, performing pressurized solid-liquid separation and washing to obtain ferric hydroxide slag and ammonium sulfate solution, performing falling film evaporation on the ammonium sulfate solution, performing pressurized separation to obtain ammonium sulfate, and returning the ammonium sulfate to the step (2) for raw material preparation and recycling;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate according to a mass ratio of 1:6 to obtain a raw material; curing the raw material to obtain clinker and ammonia gas (the ammonia gas is used for preparing ammonia water), wherein the curing temperature is 400 ℃ and the curing time is 5 hours;
(3) Dissolving the clinker in the step (2) in hot water for 1h by using a two-stage mill, and carrying out pressurized separation on four-stage countercurrent to obtain lithium aluminum leaching solution and high-silicon slag; the main components of the high silicon slag are as follows: al (Al) 2 O 3 ：21.15％、Li 2 O：0.08％、SiO 2 ：58.61％、Fe 2 O 3 ：0.02％；
(4) Adding ammonia water (from the curing treatment of the step (2)) into the lithium aluminum leaching solution in the step (3), and carrying out vacuum solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
the ammonium sulfate is subjected to forced circulation evaporation, and the ammonium sulfate obtained after centrifugal separation is returned to the step (2) for raw material preparation and recycling;
(5) Dissolving the lithium-containing aluminum hydroxide in the step (4) by adopting liquid alkali, adding a sodium hydroxide solution at 70 ℃ until the pH value is more than 12, and preparing a purer sodium aluminate solution, wherein Al (OH) is added into the solution 3 Seed crystal, adopt seed decomposition method to prepare and obtain sulfur-free lithium-containing aluminum hydroxide precipitate; roasting the sulfur-free lithium-containing aluminum hydroxide in a rotary kiln at 1100 ℃ to obtain lithium-containing aluminum oxide; and leaching the lithium-containing alumina in hot water at 90 ℃ for 1h by using a reaction tank with stirring and normal pressure to obtain lithium-rich liquid and alumina. The main components of the lithium-rich liquid are Li:1836ppm, al:33pm, fe:3ppm, mn, 21ppm, ca:9ppm, mg:16ppm, K:25ppm, na:4536ppm, S:5ppm of alumina component Al 2 O 3 ：98.8％、Fe 2 O 3 ：0.00％、Na 2 O：0.60％、SiO 2 ：0.0％、SO 3 ：0.01％。
Example 4
In this example, the conditions were the same as in example 1 except that the mass ratio of the iron-removing clay-type lithium slag to ammonium sulfate in step (2) was 1:7.
Comparative example 1
This comparative example was conducted under the same conditions as in example 1 except that the preliminary iron removal was not conducted in step (1).
Comparative example 2
The comparative example was conducted in the same manner as in example 1 except that the desulfurization treatment was not conducted on lithium-containing aluminum hydroxide in step (5) and the calcination was directly conducted. The lithium-rich liquid comprises the following components: 1412ppm, al:853pm, fe:35ppm, mn, 12ppm, ca:21ppm, mg:7ppm, K:10ppm, na:5ppm, S:7580ppm, alumina component of Al 2 O 3 ：89.2％、Fe 2 O 3 ：0.13％、Na 2 O：0.01％、SiO 2 ：0.0％、SO 3 ：9.8％。
Comparative example 3
This comparative example was conducted in the same manner as in example 1 except that the temperature of the slurry-mixing reaction in step (1) was 20 ℃.
Comparative example 4
The comparative example was conducted in the same manner as in example 1 except that the mass ratio of the iron-removing clay-type lithium slag and ammonium sulfate in step (2) was 1:1.
The lithium, aluminum and iron extraction rates of examples 1 to 4 and comparative example 1 were calculated, and the results are shown in table 1.
The calculation method of the extraction rate of aluminum and iron utilizes the conversion of the content of the added clay type lithium ore element and the content of the byproduct element, and the calculation method of the extraction rate of lithium utilizes the conversion of the content of the clay type lithium ore element and the content of the lithium-rich liquid element.
TABLE 1
| Lithium extraction yield/% | Aluminum extraction yield/% | Iron extraction yield/% | |
| Example 1 | 90.2 | 68.7 | 97.8 |
| Example 2 | 92.2 | 67.3 | 98.8 |
| Example 3 | 93.8 | 65.0 | 99.8 |
| Example 4 | 93.6 | 72.3 | 98.3 |
| Comparative example 1 | 46.5 | 63.2 | 99.5 |
| Comparative example 2 | 88.5 | 66.4 | 98.1 |
| Comparative example 3 | 61.9 | 63.7 | 30.4 |
| Comparative example 4 | 61.4 | 47.2 | 98.9 |
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A method for extracting lithium from clay-type lithium ores, which is characterized by comprising the following steps:
(1) Mixing clay type lithium ores with acid liquor for slurry mixing reaction to obtain ferric salt leaching solution and iron-removing clay type lithium slag;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate to obtain a raw material; curing the raw materials to obtain clinker;
(3) Leaching the clinker in the step (2) to obtain a lithium aluminum leaching solution and high-silicon slag;
(4) Adding ammonia gas and/or ammonia water into the lithium aluminum leaching solution obtained in the step (3), and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
(5) And (3) desulfurizing the lithium-containing aluminum hydroxide in the step (4), and roasting and leaching to obtain lithium-rich liquid and aluminum oxide.
2. The method of claim 1, wherein the acid liquor of step (1) comprises sulfuric acid.
3. The method according to claim 1 or 2, wherein the size mixing reaction in step (1) takes 1 to 3 hours;
preferably, the temperature of the slurry mixing reaction in the step (1) is 70-100 ℃.
4. A method according to any one of claims 1 to 3, wherein the mass ratio of the ammonium sulphate to the iron-removing clay-type lithium slag in step (2) is 3-7:1.
5. The method of any one of claims 1-4, wherein the curing in step (2) is at a temperature of 300-600 ℃;
preferably, the curing time in the step (2) is 1 to 5 hours.
6. The method according to any one of claims 1-5, characterized in that the ammonium sulphate solution of step (4) is returned to step (2) for the preparation of raw meal.
7. The method according to any one of claims 1 to 6, wherein the lithium-containing aluminum hydroxide of step (5) is mixed with a base for desulfurization treatment;
preferably, the base comprises any one or a combination of at least two of ammonia, sodium hydroxide and sodium carbonate.
8. The method according to any one of claims 1 to 7, wherein the temperature of the calcination in step (5) is 500 to 1100 ℃.
9. The method of any one of claims 1 to 8, wherein the temperature of the leaching of step (5) is from 70 to 100 ℃;
preferably, the leaching time in the step (5) is 0.5-3 h.
10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(1) Mixing clay type lithium ores with sulfuric acid for a slurry mixing reaction, wherein the temperature of the slurry mixing reaction is 70-100 ℃ and the time is 1-3 hours, and carrying out solid-liquid separation to obtain ferric salt leaching liquid and iron-removing clay type lithium slag;
(2) Mixing the iron-removing clay-type lithium slag obtained in the step (1) with ammonium sulfate according to a mass ratio of 1:3-7 to obtain a raw material; curing the raw materials to obtain clinker, wherein the curing temperature is 300-600 ℃ and the curing time is 1-5 h;
(3) Leaching the clinker in the step (2) to obtain a lithium aluminum leaching solution and high-silicon slag;
(4) Adding ammonia gas or ammonia water into the lithium aluminum leaching solution obtained in the step (3), and carrying out solid-liquid separation to obtain lithium-containing aluminum hydroxide and an ammonium sulfate solution;
(5) And (3) mixing the lithium-containing aluminum hydroxide and alkali in the step (4) for desulfurization treatment, roasting at 500-1100 ℃, and leaching at 70-100 ℃ for 0.5-3 h to obtain lithium-rich liquid and aluminum oxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117230323A (en) * | 2023-09-21 | 2023-12-15 | 安徽大学绿色产业创新研究院 | Method for extracting lithium, aluminum and silicon from clay lithium ore |
| CN118147456A (en) * | 2024-05-11 | 2024-06-07 | 矿冶科技集团有限公司 | Clay lithium ore raw ore calcine leaching process and leaching solution iron removal method thereof |
| CN118405712A (en) * | 2024-06-28 | 2024-07-30 | 矿冶科技集团有限公司 | Method for selectively extracting lithium oxide from clay-type lithium resources |
| CN118880064A (en) * | 2024-07-17 | 2024-11-01 | 昆明理工大学 | A method for low-temperature acid-free leaching of lithium from clay-type lithium ore |
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2023
- 2023-06-30 CN CN202310797059.7A patent/CN116770098A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117230323A (en) * | 2023-09-21 | 2023-12-15 | 安徽大学绿色产业创新研究院 | Method for extracting lithium, aluminum and silicon from clay lithium ore |
| CN118147456A (en) * | 2024-05-11 | 2024-06-07 | 矿冶科技集团有限公司 | Clay lithium ore raw ore calcine leaching process and leaching solution iron removal method thereof |
| CN118147456B (en) * | 2024-05-11 | 2024-07-16 | 矿冶科技集团有限公司 | Clay lithium ore raw ore calcine leaching process and leaching solution iron removal method thereof |
| CN118405712A (en) * | 2024-06-28 | 2024-07-30 | 矿冶科技集团有限公司 | Method for selectively extracting lithium oxide from clay-type lithium resources |
| CN118880064A (en) * | 2024-07-17 | 2024-11-01 | 昆明理工大学 | A method for low-temperature acid-free leaching of lithium from clay-type lithium ore |
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