CN116377246A - Efficient lithium extraction method for clay-type lithium ore - Google Patents
Efficient lithium extraction method for clay-type lithium ore Download PDFInfo
- Publication number
- CN116377246A CN116377246A CN202310003393.0A CN202310003393A CN116377246A CN 116377246 A CN116377246 A CN 116377246A CN 202310003393 A CN202310003393 A CN 202310003393A CN 116377246 A CN116377246 A CN 116377246A
- Authority
- CN
- China
- Prior art keywords
- leaching
- lithium
- grinding
- clay
- leached
- 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.)
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Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 81
- 238000000605 extraction Methods 0.000 title claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 69
- 238000000227 grinding Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 239000004927 clay Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 22
- -1 organic acid salt Chemical class 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 claims description 2
- 229940048053 acrylate Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229940072107 ascorbate Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 229940001468 citrate Drugs 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229940049920 malate Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229940076788 pyruvate Drugs 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229940086735 succinate Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 description 15
- 239000011707 mineral Substances 0.000 description 15
- 235000010755 mineral Nutrition 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- UBKBVPONTPMQQW-UHFFFAOYSA-N azane;2-hydroxyacetic acid Chemical compound [NH4+].OCC([O-])=O UBKBVPONTPMQQW-UHFFFAOYSA-N 0.000 description 2
- VRYNVZJQBANJOF-UHFFFAOYSA-N azane;2-oxopropanoic acid Chemical compound [NH4+].CC(=O)C([O-])=O VRYNVZJQBANJOF-UHFFFAOYSA-N 0.000 description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 2
- 239000001527 calcium lactate Substances 0.000 description 2
- 235000011086 calcium lactate Nutrition 0.000 description 2
- 229960002401 calcium lactate Drugs 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- IZZSMHVWMGGQGU-UHFFFAOYSA-L disodium;2-methylidenebutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(=C)C([O-])=O IZZSMHVWMGGQGU-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- 229940074358 magnesium ascorbate Drugs 0.000 description 2
- AIOKQVJVNPDJKA-ZZMNMWMASA-L magnesium;(2r)-2-[(1s)-1,2-dihydroxyethyl]-4-hydroxy-5-oxo-2h-furan-3-olate Chemical compound [Mg+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] AIOKQVJVNPDJKA-ZZMNMWMASA-L 0.000 description 2
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 description 2
- 239000001415 potassium malate Substances 0.000 description 2
- 235000011033 potassium malate Nutrition 0.000 description 2
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 description 2
- 229960003629 potassium salicylate Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 229940074404 sodium succinate Drugs 0.000 description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
-
- 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 high-efficiency lithium extraction method of clay type lithium ores, which comprises the following steps of: 1) Crushing and screening clay type lithium ores to obtain fine-fraction materials; 2) Grinding the fine fraction material obtained in the step 1), adding organic acid salt in the grinding process, and adjusting grinding parameters to obtain a material to be leached; 3) And (3) leaching the material to be leached, wherein parameters such as liquid-solid ratio or pulp mass concentration, pH and temperature are adjusted in the leaching process, and after the leaching reaches equilibrium, the pulp is subjected to solid-liquid separation, so that the leaching liquid rich in lithium ions can be obtained. The leaching solution rich in lithium ions obtained by the invention can further recover lithium through various modes such as precipitation, extraction, adsorption and the like. The invention can directly treat low-grade clay lithium ore under normal temperature and normal pressure to obtain higher lithium leaching rate, has low impurity content, and has the advantages of wide source, low cost, small dosage, high efficiency, environmental protection and the like, and the leaching residue can be used as an environmental protection material.
Description
Technical Field
The invention belongs to the field of hydrometallurgy and mineral processing, and particularly relates to a high-efficiency lithium extraction method for clay-type lithium ores.
Background
Lithium is known as white petroleum and is widely used in important fields such as lithium ion batteries, nuclear fusion and the like. In addition to the above fields, lithium elements are used in different industries as specific compounds, and in particular have an irreplaceable significance for achieving carbon neutralization worldwide. Since a large amount of lithium is required for new energy development, the supply amount of lithium cannot meet the market demand, and the price of lithium is rapidly increased, for example, the price of battery grade lithium carbonate is increased from 5 ten thousand yuan/ton at the beginning of 2021 to more than 60 ten thousand yuan/ton in 2022. However, the lithium ore distribution area is highly concentrated, and nearly 91% of the global reserves are mainly distributed in chile, argentina, united states, zimbabwe, portugal, australia, china, canada, brazil and other countries. The prior art proves that the lithium resource reserves are the largest according to the deposit types, and the reserves of the brine type deposit (salt lake lithium) are the second most. At present, the supply of lithium resources is mainly salt lake and spodumene, and the recovery of lepidolite and batteries is auxiliary. Clay-type lithium ores are also called as deposition-type lithium ores, and serve as undeveloped lithium ores, and have the characteristics of wide distribution and large reserves, but clay-type lithium ores are not developed and utilized on a large scale so far, and only a plurality of foreign enterprises have published expected technical routes.
Because lithium ions of clay type lithium ores exist in the form of adsorbed lithium and the like, the clay type lithium ores have the characteristics of lean, fine, impurity and the like, and are difficult to clean and efficiently treat by a conventional dressing and smelting method. At present, the lithium extraction of clay-type lithium ores is still in the preliminary research and exploration stage, and no general method and industrial production are carried out. The formation of carbonate clay type lithium ore is that the carbonate is differentiated into clay with moderate aluminum content under the deposition action, lithium ion solution is adsorbed and enriched by clay in the migration and infiltration process, and the lithium ion solution is endowed in the interlayer structure of carbonate and silicate crystal in an ion exchange mode, and the main minerals are diasporite, montmorillonite, illite, kaolinite, chlorite, anatase and the like. In recent years, a large amount of carbonate clay type lithium ore resources are found in southwest regions of China, and if the lithium ore can be effectively developed and utilized, the resource shortage problem of China and even the long-term development of global lithium industry can be effectively solved.
Based on past treatment experience of hard rock type lithium ores such as spodumene, lepidolite and the like, domestic and foreign experts and enterprises propose a direct leaching method after flotation, an auxiliary agent roasting method, a chlorination vulcanization method, a sulfuric acid leaching method after roasting and the like. The roasting leaching method is to roast clay type lithium ore and salts such as sodium carbonate, sodium sulfate and the like at a high temperature of more than 600 ℃ to destroy the layered structure of clay type minerals and form new minerals which are easy to dissolve, so that lithium ions are conveniently dissolved into leaching liquid under the corrosive action of sulfuric acid solution, and then the lithium carbonate product is obtained through impurity removal and precipitation. The direct sulfuric acid leaching method can be used for treating specific clay type lithium ores which are easy to dissolve, and mainly comprises the steps of mixing the ores with sulfuric acid under normal pressure for leaching, properly heating to improve leaching efficiency, filtering leaching liquid step by step, recovering different products, and finally obtaining lithium carbonate products from the leached liquid after filtering through ion exchange.
The method is mainly based on a conventional dressing and smelting technical route: flotation separation and enrichment of target minerals, roasting to destroy mineral structure, and sulfuric acid leaching of lithium ores, but all have the following remarkable defects:
1. conventional beneficiation methods such as flotation and the like cannot effectively separate and enrich lithium, so that lithium-containing minerals are lost, and the lithium enrichment degree cannot meet the requirement. The physical and chemical properties of lithium-containing minerals such as montmorillonite, kaolinite and the like in clay-type lithium ores are similar to those of gangue, and the grinding necessary for the ore dressing process can cause the mud slurry of the clay-type minerals.
2. The low concentration of clay type lithium ore results in the ore treatment capacity of roasting process being far greater than that of traditional hard rock type lithium ore, resulting in high energy consumption, high cost and environmental protection. For example, the lithium grade of clay type lithium ore which cannot be beneficiated and enriched is about 0.5%, and the grade of hard rock type lithium ore concentrate after beneficiation and enrichment is generally more than 5%, so that clay type lithium ore which needs roasting treatment of the lithium product with the same quality is more than ten times of that of the hard rock type lithium ore.
3. The sulfuric acid leaching process after roasting can dissolve minerals without selectivity, and the increase of the roasting treatment capacity can magnify the defect, so that a large amount of impurity ions such as iron, aluminum, calcium, magnesium and the like are released, the subsequent impurity removing process is complicated, a large amount of solid wastes are generated, the recovery efficiency and the product quality of lithium are further reduced, and the lithium recovery cost is extremely high.
Therefore, the existing research technical route cannot economically and cleanly and efficiently utilize clay-type lithium ores, so that the resources cannot be exploited and utilized at a later time.
Disclosure of Invention
The invention aims to provide a high-efficiency lithium extraction method for clay-type lithium ores, which has the advantages of high lithium leaching rate, less impurity leaching, selectivity, short flow, low cost, environmental protection and the like.
The invention relates to a high-efficiency lithium extraction method for clay type lithium ores, which comprises the following steps:
1) Crushing and screening clay type lithium ores to obtain fine-fraction materials;
2) Grinding the fine fraction material in the step 1), adding organic acid salt in the grinding process, and obtaining a material to be leached after grinding;
3) And leaching the material to be leached, and carrying out solid-liquid separation after the leaching reaches equilibrium to obtain the leaching liquid rich in lithium ions.
Preferably, in the step 1), the granularity of the fine fraction material is 50-800 mesh.
Preferably, in the step 2), the anions in the organic acid salt are organic acid radicals which do not contain benzene rings and are environment-friendly and have carbon chain lengths of less than 7; further preferably, the organic acid radical is at least one of acetate, lactate, salicylate, glycolate, ascorbate, pyruvate, acrylate, gluconate, itaconic acid, succinate, tartrate, malate and citrate; the cation of the organic acid salt is at least one of sodium salt, potassium salt, calcium salt, ammonium salt and magnesium salt.
Preferably, in the step 2), the weight ratio of the organic acid salt to the fine fraction material is 1: 100-1: 1.
preferably, in the step 2), the equipment for grinding is one of a ball mill, a planetary ball mill, a stirring mill, and a sand mill; the grinding process parameters are as follows: the rotating speed is 100-2000 rpm, and the grinding time is 10-300 min.
Preferably, in the step 2), the material of the grinding balls used in the grinding equipment is at least one of steel, tungsten, zirconia and alumina, and the medium filling rate of the grinding balls is 10% -60% of the volume of the grinding equipment.
Preferably, in the step 2), water may be added during the ore grinding process, wherein the weight ratio of water to fine fraction material is 0-5: 1.
preferably, in the step 3), the material to be leached is prepared into ore pulp for leaching; in the ore pulp, the mass concentration of the materials to be leached is 5% -60%, or the liquid-solid ratio in the ore pulp is 0.6:1-20:1; the leaching pH is 2.0-10.0, the leaching temperature is 15-90 ℃, and the leaching time is 10-300 min.
Further preferably, in said step 3), the pH of the leaching is adjusted with an acid or a base; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, and the alkali is at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
The leaching solution rich in lithium ions obtained by the invention can further recover lithium through various modes such as precipitation, extraction, adsorption and the like.
The invention provides a high-efficiency lithium extraction method for clay type lithium ores, which is based on the following principle:
1. cations released by the organic acid salt after ionization in water can be subjected to ion exchange with lithium ions among clay mineral crystal structure layers, so that the lithium ions and the cations generated by the adsorption phase are subjected to an exchange reaction and enter a liquid phase.
2. Organic functional groups such as carboxyl, hydroxyl and the like of the organic acid radical rapidly carry out complexation with lithium ions, so that the content of ionic lithium in the solution is reduced, and the chemical reaction balance of lithium ion dissolution is promoted to move forward.
3. Ore grinding can rapidly reduce the particle size of mineral particles, thereby increasing the mineral surface area. Meanwhile, the stirring of the ore grinding equipment drives the convection environment formed by the ore grinding balls to improve the wettability of clay-type lithium ores during leaching, reduce the thickness of a surface double electric layer and promote the organic acid salt to rapidly reach the particle surface to strengthen the liquid-solid reaction of leaching.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can directly treat the low-grade clay type lithium ore in a short process without adopting beneficiation enrichment and roasting treatment, thereby avoiding the problems of lithium resource loss, high cost, environmental protection and the like in the beneficiation and roasting links.
2. The method has good leaching selectivity, less impurity element leaching, and is favorable for recovering lithium in subsequent solutions.
3. The slag provided by the invention can be used for building material raw materials, environment-friendly materials and the like after being simply treated, so that the efficient and comprehensive utilization of clay resources is realized.
4. The method has the advantages of short process flow, normal temperature and normal pressure reaction, low cost, wide source, environmental protection and the like of the selected leaching agent, and is beneficial to industrial popularization and application.
Detailed Description
In order to make the technical means, the creation features, the achievement of the objects and the effects of the present invention easy to understand, the present invention is further described below with reference to specific examples and comparative examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The clay-type lithium ores in the following examples and comparative examples were mainly composed of minerals such as kaolinite, montmorillonite, chlorite, diaspore, quartz, etc., and had a lithium oxide content of 0.51g/kg, and leaching rates in the examples and comparative examples were obtained by analysis of solution components by inductively coupled plasma spectroscopy (ICP).
Example 1
Crushing and screening clay type lithium ores to obtain fine-fraction materials with the granularity of 200 meshes, adding the fine-fraction materials into a ball mill for grinding, and adding sodium citrate and water in the grinding process, wherein the weight ratio of the sodium citrate to the fine-fraction materials is 1:20, grinding time is 120min, equipment rotating speed is 150rpm, and the weight ratio of water to fine fraction material is 1:10, the material of the grinding ball is steel, and the medium filling rate is 20%, so that the material to be leached is obtained.
And (3) mixing the material to be leached into ore pulp by using water, leaching, controlling the mass concentration of the ore pulp to be 20% (the liquid-solid ratio is 4:1), adding sodium hydroxide to adjust the pH value to 8, leaching for 60min, and leaching at 90 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions was analyzed to obtain a Li leaching rate of 83%, and leaching rates of 3.1%, 0.9% and 0.7% of impurity elements Al, mg and Fe, respectively.
Example 2
Crushing and screening clay type lithium ores to obtain fine-fraction materials with the granularity of 100 meshes, adding the fine-fraction materials into a planetary ball mill for grinding, and adding calcium lactate and water in the grinding process, wherein the weight ratio of the calcium lactate to the fine-fraction materials is 6:94, grinding time is 90min, equipment rotating speed is 600rpm, and the weight ratio of water to fine fraction material is 1: and 5, the material of the grinding balls is alumina, and the medium filling rate is 40%, so that the material to be leached is obtained.
The material to be leached is prepared into ore pulp by water for leaching, the mass concentration of the ore pulp is controlled to be 40 percent (the liquid-solid ratio is 1.5:1), sulfuric acid is added to adjust the pH value to be 6, the leaching time is 30min, and the leaching temperature is 50 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rate of Li of 89%, and the leaching rates of impurity elements Al, mg and Fe of 4.6%, 1.3% and 0.9% respectively.
Example 3
Crushing and screening clay type lithium ores to obtain fine-fraction materials with 800 meshes, adding the fine-fraction materials into a sand mill for grinding, and adding ammonium acetate, magnesium ascorbate and water in the grinding process, wherein the weight ratio of the ammonium acetate to the magnesium ascorbate to the fine-fraction materials is (7): 3:90, grinding time is 20min, equipment rotating speed is 2000rpm, and the weight ratio of water to fine fraction material is 1:1, the material of the grinding ball is zirconia, the medium filling rate is 50%, and the material to be leached is obtained.
The material to be leached is prepared into ore pulp by water for leaching, the mass concentration of the ore pulp is controlled to be 20 percent (the liquid-solid ratio is 4:1), the pH value is regulated to be 10 by adding potassium hydroxide, the leaching time is 120min, and the leaching temperature is 70 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rates of Li of 87%, and the leaching rates of impurity elements Al, mg and Fe of 3.7%, 1.1% and 0.1% respectively.
Example 4
Crushing and screening clay type lithium ores to obtain a fine-fraction material with the granularity of 400 meshes, adding the fine-fraction material into a ball mill for grinding, and adding sodium succinate, potassium malate and potassium salicylate into the grinding process, wherein the weight ratio of the sodium succinate to the potassium malate to the potassium salicylate to the fine-fraction material is 3:1:1:16, grinding time is 60min, equipment rotating speed is 100rpm, grinding balls are made of steel, and medium filling rate is 10%, so that materials to be leached are obtained.
And (3) mixing the material to be leached into ore pulp by using water, leaching, controlling the mass concentration of the ore pulp to be 5% (the liquid-solid ratio to be 19:1), adding hydrochloric acid to adjust the pH value to be 2, leaching for 300min, and leaching at 30 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rates of Li of 95 percent and the leaching rates of impurity elements Al, mg and Fe of 8.9 percent, 1.9 percent and 1.5 percent respectively.
Example 5
Crushing and screening clay type lithium ores to obtain a fine-fraction material with the granularity of 50 meshes, adding the fine-fraction material into a stirring mill for grinding, adding sodium gluconate, ammonium glycolate, sodium tartrate and water in the grinding process, wherein the weight ratio of the sodium gluconate to the ammonium glycolate to the sodium tartrate to the fine-fraction material is 1:1:1:47, grinding time is 60min, equipment rotating speed is 1000rpm, and the weight ratio of water to fine fraction material is 3:1, the material of the grinding ball is alumina, and the medium filling rate is 30%, so as to obtain the material to be leached.
The material to be leached is prepared into ore pulp by water for leaching, the mass concentration of the ore pulp is controlled to be 15 percent (the liquid-solid ratio is 5.6:1), nitric acid is added to adjust the pH value to be 7, the leaching time is 30min, and the leaching temperature is 40 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rates of Li of 92.1 percent and the leaching rates of impurity elements Al, mg and Fe of 8.4 percent, 2.1 percent and 2.9 percent respectively.
Example 6
Crushing and screening clay type lithium ores to obtain a fine-fraction material with the granularity of 200 meshes, adding the fine-fraction material into a planetary ball mill for grinding, and adding ammonium pyruvate, sodium acrylate, sodium itaconate and water in the grinding process, wherein the weight ratio of the ammonium pyruvate to the sodium acrylate to the sodium itaconate to the fine-fraction material is 2:2:1:45, grinding time is 180min, equipment rotating speed is 300rpm, and the weight ratio of water to fine fraction material is 1:1, the material of the grinding ball is steel, and the medium filling rate is 60%, so as to obtain the material to be leached.
And (3) mixing the material to be leached into ore pulp by using water, leaching, controlling the mass concentration of the ore pulp to be 30% (the liquid-solid ratio to be 2.3:1), adding calcium hydroxide to adjust the pH to be 10, leaching for 20min, and leaching at 50 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rate of Li of 86.5 percent and the leaching rates of impurity elements Al, mg and Fe of 3.4 percent, 0.6 percent and 0.5 percent respectively.
Comparative example 1
Crushing and screening clay type lithium ores to obtain fine-grained materials with the granularity of 200 meshes, roasting the fine-grained materials in an air atmosphere of a muffle furnace at 800 ℃ for 2 hours, adding 98% of concentrated sulfuric acid into the roasted fine-grained materials to prepare ore pulp with the mass concentration of 30%, wherein the leaching time is 120min, and the leaching temperature is 70 ℃. And after the leaching reaches the equilibrium, carrying out solid-liquid separation on the ore pulp to obtain the leaching liquid rich in lithium ions. The leaching solution rich in lithium ions is analyzed to obtain the leaching rates of Li of 83.2 percent and the leaching rates of impurity elements Al, mg and Fe of 63.5 percent, 43.6 percent and 55.1 percent respectively.
Lithium ions are stably present in the layered structure of clay-based minerals. Comparative example 1 the layered structure of clay mineral was destroyed by high temperature calcination and new mineral which was easily dissolved was formed, and then lithium ions were dissolved into the leachate under the corrosive action of sulfuric acid solution. The method of the comparative example causes release of a large amount of impurities such as Al, mg, fe, etc., complicating the subsequent impurity removal process and producing a large amount of solid waste. In examples 1-6, the material to be leached has the characteristics of fine particle size and large surface area, and lithium therein can be fully complexed with anions and cations of organic acid salt respectively and enter the leaching solution through ion exchange. The method of the embodiment shows good leaching selectivity, and little impurity element is dissolved out, thereby being beneficial to the recovery of lithium in the subsequent solution.
While the basic principles and main features of the present invention and advantages of the present invention have been shown and described, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are described in the foregoing specification merely illustrate the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims and their equivalents.
Claims (9)
1. A high-efficiency lithium extraction method of clay-type lithium ores comprises the following steps:
1) Crushing and screening clay type lithium ores to obtain fine-fraction materials;
2) Grinding the fine fraction material in the step 1), adding organic acid salt in the grinding process, and obtaining a material to be leached after grinding;
3) And leaching the material to be leached, and carrying out solid-liquid separation after the leaching reaches equilibrium to obtain the leaching liquid rich in lithium ions.
2. The method according to claim 1, wherein in the step 1), the particle size of the fine fraction is 50 to 800 mesh.
3. The method according to claim 1, wherein in the step 2), the anions in the organic acid salt are benzene-ring-free, environment-friendly organic acid radicals with carbon chain length lower than 7; preferably, the organic acid radical is at least one of acetate, lactate, salicylate, glycolate, ascorbate, pyruvate, acrylate, gluconate, itaconic acid, succinate, tartrate, malate and citrate; the cation of the organic acid salt is at least one of sodium salt, potassium salt, calcium salt, ammonium salt and magnesium salt.
4. The method according to claim 1, wherein in the step 2), the weight ratio of the organic acid salt to the fine fraction material is 1: 100-1: 1.
5. the method according to claim 1, wherein in the step 2), the equipment for grinding is one of a ball mill, a planetary ball mill, a stirring mill, and a sand mill; the grinding process parameters are as follows: the rotating speed is 100-2000 rpm, and the grinding time is 10-300 min.
6. The method according to claim 5, wherein in the step 2), the material of the grinding balls used in the grinding apparatus is at least one of steel, tungsten, zirconia and alumina, and the medium filling rate of the grinding balls is 10% -60% of the volume of the grinding apparatus.
7. The method according to claim 1, wherein in the step 2), water may be added during the grinding process, and the weight ratio of water to fine fraction material is 0-5: 1.
8. the method according to claim 1, wherein in the step 3), the material to be leached is slurried for leaching; in the ore pulp, the mass concentration of the materials to be leached is 5% -60%, or the liquid-solid ratio in the ore pulp is 0.6:1-20:1; the leaching pH is 2.0-10.0, the leaching temperature is 15-90 ℃, and the leaching time is 10-300 min.
9. The method according to claim 8, wherein in step 3), the pH is adjusted with an acid or a base; the acid is at least one of sulfuric acid, hydrochloric acid and nitric acid, and the alkali is at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
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