CN115198108A - Method for extracting lithium - Google Patents
Method for extracting lithium Download PDFInfo
- Publication number
- CN115198108A CN115198108A CN202110394688.6A CN202110394688A CN115198108A CN 115198108 A CN115198108 A CN 115198108A CN 202110394688 A CN202110394688 A CN 202110394688A CN 115198108 A CN115198108 A CN 115198108A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- extraction
- hydrogen chloride
- chloride gas
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 296
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 296
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 160
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 146
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 118
- 239000007789 gas Substances 0.000 claims abstract description 116
- 239000012074 organic phase Substances 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 66
- 238000002156 mixing Methods 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 237
- 239000000243 solution Substances 0.000 claims description 181
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 98
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 82
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 51
- 239000011780 sodium chloride Substances 0.000 claims description 49
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 42
- 239000001569 carbon dioxide Substances 0.000 claims description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000000460 chlorine Substances 0.000 claims description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005191 phase separation Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 7
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- PPDZLUVUQQGIOJ-UHFFFAOYSA-N 1-dihexylphosphorylhexane Chemical compound CCCCCCP(=O)(CCCCCC)CCCCCC PPDZLUVUQQGIOJ-UHFFFAOYSA-N 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- FTTQCEGWFGHNDU-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-6,6-dimethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)F FTTQCEGWFGHNDU-UHFFFAOYSA-N 0.000 claims description 5
- BVPKYBMUQDZTJH-UHFFFAOYSA-N 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)F BVPKYBMUQDZTJH-UHFFFAOYSA-N 0.000 claims description 5
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- -1 5329-phenanthroline Chemical compound 0.000 claims description 4
- PVDDBYSFGBWICV-UHFFFAOYSA-N 1,4,8,11-tetraoxacyclotetradecane Chemical compound C1COCCOCCCOCCOC1 PVDDBYSFGBWICV-UHFFFAOYSA-N 0.000 claims description 3
- IFQULAPKPYIHBS-UHFFFAOYSA-N 1-phenyldecane-1,3-dione Chemical compound CCCCCCCC(=O)CC(=O)C1=CC=CC=C1 IFQULAPKPYIHBS-UHFFFAOYSA-N 0.000 claims description 3
- ZGZLRWJZGFRHHQ-UHFFFAOYSA-N 2-(3-methylimidazol-3-ium-1-yl)ethanol Chemical compound CN1C=C[N+](CCO)=C1 ZGZLRWJZGFRHHQ-UHFFFAOYSA-N 0.000 claims description 3
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 claims description 3
- SQNZLBOJCWQLGQ-UHFFFAOYSA-N 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F SQNZLBOJCWQLGQ-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- MRQIXHXHHPWVIL-ISLYRVAYSA-N Sudan I Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=CC=C1 MRQIXHXHHPWVIL-ISLYRVAYSA-N 0.000 claims description 3
- SDHNVJNECVZFNU-UHFFFAOYSA-M [Cl-].C(CCCCCCC)[S+](C)CCCCCCCC Chemical compound [Cl-].C(CCCCCCC)[S+](C)CCCCCCCC SDHNVJNECVZFNU-UHFFFAOYSA-M 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- ZYQLPCAMAXPPMD-UHFFFAOYSA-N n,n-dioctyloctan-1-amine oxide Chemical compound CCCCCCCC[N+]([O-])(CCCCCCCC)CCCCCCCC ZYQLPCAMAXPPMD-UHFFFAOYSA-N 0.000 claims description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- XNSWGVOVGKAVMY-UHFFFAOYSA-N 1,4-bis[[dibutoxy(oxido)phosphaniumyl]oxy]butane Chemical compound CCCCO[P+]([O-])(OCCCC)OCCCCO[P+]([O-])(OCCCC)OCCCC XNSWGVOVGKAVMY-UHFFFAOYSA-N 0.000 claims 1
- QZIXNDMVULFPAJ-UHFFFAOYSA-N N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound N.N.N.N.N.N.N.N.N.N.N.N.N.N QZIXNDMVULFPAJ-UHFFFAOYSA-N 0.000 claims 1
- KBZIIXCXTFPZLX-UHFFFAOYSA-N N.S.S.S.S.S Chemical compound N.S.S.S.S.S KBZIIXCXTFPZLX-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 3
- 239000012267 brine Substances 0.000 description 63
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 63
- 239000011777 magnesium Substances 0.000 description 29
- 239000013078 crystal Substances 0.000 description 27
- 239000011575 calcium Substances 0.000 description 25
- 238000009616 inductively coupled plasma Methods 0.000 description 22
- 238000001914 filtration Methods 0.000 description 19
- 239000003350 kerosene Substances 0.000 description 15
- 238000011084 recovery Methods 0.000 description 11
- 238000004611 spectroscopical analysis Methods 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000010413 mother solution Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003843 chloralkali process Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- SCPHDVDVGFRLEI-UHFFFAOYSA-N dibutyl dibutoxyphosphoryloxymethyl phosphate Chemical compound P(=O)(OCCCC)(OCCCC)OCOP(=O)(OCCCC)OCCCC SCPHDVDVGFRLEI-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Images
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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
Abstract
The invention relates to a lithium extraction method, which comprises the following steps: providing a lithium-loaded organic phase; mixing the lithium-loaded organic phase, hydrogen chloride gas and water, and performing back extraction and phase splitting to obtain back extraction solution containing lithium chloride; and separating the stripping solution to obtain the lithium-containing compound. In the extraction method of lithium, the combination of hydrogen chloride gas and water is used as a stripping agent, and during the stripping process, acid preparation and stripping are carried out simultaneously, so that the hydrogen chloride gas and hydrochloric acid coexist, the hydrogen chloride gas is continuously converted into hydrochloric acid to supplement the reacted hydrochloric acid, and therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the lithium-loaded organic phase, the hydrogen chloride gas and water can be effectively increased, the concentration of lithium ions in the obtained stripping solution is increased to about 96g/L, the lithium yield is effectively increased, and the energy consumption required in the crystallization process is reduced.
Description
Technical Field
The invention relates to the technical field of lithium extraction, in particular to a lithium extraction method.
Background
At present, lithium resources are mainly derived from salt lakes and minerals, and with the advance of recycling of waste resources in recent years, waste lithium batteries also become important sources of lithium resources. The methods for obtaining lithium resources from these raw materials mainly include precipitation, extraction, adsorption, and the like. The extraction method is a new technology for obtaining lithium resources, achieves the purpose of extracting lithium by utilizing the special extraction performance of an organic solvent on lithium, and mainly comprises two steps of extraction and back extraction.
In the traditional back extraction step, industrial hydrochloric acid is mainly used as a back extraction agent, and the mass percent of the industrial hydrochloric acid is generally 31-33%, so that the concentration of lithium ions in the back extraction solution obtained by back extraction is about 70g/L, and further a large amount of water needs to be evaporated in the crystallization process, and the energy consumption is high.
Disclosure of Invention
In view of the above, it is necessary to provide a method for extracting lithium, which has low energy consumption and high lithium yield.
A method of extracting lithium comprising:
providing a lithium-loaded organic phase;
mixing the lithium-loaded organic phase, hydrogen chloride gas and water, and performing back extraction and phase splitting to obtain back extraction solution containing lithium chloride; and
and separating the stripping solution to obtain the lithium-containing compound.
In one embodiment, the hydrogen chloride gas is prepared by the following method:
dissolving sodium chloride in water to obtain a sodium chloride solution;
electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen; and
and reacting the chlorine gas with hydrogen to obtain the hydrogen chloride gas.
In one embodiment, in the step of mixing the lithium-loaded organic phase, the hydrogen chloride gas and the water, 1mol to 2mol of the hydrogen chloride gas is introduced per 1mol of the lithium ions in terms of a molar ratio of the lithium ions in the lithium-loaded organic phase.
In one embodiment, the pressure is less than or equal to 2MPa and the temperature is-30 ℃ to 50 ℃ when the hydrogen chloride gas is introduced; the volume ratio of the hydrogen chloride gas to the water is 4:1-15.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and mixing the stripping solution with sodium carbonate to obtain a lithium-containing compound, wherein the lithium-containing compound is lithium carbonate.
In one embodiment, the temperature is 70-90 ℃ when the stripping solution is mixed with sodium carbonate.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and mixing carbon dioxide, the stripping solution and the sodium hydroxide, and carrying out heating reaction to obtain a lithium-containing compound, wherein the temperature of the heating reaction is 50-100 ℃, and the lithium-containing compound is lithium carbonate.
In one embodiment, when the stripping solution, the sodium hydroxide and the carbon dioxide are mixed and heated, newly generated carbon dioxide is also obtained.
In one embodiment, the newly generated carbon dioxide is recycled for mixing with the strip liquor, the sodium hydroxide and the heating reaction.
In one embodiment, in the step of separating the lithium-containing compound from the strip liquor, sodium chloride is also obtained.
In one embodiment, the sodium chloride is recycled for use in the preparation of the hydrogen chloride gas.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and controlling the temperature of the stripping solution to be 20-50 ℃, and cooling the stripping solution to obtain the lithium-containing compound, wherein the temperature difference of the cooling is 10-40 ℃, and the lithium-containing compound is lithium chloride.
In one embodiment, the method for preparing the lithium-loaded organic phase comprises the following steps:
providing a lithium-containing solution;
and mixing the lithium-containing solution with an extraction solution, and carrying out extraction and phase separation to obtain the lithium-loaded organic phase.
In one embodiment, the lithium-containing solution further comprises at least one of magnesium ions and calcium ions,
before the step of mixing the lithium-containing solution with the extraction solution, the lithium-containing solution is also mixed with an alkaline substance to obtain a precipitate.
In one embodiment, the alkaline substance comprises the sodium hydroxide.
In one embodiment, after the obtaining of the precipitate, the step of mixing the precipitate with the hydrogen chloride gas and water to react to obtain a mixed solution is further included.
In one embodiment, the volume ratio of the extraction liquid to the lithium-containing solution is 4:1-1:4, the extraction times are greater than or equal to 1, and the time of each extraction is 1-10 minutes.
In one embodiment, the extraction liquid comprises an extractant and a diluent, the extractant is a hydrophobic liquid and comprises trioxothiophene oxide, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2-pentafluoro-6,6 dimethyl-3,5-heptanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, benzoyl trifluoroacetone, 1-phenyl-1,3-butanedione, 1-benzoyl-2-nonanone, trialkyl phosphate, trialkyl phosphine oxide, trioctyl phosphine oxide, trihexyl phosphine oxide, dialkyl phosphate, methyl isobutyl ketone, 1-phenylazo-2-naphthol, N-octanol, isooctanol, 2-ethylhexanol, 14-crown-4 ether butyl dibutyl phosphonate, dibutyl phosphate, tetramethylene dibutyl phosphate, trioctyl amine oxide, 1,10-phenanthroline, quaternary ammonium salt N 263 At least one of dimethylbis (N-octadecyl) ammonium chloride, methyldioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
In one embodiment, after the lithium-containing compound is separated from the stripping solution, a lithium precipitation mother solution is also obtained, and the lithium precipitation mother solution is circulated and mixed with the lithium-containing solution.
In one embodiment, in the step of mixing the lithium-loaded organic phase, hydrogen chloride gas and water, performing back extraction and phase separation to obtain a back extraction solution containing lithium chloride, an idle extraction liquid is also obtained;
the no-load extraction liquid is recycled and is used for mixing with the extraction liquid to carry out extraction and phase splitting to obtain the lithium-loaded organic phase;
and/or in the step of mixing the lithium-loaded organic phase, hydrogen chloride gas and water, performing back extraction and phase separation to obtain a back extraction solution containing lithium chloride, continuously circulating part of the back extraction solution, mixing the back extraction solution with the lithium-loaded organic phase, the hydrogen chloride gas and the water, and performing back extraction and phase separation.
In the extraction method of lithium, the combination of hydrogen chloride gas and water is used as a stripping agent, and during the stripping process, acid preparation and stripping are carried out simultaneously, so that the hydrogen chloride gas and hydrochloric acid coexist, the hydrogen chloride gas is continuously converted into hydrochloric acid to supplement the reacted hydrochloric acid, and therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the lithium-loaded organic phase, the hydrogen chloride gas and water can be effectively increased, the concentration of lithium ions in the obtained stripping solution is increased to about 96g/L, the lithium yield is effectively increased, and the energy consumption required in the crystallization process is reduced.
Drawings
FIG. 1 is a process flow diagram of a lithium extraction process of the present invention.
Detailed Description
The lithium extraction method provided by the invention will be further explained in the following description with reference to the accompanying drawings.
As shown in fig. 1, the lithium extraction method provided by the present invention comprises:
(1) Providing a lithium-loaded organic phase;
(2) Mixing the lithium-loaded organic phase, hydrogen chloride gas and water, and performing back extraction and phase splitting to obtain back extraction liquid containing lithium chloride;
(3) And separating the stripping solution to obtain the lithium-containing compound.
In the step (1), the lithium-loaded organic phase is obtained by extraction with an extraction solution, and the preparation method comprises the following steps:
(11) Providing a lithium-containing solution;
(12) And mixing the lithium-containing solution with an extraction solution, and carrying out extraction and phase separation to obtain the lithium-loaded organic phase.
In the step (11), the lithium-containing solution includes at least one of salt lake brine, lithium ore leaching solution, lithium battery waste leaching solution, and lithium precipitation mother liquor.
Due to Cl in salt lake brine - 、SO 4 2- 、HCO 3 - 、CO 3 2- 、Na + 、K + 、Mg 2+ 、Ca 2+ All at high concentrations, with Mg present in large amounts 2+ 、Ca 2+ Therefore, when the lithium-containing solution is salt lake brine, the lithium-containing solution can be further mixed with alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, calcium oxide, lithium hydroxide and the like to ensure that Mg in the lithium-containing solution is Mg 2+ Conversion to magnesium hydroxide precipitate, ca 2+ Is converted into calcium hydroxide precipitate to substantially remove Mg 2+ And Ca 2+ 。
When the salt lake brineMg 2+ And/or Ca 2+ When the content is high, partial Mg can be removed by methods such as adsorption and the like 2+ Reduction of Mg 2+ Then mixing it with alkaline substance to remove Mg 2+ And Ca 2+ 。
The salt lake brine comprises at least one of carbonate type salt lake brine, sulfate type salt lake brine and chloride type salt lake brine. When the salt lake brine is chloride type salt lake brine or sulfate type salt lake brine, mixing the salt lake brine with alkaline substances to remove Mg 2+ And Ca 2+ While at the same time, the pH can be adjusted to be alkaline, so that the extraction step is more facilitated.
It should be noted that Mg is contained in a lithium-containing solution such as a lithium ore leachate, a lithium battery waste leachate, a lithium precipitation mother liquor, etc 2+ And/or Ca 2+ All can adopt the method to remove Mg 2+ And/or Ca 2+ While simultaneously adjusting the pH of the lithium-containing solution to alkaline.
In step (12), the extraction liquid comprises an extracting agent and a diluting agent. Wherein the extractant is a hydrophobic liquid comprising trioxothiophene oxide, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2-pentafluoro-6,6 dimethyl-3,5-heptanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, benzoyl trifluoroacetone, 1-phenyl-1,3-butanedione, 1-benzoyl-2-nonanone, trialkyl phosphate, trioctylphosphine oxide, trihexylphosphine oxide, dialkyl phosphate, methyl isobutyl ketone, 1-phenylazo-2-naphthol, N-octanol, 2-ethylhexanol, 14-crown-4 ether butyl phosphine, dibutyl phosphate, methylene tetrabutyl diphosphate, trioctyl amine oxide, 1,10, 4325-phenanthroline, N-phenanthroline 263 At least one of dimethylbis (N-octadecyl) ammonium chloride, methyldioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, wherein the trialkyl phosphate includes tributyl phosphate. The diluent comprises n-hexane, n-dodecane, cyclohexane, D70 special solvent oil, D80 special solvent oil, no. 120 solvent oil, no. 160 solvent oil, no. 200 solvent oil, common kerosene, aviation kerosene, and sulfurAnd (3) at least one of kerosene.
Further, the volume ratio of the extracting agent in the extraction liquid is not limited, and is specifically adjusted according to the selection of the extracting agent and the diluent, and in an embodiment, the volume percentage of the extracting agent in the extraction liquid is 40% to 50%.
When the lithium-containing solution and the extraction liquid are mixed, the volume ratio of the extraction liquid to the lithium-containing solution is 4:1-1:4, the extraction frequency is more than or equal to 1, and the time of each extraction is 1-10 minutes.
In the extraction process, lithium ions in the lithium-containing solution and the extraction liquid are exchanged with hydrogen ions, so that after extraction is finished, an organic phase loaded with lithium and a raffinate incompatible with the organic phase can be obtained through phase separation, the raffinate can be discharged after environmental protection treatment, and the method is simple.
When the extraction times are more than 1, namely, when multi-stage extraction is carried out, the raffinate can replace the lithium-containing solution, and the raffinate and the extraction liquid are continuously mixed for extraction under the extraction conditions. If the three-stage extraction is carried out, the lithium-containing solution and the extraction liquid are mixed for extraction to obtain a first-stage lithium-loaded organic phase and a first-stage raffinate, the first-stage raffinate is mixed with the extraction liquid again for second extraction to obtain a second-stage lithium-loaded organic phase and a second-stage raffinate, the second-stage raffinate is continuously subjected to third extraction with the extraction liquid to obtain a third-stage lithium-loaded organic phase and a third-stage raffinate, the first-stage lithium-loaded organic phase and the third-stage lithium-loaded organic phase are combined to enter the step (2) for back extraction, and the third-stage raffinate is discharged after being subjected to environmental protection treatment.
In the step (2), the combination of hydrogen chloride gas and water is used as a stripping agent, and when the lithium-loaded organic phase, the hydrogen chloride gas and the water are mixed for stripping, acid preparation and stripping are carried out simultaneously, so that the hydrogen chloride gas and hydrochloric acid coexist, the hydrogen chloride gas is continuously converted into hydrochloric acid to supplement the reacted hydrochloric acid, and therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the lithium-loaded organic phase, the hydrogen chloride gas and the water can be effectively improved.
The step of mixing the lithium-loaded organic phase, the hydrogen chloride gas, and the water comprises: hydrogen chloride gas and water are continuously introduced into the lithium-bearing organic phase while being mixed with the lithium-bearing organic phase.
In the step of mixing the lithium-loaded organic phase, the hydrogen chloride gas, and the water, 1mol to 2mol, preferably 1mol to 1.5mol, of the hydrogen chloride gas is introduced per 1mol of the lithium ions in terms of a molar ratio of the lithium ions in the lithium-loaded organic phase. When the hydrogen chloride gas is introduced, the pressure is less than or equal to 2MPa, preferably 0-1MPa, the temperature is-30 ℃ to 50 ℃, preferably-20 ℃ to 30 ℃, and the volume ratio of the hydrogen chloride gas to the water is 4:1-15, preferably 4:1-10.
Specifically, the number of back extraction is greater than or equal to 1, and the time of each back extraction is 1 minute to 10 minutes, preferably 5 minutes to 10 minutes.
Therefore, the concentration of lithium ions in the stripping solution obtained by phase separation is increased to about 96g/L, the lithium yield is effectively improved, and meanwhile, the higher the concentration of the lithium ions in the stripping solution is, the lower the energy consumption required in the crystallization process is.
In the step (2), after the back extraction is finished, when the phase separation is carried out to obtain the back extraction solution containing lithium chloride, an idle-load extraction solution is also obtained, and the idle-load extraction solution can be recycled, for example, the recovered idle-load extraction solution is circulated to the step (12) to be mixed with the extraction solution and is used for extracting the lithium-containing solution again to obtain the lithium-loaded organic phase.
Considering that lithium ions which are not completely stripped may exist in the unloaded extraction liquid, the unloaded extraction liquid can be subjected to multi-stage stripping by referring to a multi-stage extraction scheme during extraction.
In addition, when the concentration of lithium ions in the stripping solution obtained by phase separation is low, the stripping solution can be continuously circulated and mixed with the lithium-loaded organic phase for stripping, and during circulation, water and/or hydrogen chloride gas is introduced into the stripping solution, and the circulation frequency can be more than 1 time.
Further, when the concentration of lithium ions in the stripping solution reaches the equilibrium, part of the stripping solution may also enter step (3), and part of the stripping solution continues to circulate and is mixed with the lithium-loaded organic phase, the hydrogen chloride gas and the water for stripping and phase separation, preferably, during circulation, water and/or hydrogen chloride gas is introduced into the stripping solution.
In the step (3), there are many methods for separating and obtaining lithium-containing compounds from the stripping solution, and when different methods are adopted, the obtained lithium-containing compounds are different, including lithium carbonate, lithium chloride and the like.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and mixing the stripping solution with sodium carbonate to obtain a lithium-containing compound precipitate, wherein the lithium-containing compound is lithium carbonate. In order to improve the yield of lithium carbonate, the temperature of the stripping solution and the sodium carbonate is preferably 70-90 ℃, and the stripping solution is slowly dripped into the sodium carbonate solution during mixing, wherein the molar ratio of lithium ions to carbonate ions is 2:1-2.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and mixing the stripping solution, the sodium hydroxide and the carbon dioxide, and carrying out heating reaction at the temperature of 50-100 ℃, preferably 70-90 ℃ to obtain a lithium-containing compound precipitate, wherein the lithium-containing compound is lithium carbonate.
When the stripping solution, the sodium hydroxide and the carbon dioxide are mixed, when the molar ratio of the lithium ions to the carbonate ions to the carbon dioxide is 1.
In view of the solubility of carbon dioxide, the stripping solution, the sodium hydroxide and the carbon dioxide may be mixed and then subjected to a heating reaction in order to sufficiently dissolve the carbon dioxide into the solution, and the mixing temperature is preferably not higher than 30 ℃, and more preferably, the mixing is directly performed at normal temperature. Of course, the heating reaction can also be carried out while introducing the carbon dioxide, so that the introduced carbon dioxide can be immediately reacted, and the carbon dioxide can be continuously dissolved into the solution.
In order to increase the yield of lithium carbonate, excess carbon dioxide may be used, preferably the mole percentage of carbon dioxide is within 110% of the mole percentage of lithium ions, in which case lithium chloride, sodium hydroxide and carbon dioxide are reacted to generate lithium bicarbonate, and lithium bicarbonate is decomposed into lithium carbonate and carbon dioxide under heating, and the carbon dioxide is recycled to be mixed with the stripping solution and the sodium hydroxide and to perform the heating reaction.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: controlling the temperature of the stripping solution to be 20-50 ℃, cooling the stripping solution, wherein the temperature difference of the cooling is 10-40 ℃, preferably 20-40 ℃, for example, the temperature of the stripping solution obtained by phase separation is 30 ℃, and the temperature of the stripping solution is reduced to be 0 ℃ or-10 ℃, at the moment, lithium chloride is separated out due to supersaturation.
In this embodiment, if the stripping solution further contains Mg 2+ And/or Ca 2+ To avoid Mg 2+ And/or Ca 2+ Before cooling, the strip liquor may be first adsorbed to remove Mg 2+ And/or Ca 2+ 。
The lithium chloride precipitated in this embodiment also contains a part of sodium chloride, and lithium chloride can be dissolved in water again, and then sodium carbonate can be added to obtain a lithium carbonate precipitate and a sodium chloride solution.
The lithium carbonate obtained by the embodiments of the present invention is high in purity, and the purity can reach more than 98.5%.
And (3) separating the stripping solution to obtain a lithium-containing compound, and then obtaining a lithium precipitation mother solution, wherein the lithium precipitation mother solution can be circulated to the step (11), mixed with the lithium-containing solution, and re-enter the extraction step.
Considering Mg in lithium precipitation mother liquor 2+ And/or Ca 2+ The plasma is basically removed, the influence on the extraction of lithium is small, so the lithium precipitation mother liquor can be independently mixed with the extraction liquid for extraction and back extraction, namely the lithium precipitation mother liquor is used as a new lithium-containing solution for extraction and back extraction, so as to obtain a lithium-containing compound with higher purity.
As shown in fig. 1, the hydrogen chloride gas of the present invention can be prepared by the following method:
(21) Dissolving sodium chloride in water to obtain a sodium chloride solution;
(22) Electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen;
(23) And reacting the chlorine gas with hydrogen to obtain the hydrogen chloride gas.
Therefore, a chlor-alkali process can be adopted to prepare hydrogen chloride gas and sodium hydroxide, then the hydrogen chloride gas is used in the step (2) and mixed with the lithium-loaded organic phase and water for back extraction, the sodium hydroxide is used for mixing with the lithium-containing solution in the step (11), and Mg is added 2+ Conversion to magnesium hydroxide precipitate, ca 2+ Converting into calcium hydroxide precipitate, removing Mg 2+ And Ca 2+ And adjusting the pH value of the lithium-containing solution, and mixing with the stripping solution and carbon dioxide to prepare the lithium carbonate in the step (3).
When the lithium-containing solution is salt lake brine, taking the example of extracting lithium from the salt lake brine as an example, the salt lake brine contains a large amount of sodium chloride, so that the sodium chloride can be directly obtained from the salt lake brine for preparing hydrogen chloride gas and sodium hydroxide.
The precipitate such as magnesium hydroxide and calcium hydroxide precipitated by sodium hydroxide can be mixed with the hydrogen chloride gas and water again to obtain a mixed solution containing Cl - 、Na + 、Mg 2+ And Ca 2+ And the like. Therefore, the mixed solution can be directly discharged into salt lake brine.
According to the analysis of the ion conservation, when the process is used for circularly extracting lithium from the salt lake brine, only lithium ions and Cl are extracted from the salt lake brine - 、Na + 、Mg 2+ And Ca 2+ The plasma can be circulated back to the salt lake brine, so that the ecology of the salt lake can be greatly protected.
Meanwhile, when carbon dioxide and sodium hydroxide are used for preparing the lithium carbonate, the whole extraction and back extraction steps do not need to use any other chemical reagent except the extraction liquid and the carbon dioxide, and the extraction agent and the carbon dioxide can be recycled without conveying any acidic and/or alkaline chemical reagent to a salt lake area, so that on one hand, the ecological environment of the salt lake is greatly protected, on the other hand, the production cost is greatly reduced, and meanwhile, the industrial waste gas carbon dioxide can be secondarily utilized.
Similarly, when sodium carbonate is used for preparing lithium carbonate, the whole extraction and back extraction steps do not need to use any other chemical combination reagent except the extraction liquid and the sodium carbonate; when lithium chloride is directly prepared, the whole extraction and back extraction does not need to use any other chemical reagent except the extraction liquid.
In addition to the lithium-containing compound, in step (3) of the present invention, sodium chloride can be obtained from the lithium precipitation mother liquor, and the sodium chloride can be recycled to step (21) for dissolving in the water to obtain the sodium chloride solution and preparing the hydrogen chloride gas, so that the reagents of the whole extraction and back extraction steps can be recycled.
Because the sodium chloride can be obtained in the step (3), it can be understood that when the lithium-containing solution is the lithium ore leaching solution, the lithium battery waste leaching solution and the lithium precipitation mother solution, the hydrogen chloride gas can also be obtained in the steps (21) to (24), so that the sodium chloride in the whole preparation process can be recycled, and the cost is reduced.
In this case, the precipitates such as magnesium hydroxide and calcium hydroxide precipitated with sodium hydroxide can be used as auxiliary products as they are.
Hereinafter, the method of extracting lithium will be further described by the following specific examples.
Example 1:
dissolving 1.96g of sodium chloride in 7.84g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium, magnesium and calcium in the salt lake brine are respectively 2g/L, 0.15g/L and 0.08g/L, adding 0.57g of sodium hydroxide prepared in the previous step into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking quantitative methyl isobutyl ketone and kerosene, and uniformly mixing the quantitative methyl isobutyl ketone and the kerosene in a separating funnel to obtain an extract liquor, wherein the volume percentage of the methyl isobutyl ketone is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to the water is 7.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.5g/L and a density of about 1.29g/mL.
398g of sodium carbonate solution (79.54 g of sodium carbonate, 20 wt%) was put in an oil bath and heated at 80 ℃ and 128.97g of the above strip liquor was slowly added dropwise after 20min when the water temperature rose to about 80 ℃. Then the heating reaction is continued for 90min, 481g of lithium precipitation mother liquor (the lithium content is about 2.05 g/L) and white lithium carbonate crystals are obtained by hot filtration, the white lithium carbonate crystals are washed twice with 100 ℃ ultrapure water, each time with 100g of water (the lithium content is about 1.516 g/L), and finally the lithium carbonate crystals are dried overnight at 100 ℃ to obtain 43.41g of white lithium carbonate powder, and the lithium recovery rate is about 86.00%.
Example 2:
dissolving 2.22g of sodium chloride in 8.88g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the preparation process into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking quantitative 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and kerosene, and uniformly mixing the materials in a separating funnel to obtain an extract liquid, wherein the volume ratio of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione is 40%. And (3) adding the pretreated salt lake brine into 100mL of extract liquor, oscillating and extracting for 5 minutes, separating a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 8.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.8g/L and a density of about 1.29g/mL.
398g sodium carbonate solution (79.54 g sodium carbonate, 20 wt%) was put into an oil bath and heated at 80 deg.C, 128.98g of the above strip liquor was slowly added dropwise after 20 min. Then the heating reaction is continued for 90min, 478g of lithium precipitation mother liquor (the lithium content is about 2.112 g/L) and white lithium carbonate crystals are obtained by filtering while the solution is hot, the white lithium carbonate crystals are washed twice by 100 ℃ ultrapure water, each time, 100g of water (the lithium content is about 1.525 g/L) is added, and finally the lithium carbonate crystals are dried for one night at 100 ℃ to obtain about 43.60g of white lithium carbonate powder, and the lithium recovery rate is about 86.10%.
Example 3:
dissolving 2.60g of sodium chloride in 10.4g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the above way into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking a certain amount of dimethyl di (N-octadecyl) ammonium chloride and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume percentage of the dimethyl di (N-octadecyl) ammonium chloride is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 10, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) and had a lithium concentration of 96.0g/L and a density of about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution at room temperature, and 17L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed. Then heating to 90 ℃ for reaction for 90min, filtering while hot to obtain 482g of lithium precipitation mother liquor (the lithium content is about 2.065 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water (the lithium content is about 1.471 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 43.88g of white lithium carbonate powder, wherein the lithium recovery rate is about 86.48%.
Example 4:
dissolving 2.60g of sodium chloride in 10.4g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the preparation process into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking quantitative trialkyl phosphine oxide and kerosene, and uniformly mixing in a separating funnel to obtain an extract liquor, wherein the volume percentage of the trialkyl phosphine oxide is 40%. And (3) adding the pretreated salt lake brine into 100mL of extract liquor, oscillating and extracting for 5 minutes, separating a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 10, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.7g/L and a density of about 1.29g/ml.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution at room temperature, 20L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and the strip liquor was completed. Then heating to 80 ℃ for reaction for 90min, filtering while hot to obtain 485g of lithium precipitation mother liquor (the lithium content is about 1.987 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water (the lithium content is about 1.463 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 43.79g of white lithium carbonate powder, wherein the lithium recovery rate is about 86.57%.
Example 5:
dissolving 2.60g of sodium chloride in 10.4g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, performing combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously performing evaporation concentration to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the preparation process into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking quantitative trihexylphosphine oxide and kerosene, and uniformly mixing the quantitative trihexylphosphine oxide and the kerosene in a separating funnel to obtain an extract liquor, wherein the volume percentage of the trihexylphosphine oxide is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 10, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.5g/L and a density of about 1.29g/mL.
Taking 128.96g of stripping solution, controlling the temperature of the stripping solution at 30 ℃, starting stirring for 10min, and then rapidly cooling the stripping solution to 0 ℃ to obtain 46.31g of lithium chloride, wherein the lithium recovery rate is about 79.87%.
Example 6:
dissolving 2.60g of sodium chloride in 10.4g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the preparation process into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80. The precipitate can be mixed with the hydrogen chloride gas and water to react to obtain a mixed solution, and the mixed solution is directly discharged into salt lake brine.
Firstly, respectively taking quantitative dimethyl di (N-octadecyl) ammonium chloride and kerosene, and uniformly mixing in a separating funnel to obtain an extract liquor, wherein the volume of the dimethyl di (N-octadecyl) ammonium chloride accounts for 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 10, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.8g/L and a density of about 1.29g/mL.
128.97g of stripping solution is taken, the temperature is controlled at 30 ℃, stirring is started for 10min, then the stripping solution is rapidly cooled to-10 ℃, 51.55g of lithium chloride is obtained, and the recovery rate of lithium is about 88.91%.
Example 7:
dissolving 1.54g of sodium chloride in 6.16g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, carrying out combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously, evaporating and concentrating to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 105mL (the density is about 1.09 g/mL) of lithium ore leachate, wherein the concentration of lithium in the lithium ore leachate is 1.2g/L, the concentration of magnesium is 0.1g/L, and the concentration of calcium is 0.08g/L, adding 0.68g of sodium hydroxide prepared in the preparation process into the lithium ore leachate, and filtering to obtain a precipitate and 100mL of pretreated lithium ore leachate, wherein the pH value is 12.80.
Firstly, respectively taking quantitative 1,1,1,2,2-pentafluoro-6,6 dimethyl-3,5-heptanedione, n-octanol and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of 1,1,1,2,2-pentafluoro-6,6 dimethyl-3,5-heptanedione, n-octanol and kerosene is 1. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase, and mixing, wherein the temperature of the hydrogen chloride gas at the time of introduction is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 6:1, and the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1:1.5, back extraction is carried out for three times, the single back extraction time is 5 minutes, water phase is collected after back extraction to obtain back extraction solution containing lithium chloride and no-load extraction solution, and the no-load extraction solution is circulated to the extraction stage for continuous use.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.9g/L and a density of about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution at room temperature, 20L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed. Then heating to 85 ℃ for reaction for 90min, filtering while hot to obtain 476g of lithium precipitation mother liquor (the lithium content is about 1.965 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, and drying the lithium carbonate crystals at 100 ℃ overnight to obtain 44.04g of white lithium carbonate powder with the lithium recovery rate of about 86.90 percent.
Example 8:
dissolving 1.2g of sodium chloride in 4.8g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, performing combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously performing evaporation concentration to obtain sodium hydroxide from the sodium hydroxide solution.
Taking 103mL (the density is about 1.02 g/mL) of lithium battery waste leachate, wherein the concentration of lithium in the lithium battery waste leachate is 0.850g/L, the concentration of magnesium in the lithium battery waste leachate is 0.003g/L, and the concentration of calcium in the lithium battery waste leachate is 0.001g/L, adding 0.60g of sodium hydroxide prepared in the above manner into the lithium battery waste leachate, and filtering to obtain a precipitate and 100mL of pretreated lithium battery waste leachate, wherein the pH is 12.8.
Firstly, respectively taking a certain amount of tributyl phosphate and kerosene, and uniformly mixing in a separating funnel to obtain an extract liquor, wherein the volume percentage of the tributyl phosphate is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 4:1, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5, performing back extraction for three times, the time of single back extraction is 5 minutes, collecting the water phase after the back extraction to obtain a back extraction solution containing the lithium chloride and an idle extraction solution, and circulating the idle extraction solution to an extraction stage for continuous use.
After the strip liquor was subjected to several cycles of the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) and had a lithium concentration of 95.6g/L and a density of about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution at room temperature, 20L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed. Then heating to 90 ℃ for reaction for 90min, filtering while hot to obtain 488g of lithium precipitation mother liquor (the lithium content is 1.911 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water is (the lithium content is about 1.459 g/L), and finally drying the lithium carbonate crystals for one night at 100 ℃ to obtain 43.95g of white lithium carbonate powder, wherein the lithium recovery rate is about 86.97%.
Example 9:
dissolving 2.60g of sodium chloride in 10.4g of water to obtain a sodium chloride solution, electrolyzing the sodium chloride solution to obtain a sodium hydroxide solution, chlorine and hydrogen, performing combustion reaction on the chlorine and the hydrogen to obtain hydrogen chloride gas, and simultaneously performing evaporation concentration to obtain sodium hydroxide from the sodium hydroxide solution.
102mL of the lithium precipitation mother liquor obtained in example 1 was taken, the concentration of lithium in the lithium precipitation mother liquor was 2.05g/L, the concentration of magnesium was 0.001g/L, and the concentration of calcium was 0.002g/L, 0.54g of the sodium hydroxide obtained in the above-mentioned preparation was added to the lithium precipitation mother liquor, and the precipitate and 100mL of the pretreated lithium precipitation mother liquor were obtained by filtration, with a pH of 12.80.
Firstly, respectively taking quantitative 1-phenyl-1,3-butanedione and cyclohexane, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the 1-phenyl-1,3-butanedione is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to water is 10, the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1.5.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.9g/L and a density of about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution at room temperature, 20L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed. Then heating to 80 ℃ for reaction for 90min, filtering while hot to obtain 483g of lithium precipitation mother liquor (the lithium content is about 2.011 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water (the lithium content is about 1.478 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 43.98g of white lithium carbonate powder, wherein the lithium recovery rate is about 86.77%.
Example 10:
taking 102mL (the density is about 1.11 g/mL) of salt lake brine, wherein the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, and the concentration of calcium is 0.002g/L, adding 0.57g of sodium hydroxide prepared in the preparation process into the salt lake brine, and filtering to obtain a precipitate and about 100mL of pretreated salt lake brine, wherein the pH value is 12.80.
Firstly, respectively taking a certain amount of dibutyl butyl phosphate and kerosene, and uniformly mixing in a separating funnel to obtain an extract liquor, wherein the volume percentage of the dibutyl butyl phosphate is 40%. And (3) adding 100mL of extract liquor into the pretreated salt lake brine, performing oscillation extraction for 5 minutes, separating a water phase and a lithium-loaded organic phase, performing extraction for three times, and combining the lithium-loaded organic phases.
Taking 100mL of a lithium-loaded organic phase, introducing hydrogen chloride gas and pure water purchased from the market into the lithium-loaded organic phase for mixing, wherein the temperature of the hydrogen chloride gas when the hydrogen chloride gas is introduced is 25 ℃, the pressure is 0.1MPa, the volume ratio of the hydrogen chloride gas to the water is 10.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 95.8g/L and a density of about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above strip liquor was slowly dropped into the sodium hydroxide solution, and 20L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed. Then heating to 85 ℃ for reaction for 90min, filtering while hot to obtain 475g of lithium precipitation mother liquor (the lithium content is 2.056 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water (the lithium content is about 1.458 g/L), and finally drying the lithium carbonate crystals for one night at 100 ℃ to obtain 43.90g of white lithium carbonate powder, wherein the lithium recovery rate is about 86.70%.
Comparative example 1
Comparative example 1 differs from example 1 in that the lithium-loaded organic phase is stripped with hydrochloric acid, comprising the steps of: taking 100mL of the lithium-loaded organic phase prepared in example 1, adding industrial hydrochloric acid (31% by mass fraction) into the lithium-loaded organic phase for mixing, wherein the molar ratio of the industrial hydrochloric acid to the lithium in the lithium-loaded organic phase is 1.5, performing back extraction for three times, wherein the single back extraction time is 5 minutes, collecting an aqueous phase after the back extraction to obtain a back extraction solution containing lithium chloride and an idle extraction solution, and circulating the idle extraction solution to an extraction stage for continuous use.
After the strip liquor was used for several cycles under the above conditions, the lithium chloride-containing strip liquor obtained was analyzed by ICP (inductively coupled plasma Spectroscopy) to have a lithium concentration of 68.7g/L and a density of about 1.25g/mL.
260g of sodium carbonate solution (42.67 g of sodium hydroxide, 16.43 wt%) was put in an oil bath and heated at 80 ℃, 124.6g of the above strip liquor was slowly added dropwise when the temperature of water was raised to about 80 ℃, 14.0L of carbon dioxide was simultaneously introduced, and after 20min, the addition of carbon dioxide and strip liquor was completed simultaneously. Then raising the temperature to 90 ℃, heating for reaction for 90min, filtering while the solution is hot to obtain 371.3g of lithium precipitation mother solution (the lithium content is about 1.958 g/L) and white lithium carbonate crystals, washing the white lithium carbonate crystals twice with 100 ℃ ultrapure water, wherein each time the amount of 100g of water (the lithium content is about 1.472 g/L), and finally drying the lithium carbonate crystals for one night at 100 ℃ to obtain 30.80g of white lithium carbonate powder, wherein the lithium recovery rate is about 84.82%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (20)
1. A method of extracting lithium, comprising:
providing a lithium-loaded organic phase;
mixing the lithium-loaded organic phase, hydrogen chloride gas and water, and performing back extraction and phase splitting to obtain back extraction solution containing lithium chloride; and
and separating the stripping solution to obtain the lithium-containing compound.
2. The method of claim 1, wherein the hydrogen chloride gas is prepared by:
dissolving sodium chloride in water to obtain a sodium chloride solution;
electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen; and
and reacting the chlorine gas with hydrogen to obtain the hydrogen chloride gas.
3. The method according to claim 1, wherein in the step of mixing the lithium-supporting organic phase, the hydrogen chloride gas, and the water, 1mol to 2mol of the hydrogen chloride gas is introduced per 1mol of the lithium ions in the lithium-supporting organic phase.
4. The method of claim 3, wherein the pressure is less than or equal to 2MPa and the temperature is from-30 ℃ to 50 ℃ when the hydrogen chloride gas is introduced; the volume ratio of the hydrogen chloride gas to the water is 4:1-15.
5. The method of claim 2, wherein the step of separating the lithium-containing compound from the strip liquor comprises: and mixing the stripping solution with sodium carbonate to obtain a lithium-containing compound, wherein the lithium-containing compound is lithium carbonate.
6. The lithium extraction process according to claim 5, wherein the temperature of the strip liquor is 70-90 ℃ when mixing with sodium carbonate.
7. The method of claim 2, wherein the step of separating the lithium-containing compound from the strip liquor comprises: and mixing carbon dioxide, the stripping solution and the sodium hydroxide, and carrying out heating reaction to obtain a lithium-containing compound, wherein the temperature of the heating reaction is 50-100 ℃, and the lithium-containing compound is lithium carbonate.
8. The method of claim 7, wherein the back-extraction solution, the sodium hydroxide and the carbon dioxide are mixed and heated to react, and newly generated carbon dioxide is also obtained.
9. The lithium extraction process according to claim 8, wherein the newly generated carbon dioxide is recycled for mixing with the strip liquor, the sodium hydroxide and the heating reaction.
10. The method of claim 5 or 7, wherein in the step of separating the lithium-containing compound from the strip liquor, sodium chloride is also obtained.
11. The method of claim 10, wherein the sodium chloride is recycled for use in the preparation of the hydrogen chloride gas.
12. The method of claim 1, wherein the step of separating the lithium-containing compound from the strip liquor comprises: and controlling the temperature of the stripping solution to be 20-50 ℃, and cooling the stripping solution to obtain the lithium-containing compound, wherein the temperature difference of the cooling is 10-40 ℃, and the lithium-containing compound is lithium chloride.
13. The method of claim 2, wherein the lithium-loaded organic phase is prepared by a method comprising:
providing a lithium-containing solution;
and mixing the lithium-containing solution with an extraction solution, and carrying out extraction and phase separation to obtain the lithium-loaded organic phase.
14. The method of claim 13, wherein the lithium-containing solution further comprises at least one of magnesium ions and calcium ions,
before the step of mixing the lithium-containing solution with the extraction solution, the lithium-containing solution is also mixed with an alkaline substance to obtain a precipitate.
15. The method of claim 14, wherein the alkaline material comprises the sodium hydroxide.
16. The method of claim 14, further comprising mixing the precipitate with the hydrogen chloride gas and water to react to obtain a mixed solution after the precipitate is obtained.
17. The method of claim 13, wherein the volume ratio of the extraction solution to the lithium-containing solution is 4:1-1:4, the number of extractions is greater than or equal to 1, and the time of each extraction is 1-10 minutes.
18. The lithium extraction process according to claim 13, wherein the extraction solution comprises an extractant and a diluent, the extractant is a hydrophobic liquid, including trioxothiophene oxide, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2-pentafluoro-6,6 dimethyl-3,5-heptanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, benzoyl trifluoroacetone, 1-phenyl-1,3-butanedione, 1-benzoyl-2-nonanone, trialkyl phosphate, trialkyl phosphine oxide, trioctylphosphine oxide, trihexylphosphine oxide, dialkyl phosphate, methyl isobutyl ketone, 1-phenylazo-2-naphthol, N-octanol, 2-ethylhexanol, dibutyl 14-crown-4 ether butyl phosphine, dibutyl phosphate, tetramethylene tetrabutyl bis phosphate, trioctyl amine oxide, 5329-phenanthroline, N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.S.S.S.S.S.S.S. 263 At least one of dimethylbis (N-octadecyl) ammonium chloride, methyldioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
19. The method of claim 13, wherein a lithium precipitation mother liquor is obtained after separating the lithium-containing compound from the strip liquor, and the lithium precipitation mother liquor is recycled and mixed with the lithium-containing solution.
20. The method of claim 13, wherein in the step of mixing the lithium-loaded organic phase, hydrogen chloride gas and water, performing stripping and phase separation to obtain a stripping solution containing lithium chloride, an idle extraction solution is also obtained;
the no-load extraction liquid is recycled and is used for being mixed with the extraction liquid to carry out extraction and phase splitting to obtain the lithium-loaded organic phase;
and/or in the step of mixing the lithium-loaded organic phase, hydrogen chloride gas and water, performing back extraction and phase separation to obtain a back extraction solution containing lithium chloride, continuously circulating part of the back extraction solution, mixing the back extraction solution with the lithium-loaded organic phase, the hydrogen chloride gas and the water, and performing back extraction and phase separation.
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