CN115198108B - Method for extracting lithium - Google Patents
Method for extracting lithium Download PDFInfo
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- CN115198108B CN115198108B CN202110394688.6A CN202110394688A CN115198108B CN 115198108 B CN115198108 B CN 115198108B CN 202110394688 A CN202110394688 A CN 202110394688A CN 115198108 B CN115198108 B CN 115198108B
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- Prior art keywords
- lithium
- hydrogen chloride
- solution
- organic phase
- chloride gas
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 313
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 313
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 191
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000012074 organic phase Substances 0.000 claims abstract description 104
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 102
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 238000002156 mixing Methods 0.000 claims abstract description 61
- 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 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 238000005191 phase separation Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 237
- 239000000243 solution Substances 0.000 claims description 177
- 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 78
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 51
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 50
- 239000011780 sodium chloride Substances 0.000 claims description 49
- 239000001569 carbon dioxide Substances 0.000 claims description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 39
- 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 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 239000000126 substance Substances 0.000 claims description 7
- 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
- PPDZLUVUQQGIOJ-UHFFFAOYSA-N 1-dihexylphosphorylhexane Chemical class CCCCCCP(=O)(CCCCCC)CCCCCC PPDZLUVUQQGIOJ-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- PVDDBYSFGBWICV-UHFFFAOYSA-N 1,4,8,11-tetraoxacyclotetradecane Chemical compound C1COCCOCCCOCCOC1 PVDDBYSFGBWICV-UHFFFAOYSA-N 0.000 claims description 3
- RZNHHGMCDDENDY-UHFFFAOYSA-N 1-(1-methylimidazol-2-yl)ethanol Chemical compound CC(O)C1=NC=CN1C RZNHHGMCDDENDY-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
- KBOBBVDOPFIWIT-UHFFFAOYSA-N 2,2-dimethyloctane-3,5-dione Chemical compound CCCC(=O)CC(=O)C(C)(C)C KBOBBVDOPFIWIT-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
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-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
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-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
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 claims description 3
- SCPHDVDVGFRLEI-UHFFFAOYSA-N dibutyl dibutoxyphosphoryloxymethyl phosphate Chemical compound P(=O)(OCCCC)(OCCCC)OCOP(=O)(OCCCC)OCCCC SCPHDVDVGFRLEI-UHFFFAOYSA-N 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 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
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical class CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000002360 preparation method 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 64
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 64
- 239000011777 magnesium Substances 0.000 description 29
- 239000011575 calcium Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 25
- 238000009616 inductively coupled plasma Methods 0.000 description 22
- 239000012071 phase Substances 0.000 description 22
- 238000001914 filtration Methods 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 15
- 238000002386 leaching Methods 0.000 description 14
- 239000003350 kerosene Substances 0.000 description 13
- 238000011084 recovery Methods 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
- 230000008020 evaporation Effects 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- -1 hydrogen ions Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate 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
- 230000008021 deposition Effects 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
- 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
- OJGXEKSQTVUPSN-UHFFFAOYSA-N [PH3]=O.C(CCCCCCC)P(CCCCCCCC)(CCCCCCCC)=O Chemical compound [PH3]=O.C(CCCCCCC)P(CCCCCCCC)(CCCCCCCC)=O OJGXEKSQTVUPSN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 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
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 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
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 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
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Extraction Or Liquid Replacement (AREA)
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 carrying out back extraction and phase separation to obtain a back extraction solution containing lithium chloride; and separating the lithium-containing compound from the strip liquor. In the lithium extraction method, the combination of the hydrogen chloride gas and the water is used as the stripping agent, and the acid preparation and the stripping are simultaneously carried out in the process of stripping, so that the hydrogen chloride gas and the hydrochloric acid coexist, and the hydrogen chloride gas is continuously converted into the hydrochloric acid to supplement the reacted hydrochloric acid, therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the organic phase loaded with lithium, the hydrogen chloride gas and the water can be effectively improved, the concentration of lithium ions in the obtained stripping liquid is improved to about 96g/L, the yield of lithium is further effectively improved, and the energy consumption required in the crystallization process is also 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 along with the promotion of the reuse of waste resources in recent years, waste lithium batteries also become an important source of lithium resources. 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, and 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 percentage of the industrial hydrochloric acid is generally 31% -33%, so that the concentration of lithium ions in the back extraction liquid obtained by back extraction is about 70g/L, and a large amount of water is required 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 lithium extraction method that is low in energy consumption and high in 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 carrying out back extraction and phase separation to obtain a back extraction solution containing lithium chloride; and
and separating the lithium-containing compound from the strip liquor.
In one embodiment, the hydrogen chloride gas is prepared by the following method:
dissolving sodium chloride in water to obtain sodium chloride solution;
electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen; and
and reacting the chlorine 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, 1 to 2 moles of the hydrogen chloride gas per 1 mole of lithium ions in the lithium-loaded organic phase are introduced.
In one embodiment, when the hydrogen chloride gas is introduced, the pressure is less than or equal to 2MPa, and the temperature is between-30 ℃ and 50 ℃; the volume ratio of the hydrogen chloride gas to the water is 4:1-15:1.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: and mixing the strip liquor with sodium carbonate to obtain a lithium-containing compound, wherein the lithium-containing compound is lithium carbonate.
In one embodiment, the temperature is 70 ℃ to 90 ℃ when the strip liquor is mixed with sodium carbonate.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: mixing carbon dioxide, the back extraction liquid and the sodium hydroxide, and performing a 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, the newly generated carbon dioxide is also obtained when the strip liquor, the sodium hydroxide and the carbon dioxide are mixed and heated for reaction.
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, sodium chloride is also obtained in the step of separating the lithium-containing compound from the strip liquor.
In one embodiment, the sodium chloride is recycled for use in preparing 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 back extraction liquid to be 20-50 ℃, and cooling the back extraction liquid to obtain the lithium-containing compound, wherein the temperature difference of cooling is 10-40 ℃, and the lithium-containing compound is lithium chloride.
In one embodiment, the method for preparing the lithium-loaded organic phase includes:
providing a lithium-containing solution;
and mixing the lithium-containing solution with the extract, and extracting and phase-separating to obtain the lithium-loaded organic phase.
In one embodiment, the lithium-containing solution also comprises at least one of magnesium ions and calcium ions,
the lithium-containing solution is further mixed with an alkaline substance to obtain a precipitate, before the step of mixing the lithium-containing solution with the extract.
In one embodiment, the alkaline substance comprises the sodium hydroxide.
In one embodiment, after the precipitate is obtained, the method further comprises mixing the precipitate with the hydrogen chloride gas and water, and reacting to obtain a mixed solution.
In one embodiment, 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 minute-10 minutes.
In one embodiment, the extraction fluid comprises an extractant and a diluent, the extractant being a hydrophobic liquid, comprising trioxythiophene oxide, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione, 1, 2-pentafluoro-6, 6-dimethyl-3, 5-heptanedione, 1,2, 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, isooctanol, 2-ethylhexanol, dibutyl 14-crown-4 ether butylphosphonate, dibutyl phosphate, methylene tetrabutyl bisphosphate, trioctylamine oxide, 1, 10-phenanthroline, quaternary ammonium salt N 263 At least one of dimethyl di (N-octadecyl) ammonium chloride, methyl dioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide.
In one embodiment, after separation of the lithium-containing compound from the strip liquor, a lithium-precipitating mother liquor is also obtained, which is recycled 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, a no-load extraction solution is also obtained;
the unloaded extraction liquid is recycled and is used for mixing with the extraction liquid, extracting and phase-separating to obtain the organic phase loaded with lithium;
and/or mixing the lithium-loaded organic phase, hydrogen chloride gas and water, carrying out back extraction and phase separation, and obtaining a back extraction liquid containing lithium chloride, wherein part of the back extraction liquid continues to circulate, and mixing with the lithium-loaded organic phase, the hydrogen chloride gas and the water, and carrying out back extraction and phase separation.
In the lithium extraction method, the combination of the hydrogen chloride gas and the water is used as the stripping agent, and the acid preparation and the stripping are simultaneously carried out in the process of stripping, so that the hydrogen chloride gas and the hydrochloric acid coexist, and the hydrogen chloride gas is continuously converted into the hydrochloric acid to supplement the reacted hydrochloric acid, therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the organic phase loaded with lithium, the hydrogen chloride gas and the water can be effectively improved, the concentration of lithium ions in the obtained stripping liquid is improved to about 96g/L, the yield of lithium is further effectively improved, and the energy consumption required in the crystallization process is also reduced.
Drawings
Fig. 1 is a process flow diagram of the lithium extraction method of the present invention.
Detailed Description
The method for extracting lithium provided by the invention will be further described with reference to the accompanying drawings.
As shown in fig. 1, the method for extracting lithium provided by the invention comprises the following steps:
(1) Providing a lithium-loaded organic phase;
(2) Mixing the lithium-loaded organic phase, hydrogen chloride gas and water, and carrying out back extraction and phase separation to obtain a back extraction solution containing lithium chloride;
(3) And separating the lithium-containing compound from the strip liquor.
In the step (1), the organic phase loaded with lithium is obtained by extraction through an extraction liquid, and the preparation method comprises the following steps:
(11) Providing a lithium-containing solution;
(12) Mixing the lithium-containing solution with the extract, extracting and separating phases to obtain the lithium-loaded organic phase.
In the step (11), the lithium-containing solution comprises at least one of salt lake brine, lithium ore leaching solution, lithium battery waste leaching solution and lithium precipitation mother solution.
Due to Cl in the salt lake brine - 、SO 4 2- 、HCO 3 - 、CO 3 2- 、Na + 、K + 、Mg 2+ 、Ca 2+ The equiconcentration is high, wherein a large amount of Mg exists 2+ 、Ca 2+ The separation of lithium is difficult, so 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 so as to ensure that the Mg in the lithium-containing solution 2+ Converted into magnesium hydroxide precipitate, ca 2+ Conversion to calcium hydroxide precipitate to substantially remove Mg 2+ And Ca 2+ 。
When salt lake brine Mg 2+ And/or Ca 2+ When the content is higher, partial Mg can be removed by adopting methods such as adsorption and the like 2+ Reduce Mg 2+ Is then mixed with alkaline substances 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+ And the pH can be adjusted to be alkaline so as to be more beneficial to the extraction step.
When Mg is contained in a lithium-containing solution such as a lithium ore leaching solution, a lithium battery waste leaching solution, or a lithium precipitation mother solution 2+ And/or Ca 2+ The Mg can be removed by the method 2+ And/or Ca 2+ At the same time dissolve lithium-containingThe pH of the solution was adjusted to alkaline.
In step (12), the extract includes an extractant and a diluent. Wherein the extractant is hydrophobic liquid, comprising trioxythiophene oxide, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione, 1, 2-pentafluoro-6, 6-dimethyl-3, 5-heptanedione, 1,2, 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, isooctanol, 2-ethylhexanol, dibutyl 14-crown-4 ether butylphosphonate, dibutyl phosphate, methylene tetrabutyl bisphosphate, trioctylamine oxide, 1, 10-phenanthroline, quaternary ammonium salt N 263 At least one of dimethyl di (N-octadecyl) ammonium chloride, methyl dioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazole bis (trifluoromethyl sulfonyl) imide, wherein the trialkyl phosphate comprises tributyl phosphate and the like. The diluent comprises at least one of 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 sulfonated kerosene.
Further, the volume ratio of the extractant in the extract is not limited, and is specifically adjusted according to the selection of the extractant and the diluent, and in one embodiment, the volume percentage of the extractant in the extract is 40% -50%.
When the lithium-containing solution is mixed with the extracting solution, the volume ratio of the extracting solution to the lithium-containing solution is 4:1-1:4, the extraction times are 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 the extraction is finished, an organic phase loaded with lithium and raffinate incompatible with the organic phase are obtained through phase separation, and the raffinate can be discharged after environmental protection treatment, and the method is simple.
When the number of extraction times is more than 1, that is, when multi-stage extraction is performed, the raffinate may be substituted for the lithium-containing solution, and extraction may be continued by mixing with the extract under the conditions of the extraction. When three-stage extraction is carried out, mixing lithium-containing solution with extract liquor for extraction to obtain a first-stage lithium-loaded organic phase and a first-stage raffinate, mixing the first-stage raffinate with the extract liquor for secondary extraction to obtain a second-stage lithium-loaded organic phase and a second-stage raffinate, continuing to carry out third extraction with the extract liquor to obtain a third-stage lithium-loaded organic phase and a third-stage raffinate, merging the first-stage lithium-loaded organic phase and the third-stage lithium-loaded organic phase, carrying out back extraction in the step (2), and discharging the third-stage raffinate after environmental protection treatment.
In the step (2), the combination of the hydrogen chloride gas and water is used as a stripping agent, when the organic phase loaded with lithium, the hydrogen chloride gas and the water are mixed for stripping, the acid preparation and the stripping are simultaneously carried out, so that the hydrogen chloride gas and the hydrochloric acid coexist, and the hydrogen chloride gas is continuously converted into the hydrochloric acid to supplement the reacted hydrochloric acid, therefore, the concentration of the hydrogen chloride in a stripping system obtained by mixing the organic phase loaded with lithium, 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 includes: the hydrogen chloride gas and water are continuously fed into the lithium-loaded organic phase while being mixed with the lithium-loaded 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, based on the 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 4:1-15:1, preferably 4:1-10:1.
Specifically, the number of times 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 strip liquor obtained by phase separation is improved to about 96g/L, so that the yield of lithium is effectively improved, and meanwhile, the higher the concentration of lithium ions in the strip liquor is, the lower the energy consumption required in the crystallization process is.
In the step (2), after back extraction, when the back extraction liquid containing lithium chloride is obtained by phase separation, no-load extraction liquid is also obtained, and the no-load extraction liquid can be recycled, for example, recycled to the step (12) to be mixed with the extraction liquid after recycling, and is used for extracting lithium-containing solution again to obtain an organic phase containing lithium.
Considering that lithium ions which are not completely stripped may also exist in the empty extract, the empty extract may be subjected to multistage stripping with reference to a multistage extraction scheme in the extraction.
In addition, when the concentration of lithium ions in the stripping liquid obtained by phase separation is low, the stripping liquid can be continuously circulated and mixed with the organic phase loaded with lithium for stripping, and when the circulation is performed, water and/or hydrogen chloride gas is introduced into the stripping liquid, and the circulation time can be more than 1 time.
Further, when the concentration of lithium ions in the strip liquor reaches equilibrium, part of the strip liquor can also enter the step (3), part of the strip liquor continues to circulate, and is mixed with the organic phase loaded with lithium, the hydrogen chloride gas and the water for strip and phase separation, preferably, when the strip liquor circulates, water and/or hydrogen chloride gas is introduced into the strip liquor.
In the step (3), the method for separating the lithium-containing compound from the strip liquor is numerous, and when different methods are adopted, the obtained lithium-containing compound is different and comprises 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 strip liquor 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 back extraction liquid when the back extraction liquid is mixed with sodium carbonate is preferably 70-90 ℃, and the back extraction liquid is slowly dripped into the sodium carbonate solution when the back extraction liquid is mixed, wherein the molar ratio of lithium ions to carbonate ions is 2:1-2:1.1.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: mixing the back extraction liquid, the sodium hydroxide and the carbon dioxide, and carrying out heating reaction, wherein the temperature of the heating reaction is 50-100 ℃, preferably 70-90 ℃, so as to obtain lithium-containing compound precipitate, and the lithium-containing compound is lithium carbonate.
When the back extraction liquid, the sodium hydroxide and the carbon dioxide are mixed, and the molar ratio of the lithium ions, the carbonate ions and the carbon dioxide is 1:1:1, the lithium carbonate is directly obtained by reaction.
In view of the solubility of carbon dioxide, the stripping solution, sodium hydroxide and carbon dioxide may be mixed first and then heated for reaction, and the temperature at the time of mixing is preferably not higher than 30 ℃, more preferably directly at normal temperature, in order to sufficiently dissolve carbon dioxide into the solution. Of course, the heating reaction can be performed while introducing 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, the carbon dioxide may be in excess, preferably in a molar percentage of less than 110% of the molar percentage of lithium ions, at which time lithium chloride, sodium hydroxide and carbon dioxide react to form lithium bicarbonate, which is decomposed under heating to lithium carbonate and carbon dioxide, which can be recycled for mixing with the strip liquor, the sodium hydroxide and carrying out the heating reaction.
In one embodiment, the step of separating the lithium-containing compound from the strip liquor comprises: the temperature of the back extraction liquid is controlled to be 20-50 ℃, the temperature of the back extraction liquid is reduced to be 10-40 ℃, the temperature difference of the temperature reduction is preferably 20-40 ℃, for example, the temperature of the back extraction liquid obtained by phase separation is 30 ℃, the temperature of the back extraction liquid is reduced to be 0 ℃ or-10 ℃, and at the moment, lithium chloride is separated out due to supersaturation.
In this embodiment, if Mg is further contained in the strip solution 2+ And/or Ca 2+ To avoid Mg 2+ And/or Ca 2+ Before cooling, the back extraction liquid can be adsorbed to remove Mg 2+ And/or Ca 2+ 。
In this embodiment, the precipitated lithium chloride may further contain a part of sodium chloride, and the lithium chloride may be redissolved in water, and then sodium carbonate may be added to obtain a lithium carbonate precipitate and a sodium chloride solution.
The lithium carbonate obtained by the embodiments of the invention is lithium carbonate with higher purity, and the purity can reach more than 98.5%.
In the step (3), after the lithium-containing compound is separated from the strip liquor, a lithium precipitation mother liquor is also obtained, and the lithium precipitation mother liquor can be recycled to the step (11) and mixed with the lithium-containing solution to enter the extraction step again.
Taking into account Mg in the lithium precipitation mother liquor 2+ And/or Ca 2+ The plasma is basically removed, and the influence on the extraction of lithium is small, so that the lithium precipitation mother liquor can be independently mixed with the extraction liquor 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 that the lithium-containing compound with higher purity is obtained.
As shown in fig. 1, the hydrogen chloride gas according to the present invention can be prepared by:
(21) Dissolving sodium chloride in water to obtain sodium chloride solution;
(22) Electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen;
(23) And reacting the chlorine with hydrogen to obtain the hydrogen chloride gas.
Thus, the chlorine alkali process can be adopted to prepare the hydrogen chloride gas and sodium hydroxide, then the hydrogen chloride gas is used in the step (2) to be mixed with the organic phase loaded with lithium and water for back extraction, and the sodium hydroxide is used for being mixed with the lithium-containing solution in the step (11) to mix Mg 2+ Converted into magnesium hydroxide precipitate, ca 2+ Converting into calcium hydroxide precipitate, removing Mg 2+ And Ca 2+ And adjusting the pH of the lithium-containing solution, and, for use in step (3), with the strip liquor and carbon dioxide Mixing to prepare the lithium carbonate.
When the lithium-containing solution is salt lake brine, taking the extraction of 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.
And the precipitates such as magnesium hydroxide, calcium hydroxide and the like precipitated by sodium hydroxide can be mixed with the hydrogen chloride gas and water again to react to obtain a mixed solution, wherein the mixed solution contains Cl - 、Na + 、Mg 2+ And Ca 2+ Etc. Therefore, the mixed liquor can be directly discharged into salt lake brine.
From the aspect of ion conservation analysis, when the process is used for circularly extracting lithium from 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 recycled into the salt lake brine, so that the ecology of the salt lake can be greatly protected.
Meanwhile, when the carbon dioxide and the sodium hydroxide are used for preparing the lithium carbonate, besides the extraction liquid and the carbon dioxide, the whole extraction and back extraction steps do not need to use any other chemical reagent, the extraction agent and the carbon dioxide can be recycled, and any acidic and/or alkaline chemical reagent is not required to be transported to a salt lake region, 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 reused.
Similarly, when sodium carbonate is used to prepare lithium carbonate, no other chemical reagent is needed for the whole extraction and stripping steps except the extract and 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 extract liquid.
In addition to the lithium-containing compound obtained in step (3), 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 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 lithium ore leaching solution, lithium battery waste leaching solution or lithium precipitation mother solution, the hydrogen chloride gas can be obtained from the steps (21) to (24), so that the sodium chloride can be recycled in the whole preparation process, and the cost is reduced.
In this case, if the precipitate such as magnesium hydroxide or calcium hydroxide is precipitated with sodium hydroxide, the precipitate may be directly used as an accessory product.
Hereinafter, the extraction method of lithium will be further described by the following specific examples.
Example 1:
1.96g of sodium chloride was dissolved in 7.84g of water to obtain a sodium chloride solution, the sodium chloride solution was electrolyzed to obtain a sodium hydroxide solution, chlorine gas and hydrogen gas, and then the chlorine gas and the hydrogen gas were reacted by combustion to obtain a hydrogen chloride gas, and at the same time, sodium hydroxide was obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.15g/L, the concentration of calcium is 0.08g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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 in a separating funnel to obtain an extract, wherein the volume ratio of the methyl isobutyl ketone is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 7.5:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is about 1.11:1, the back extraction is performed three times, the single back extraction time is 5 minutes, and collecting the water phase after the back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.5g/L, and the density is about 1.29g/mL.
398g of sodium carbonate solution (79.54 g of sodium carbonate, 20 wt%) is taken and put into an oil bath for heating at 80 ℃, 128.97g of the back extraction liquid is slowly dripped when the water temperature is raised to about 80 ℃, and the dripping is completed after 20 minutes. The reaction was then continued for 90min with heating, and the filtrate was filtered while hot to give 481g of a precipitated lithium mother liquor (lithium content: about 2.05 g/L) and a white lithium carbonate crystal, which was washed twice with 100 ℃ ultrapure water, each time with 100g of water (lithium content: about 1.516 g/L), and finally the lithium carbonate crystal was dried overnight at 100 ℃ to give 43.41g of a white lithium carbonate powder, the lithium recovery rate being about 86.00%.
Example 2:
2.22g of sodium chloride was dissolved in 8.88g of water to obtain a sodium chloride solution, the sodium chloride solution was electrolyzed to obtain a sodium hydroxide solution, chlorine gas and hydrogen gas, and then the chlorine gas and the hydrogen gas were reacted by combustion to obtain a hydrogen chloride gas, and at the same time, sodium hydroxide was obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 8.5:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.25:1, the back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after the back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.8g/L, and the density is about 1.29g/mL.
398g of sodium carbonate solution (79.54 g of sodium carbonate, 20 wt%) is taken and put into an oil bath for heating at 80 ℃, 128.98g of the back extraction liquid is slowly dripped when the water temperature is raised to about 80 ℃, and the dripping is completed after 20 minutes. The reaction was then continued for 90 minutes with heating, and filtration while hot gave 478g of a precipitated lithium mother liquor (lithium content about 2.112 g/L) and lithium carbonate white crystals, which were washed twice with 100℃ultra pure water, each time with 100g of water (lithium content about 1.525 g/L), and finally the lithium carbonate crystals were dried overnight at 100℃to give about 43.60g of lithium carbonate white powder, with a lithium recovery of about 86.10%.
Example 3:
2.60g of sodium chloride is dissolved in 10.4g of water to obtain a sodium chloride solution, the sodium chloride solution is electrolyzed to obtain a sodium hydroxide solution, chlorine and hydrogen, then the chlorine and the hydrogen are subjected to combustion reaction to obtain a hydrogen chloride gas, and simultaneously sodium hydroxide is obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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, wherein the volume ratio of the dimethyl di (N-octadecyl) ammonium chloride is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 96.0g/L, and the density is about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above-mentioned stripping solution was slowly added dropwise to the sodium hydroxide solution at room temperature, 17L of carbon dioxide was simultaneously introduced, and after 20 minutes, the carbon dioxide and the stripping solution were simultaneously added. Then heating to 90 ℃ for reaction for 90min, filtering while the mixture is hot to obtain 482g of lithium precipitation mother liquor (the lithium content is about 2.065 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, each time, 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 lithium carbonate white powder, wherein the lithium recovery rate is about 86.48%.
Example 4:
2.60g of sodium chloride is dissolved in 10.4g of water to obtain a sodium chloride solution, the sodium chloride solution is electrolyzed to obtain a sodium hydroxide solution, chlorine and hydrogen, then the chlorine and the hydrogen are subjected to combustion reaction to obtain a hydrogen chloride gas, and simultaneously sodium hydroxide is obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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 trialkylphosphine oxide and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the trialkylphosphine oxide is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.7g/L, and the density is about 1.29g/ml.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above-mentioned stripping solution was slowly added dropwise to the sodium hydroxide solution at room temperature, and 20L of carbon dioxide was simultaneously introduced, after 20min, the carbon dioxide and the stripping solution were added simultaneously. Then heating to 80 ℃ for reaction for 90min, filtering while the solution is hot to obtain 485g of lithium precipitation mother solution (the lithium content is about 1.987 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, wherein the water content is 100g each time (the lithium content is about 1.463 g/L), and finally drying the lithium carbonate crystals at 100 ℃ for one night to obtain 43.79g of lithium carbonate white powder, wherein the lithium recovery rate is about 86.57%.
Example 5:
2.60g of sodium chloride is dissolved in 10.4g of water to obtain a sodium chloride solution, the sodium chloride solution is electrolyzed to obtain a sodium hydroxide solution, chlorine and hydrogen, then the chlorine and the hydrogen are subjected to combustion reaction to obtain a hydrogen chloride gas, and simultaneously sodium hydroxide is obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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 trihexyl phosphine oxide and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the trihexyl phosphine oxide is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.5g/L, and the density is about 1.29g/mL.
128.96g of back extraction liquid is taken, the temperature is controlled at 30 ℃, stirring is started for 10min, and then the back extraction liquid is rapidly cooled to 0 ℃ to obtain 46.31g of lithium chloride, and the recovery rate of lithium is about 79.87%.
Example 6:
2.60g of sodium chloride is dissolved in 10.4g of water to obtain a sodium chloride solution, the sodium chloride solution is electrolyzed to obtain a sodium hydroxide solution, chlorine and hydrogen, then the chlorine and the hydrogen are subjected to combustion reaction to obtain a hydrogen chloride gas, and simultaneously sodium hydroxide is obtained from the sodium hydroxide solution by evaporation concentration.
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH 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, wherein the volume ratio of the dimethyl di (N-octadecyl) ammonium chloride is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.8g/L, and the density is about 1.29g/mL.
128.97g of back extraction liquid is taken, the temperature is controlled at 30 ℃, stirring is started for 10min, and then the back extraction liquid is rapidly cooled to-10 ℃ to obtain 51.55g of lithium chloride, and the lithium recovery rate is about 88.91%.
Example 7:
1.54g of sodium chloride was dissolved in 6.16g of water to obtain a sodium chloride solution, the sodium chloride solution was electrolyzed to obtain a sodium hydroxide solution, chlorine gas and hydrogen gas, and then the chlorine gas and the hydrogen gas were reacted by combustion to obtain a hydrogen chloride gas, and at the same time, sodium hydroxide was obtained from the sodium hydroxide solution by evaporation concentration.
105mL (density of about 1.09 g/mL) of lithium ore leaching solution was taken, the concentration of lithium in the lithium ore leaching solution was 1.2g/L, the concentration of magnesium was 0.1g/L, the concentration of calcium was 0.08g/L, 0.68g of sodium hydroxide prepared as described above was added to the lithium ore leaching solution, and the obtained precipitate and 100mL of pretreated lithium ore leaching solution were filtered, and the pH was 12.80.
Firstly, respectively taking quantitative 1, 2-pentafluoro-6, 6-dimethyl-3, 5-heptanedione, n-octanol and kerosene, uniformly mixing in a separating funnel to obtain an extract, the volume ratio of 1, 2-pentafluoro-6, 6-dimethyl-3, 5-heptanedione, n-octanol and kerosene is 1:1:2. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out 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, and introducing the hydrogen chloride gas and pure water into the lithium-loaded organic phase to mix, 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 6:1, and the molar ratio of the hydrogen chloride gas to the lithium in the lithium-loaded organic phase is 1: and 1.5:1, back-extracting for three times, wherein the single back-extracting time is 5 minutes, and collecting water phase after back-extracting to obtain back-extracting solution containing lithium chloride and no-load extracting solution, wherein the no-load extracting solution is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.9g/L, and the density is about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above-mentioned stripping solution was slowly added dropwise to the sodium hydroxide solution at room temperature, and 20L of carbon dioxide was simultaneously introduced, after 20min, the carbon dioxide and the stripping solution were added simultaneously. Then heating to 85 ℃ for reaction for 90min, filtering while the solution is hot to obtain 476g of precipitated lithium mother solution (the lithium content is about 1.965 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, each time with 100g of water (the lithium content is about 1.498 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 44.04g of lithium carbonate white powder, wherein the lithium recovery rate is about 86.90%.
Example 8:
1.2g of sodium chloride was dissolved in 4.8g of water to obtain a sodium chloride solution, the sodium chloride solution was electrolyzed to obtain a sodium hydroxide solution, chlorine gas and hydrogen gas, and then the chlorine gas and the hydrogen gas were reacted by combustion to obtain a hydrogen chloride gas, and at the same time, sodium hydroxide was obtained from the sodium hydroxide solution by evaporation concentration.
103mL (density is about 1.02 g/mL) of lithium battery waste leaching solution is taken, the concentration of lithium in the lithium battery waste leaching solution is 0.850g/L, the concentration of magnesium is 0.003g/L, the concentration of calcium is 0.001g/L, 0.60g of sodium hydroxide prepared by the method is added into the lithium battery waste leaching solution, and a precipitate and 100mL of pretreated lithium battery waste leaching solution are obtained by filtering, wherein the pH is 12.8.
Firstly, respectively taking quantitative tributyl phosphate and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the tributyl phosphate is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.6g/L, and the density is about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above-mentioned stripping solution was slowly added dropwise to the sodium hydroxide solution at room temperature, and 20L of carbon dioxide was simultaneously introduced, after 20min, the carbon dioxide and the stripping solution were added simultaneously. Then heating to 90 ℃ for reaction for 90min, filtering while the mixture is hot to obtain 488g of lithium precipitation mother liquor (the lithium content is about 1.911 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, wherein the water content is 100g each time (the lithium content is about 1.459 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 43.95g of lithium carbonate white powder, wherein the lithium recovery rate is about 86.97%.
Example 9:
2.60g of sodium chloride is dissolved in 10.4g of water to obtain a sodium chloride solution, the sodium chloride solution is electrolyzed to obtain a sodium hydroxide solution, chlorine and hydrogen, then the chlorine and the hydrogen are subjected to combustion reaction to obtain a hydrogen chloride gas, and simultaneously sodium hydroxide is obtained from the sodium hydroxide solution by evaporation concentration.
102mL of the lithium deposition mother liquor of example 1 was taken, the concentration of lithium in the lithium deposition mother liquor was 2.05g/L, the concentration of magnesium was 0.001g/L, the concentration of calcium was 0.002g/L, 0.54g of sodium hydroxide prepared as described above was added to the lithium deposition mother liquor, and the precipitate and 100mL of the pretreated lithium deposition mother liquor were obtained by filtration, and the pH was 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%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, back extraction is carried out three times, the single back extraction time is 5 minutes, and collecting the water phase after back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.9g/L, and the density is about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above-mentioned stripping solution was slowly added dropwise to the sodium hydroxide solution at room temperature, and 20L of carbon dioxide was simultaneously introduced, after 20min, the carbon dioxide and the stripping solution were added simultaneously. Then heating to 80 ℃ for reaction for 90min, filtering while the solution is hot to obtain 483g of lithium precipitation mother solution (the lithium content is about 2.011 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, each time, 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 lithium carbonate white powder, wherein the lithium recovery rate is about 86.77%.
Example 10:
102mL (density is about 1.11 g/mL) of salt lake brine is taken, the concentration of lithium in the salt lake brine is 2g/L, the concentration of magnesium is 0.002g/L, the concentration of calcium is 0.002g/L, 0.57g of sodium hydroxide prepared by the method is added into the salt lake brine, and a precipitate and about 100mL of pretreated salt lake brine are obtained by filtering, wherein the pH is 12.80.
Firstly, respectively taking quantitative dibutyl butyl phosphate and kerosene, and uniformly mixing in a separating funnel to obtain an extract, wherein the volume ratio of the dibutyl butyl phosphate is 40%. Taking 100mL of extract, adding the pretreated salt lake brine, oscillating and extracting for 5 minutes, separating out a water phase and a lithium-loaded organic phase, extracting for three times, and combining the lithium-loaded organic phases.
And (3) taking 100mL of lithium-loaded organic phase, introducing hydrogen chloride gas purchased in a market and pure water into the lithium-loaded organic phase to mix, 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 10:1, the molar ratio of the hydrogen chloride gas to lithium in the lithium-loaded organic phase is 1.5:1, the back extraction is performed three times, the single back extraction time is 5 minutes, and collecting water phase after the back extraction to obtain a back extraction liquid and an empty extraction liquid containing lithium chloride, wherein the empty extraction liquid is recycled to the extraction stage to be used continuously.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 95.8g/L, and the density is about 1.29g/mL.
375g of sodium hydroxide solution (60 g of sodium hydroxide, 16 wt%) was taken, 128.92g of the above stripping solution was slowly added dropwise to the sodium hydroxide solution, 20L of carbon dioxide was simultaneously introduced, and after 20 minutes, the carbon dioxide and the stripping solution were simultaneously added. Then heating to 85 ℃ for reaction for 90min, filtering while the solution is hot to obtain 475g of precipitated lithium mother solution (the lithium content is about 2.056 g/L) and lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, wherein the water content is 100g each time (the lithium content is about 1.458 g/L), and finally drying the lithium carbonate crystals at 100 ℃ for one night to obtain 43.90g of lithium carbonate white 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 back-extracted with hydrochloric acid, the steps comprising: 100mL of the lithium-loaded organic phase prepared in example 1 is taken, industrial hydrochloric acid (31% mass fraction) is added into the lithium-loaded organic phase for mixing, the molar ratio of the industrial hydrochloric acid to the lithium in the lithium-loaded organic phase is 1.5:1, the stripping is carried out three times, the single stripping time is 5 minutes, and water phase is collected after the stripping to obtain stripping solution containing lithium chloride and no-load extract, and the no-load extract is recycled to the extraction stage for continuous use.
After the stripping solution is recycled for a plurality of times under the conditions, the stripping solution containing lithium chloride is analyzed by ICP (inductively coupled plasma spectrometer), wherein the concentration of lithium in the obtained stripping solution containing lithium chloride is 68.7g/L, and the density is about 1.25g/mL.
260g of sodium carbonate solution (42.67 g of sodium hydroxide, 16.43 wt%) is taken and put into an oil bath for heating at 80 ℃, 124.6g of the back extraction liquid is slowly dripped when the water temperature is raised to about 80 ℃, and 14.0L of carbon dioxide is simultaneously introduced, and after 20min, the carbon dioxide and the back extraction liquid are simultaneously added. Then heating to 90 ℃ 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 lithium carbonate white crystals, washing the lithium carbonate white crystals twice with 100 ℃ ultrapure water, each time with 100g of water (the lithium content is about 1.472 g/L), and finally drying the lithium carbonate crystals at 100 ℃ overnight to obtain 30.80g of lithium carbonate white powder, wherein the lithium recovery rate is about 84.82%.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (20)
1. A method for extracting lithium, comprising:
providing a lithium-loaded organic phase;
continuously introducing hydrogen chloride gas and water into the lithium-loaded organic phase, mixing the hydrogen chloride gas and the water with the lithium-loaded organic phase, carrying out back extraction and phase separation to obtain a back extraction liquid containing lithium chloride, continuously circulating the back extraction liquid when the concentration of lithium ions in the back extraction liquid is low, mixing the back extraction liquid with the lithium-loaded organic phase for back extraction, and introducing water and/or hydrogen chloride gas into the back extraction liquid when the concentration of lithium ions in the back extraction liquid is low; and
And separating the lithium-containing compound from the strip liquor.
2. The method for extracting lithium according to claim 1, wherein the hydrogen chloride gas is prepared by:
dissolving sodium chloride in water to obtain sodium chloride solution;
electrolyzing the sodium chloride solution to obtain sodium hydroxide, chlorine and hydrogen; and
and reacting the chlorine with hydrogen to obtain the hydrogen chloride gas.
3. The method for extracting lithium according to claim 1, wherein 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 per 1mol of lithium ions are introduced based on a molar ratio of lithium ions in the lithium-loaded organic phase.
4. The method for extracting lithium according to claim 3, wherein the pressure is 2MPa or less 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 4:1-15:1.
5. The method of extracting lithium according to claim 2, wherein the step of separating a lithium-containing compound from the strip liquor comprises: and mixing the strip liquor with sodium carbonate to obtain a lithium-containing compound, wherein the lithium-containing compound is lithium carbonate.
6. The method for extracting lithium according to claim 5, wherein the temperature is 70 ℃ to 90 ℃ when the strip liquor is mixed with sodium carbonate.
7. The method of extracting lithium according to claim 2, wherein the step of separating a lithium-containing compound from the strip liquor comprises: mixing carbon dioxide, the back extraction liquid and the sodium hydroxide, and performing a 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 according to claim 7, wherein the newly generated carbon dioxide is obtained when the strip solution, the sodium hydroxide and the carbon dioxide are mixed and heated for reaction.
9. The method of claim 8, wherein the newly generated carbon dioxide is recycled for mixing with the strip liquor, the sodium hydroxide and performing the heating reaction.
10. The method according to claim 5 or 7, wherein sodium chloride is also obtained in the step of separating the lithium-containing compound from the strip liquor.
11. The method for extracting lithium according to claim 10, wherein the sodium chloride is recycled for use in preparing the hydrogen chloride gas.
12. The method of extracting lithium according to claim 1, wherein the step of separating a lithium-containing compound from the strip liquor comprises: and controlling the temperature of the back extraction liquid to be 20-50 ℃, and cooling the back extraction liquid to obtain the lithium-containing compound, wherein the temperature difference of cooling is 10-40 ℃, and the lithium-containing compound is lithium chloride.
13. The method for extracting lithium according to claim 2, wherein the method for preparing the lithium-loaded organic phase comprises:
providing a lithium-containing solution;
and mixing the lithium-containing solution with the extract, and extracting and phase-separating to obtain the lithium-loaded organic phase.
14. The method for extracting lithium according to claim 13, wherein the lithium-containing solution further contains at least one of magnesium ions and calcium ions,
the lithium-containing solution is further mixed with an alkaline substance to obtain a precipitate, before the step of mixing the lithium-containing solution with the extract.
15. The method of extracting lithium of claim 14, wherein the alkaline substance comprises the sodium hydroxide.
16. The method of claim 14, further comprising mixing the precipitate with the hydrogen chloride gas and water after the precipitate is obtained, and reacting to obtain a mixed solution.
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 1 or more, and the time of each extraction is 1-10 minutes.
18. The method for extracting lithium according to claim 13, wherein the extraction liquid comprises an extractant and a diluent, the extractant is a hydrophobic liquid, comprising trioxythiophene oxide, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione, 1, 2-pentafluoro-6, 6-dimethyl-3, 5-heptanedione 1,2, 3-heptafluoro-7, 7-dimethyl-4, 6-octanedione, benzoyl trifluoroacetone, 1-phenyl-1, 3-butanedione, 1-benzoyl-2-nonanone trialkyl phosphates, trialkyl phosphine oxides, trioctyl phosphine oxides, trihexyl phosphine oxides, dialkyl phosphates, methyl isobutyl ketone, 1-phenylazo-2-naphthol, n-octanol, isooctanol, 2-ethylhexanol, 14-crown-4 ether butyl phosphonate dibutyl, dibutyl phosphate, Methylene tetrabutyl bisphosphate, trioctylamine oxide, 1, 10-phenanthroline and quaternary ammonium salt N 263 At least one of dimethyl di (N-octadecyl) ammonium chloride, methyl dioctylsulfonium chloride and 1-hydroxyethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide.
19. The method according to claim 13, wherein after separating the lithium-containing compound from the strip liquor, a lithium-precipitating mother liquor is also obtained, which is circulated and mixed with the lithium-containing solution.
20. The method according to claim 13, wherein in the step of continuously introducing hydrogen chloride gas and water into the lithium-loaded organic phase while mixing with the lithium-loaded organic phase, back extraction and phase separation are performed to obtain a back extraction solution containing lithium chloride, a no-load extraction solution is also obtained;
the unloaded extraction liquid is recycled and is used for mixing with the extraction liquid, extracting and phase-separating to obtain the organic phase loaded with lithium;
and/or continuously introducing hydrogen chloride gas and water into the organic phase loaded with lithium, mixing the hydrogen chloride gas and the water with the organic phase loaded with lithium, carrying out back extraction and phase separation, and carrying out back extraction and phase separation by mixing part of the back extraction liquid with the organic phase loaded with lithium, the hydrogen chloride gas and the water in the step of obtaining the back extraction liquid containing lithium.
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