CN116356142A - Bipyridyl extractant, preparation method thereof and application of bipyridyl extractant as nickel-cobalt extractant - Google Patents
Bipyridyl extractant, preparation method thereof and application of bipyridyl extractant as nickel-cobalt extractant Download PDFInfo
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- CN116356142A CN116356142A CN202310192475.4A CN202310192475A CN116356142A CN 116356142 A CN116356142 A CN 116356142A CN 202310192475 A CN202310192475 A CN 202310192475A CN 116356142 A CN116356142 A CN 116356142A
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- Prior art keywords
- extractant
- bipyridyl
- nickel
- cobalt
- extraction
- Prior art date
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 106
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 253
- 238000000605 extraction Methods 0.000 claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 76
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 43
- 239000010941 cobalt Substances 0.000 claims abstract description 43
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 primary amine compound Chemical class 0.000 claims abstract description 18
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical compound Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000012074 organic phase Substances 0.000 claims description 43
- 238000000926 separation method Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 29
- 229910001453 nickel ion Inorganic materials 0.000 claims description 27
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 22
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 claims description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 230000002195 synergetic effect Effects 0.000 abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000284 extract Substances 0.000 abstract description 16
- 230000000536 complexating effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 230000000269 nucleophilic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 59
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 21
- 125000004433 nitrogen atom Chemical group N* 0.000 description 21
- 239000008346 aqueous phase Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 15
- 229910001710 laterite Inorganic materials 0.000 description 14
- 239000011504 laterite Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- 238000005191 phase separation Methods 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 9
- 238000009854 hydrometallurgy Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000003512 tertiary amines Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000013522 chelant Substances 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000004993 emission spectroscopy Methods 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000005595 deprotonation Effects 0.000 description 5
- 238000010537 deprotonation reaction Methods 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 125000004076 pyridyl group Chemical group 0.000 description 5
- 239000010926 waste battery Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000009920 chelation Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical group CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RVRHBLSINNOLPI-UHFFFAOYSA-N Lythridin Natural products COc1ccc(cc1OC)C2CC(CC3CCCCN23)OC(=O)CC(O)c4ccc(O)cc4 RVRHBLSINNOLPI-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
- C22B3/362—Heterocyclic compounds of a single type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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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- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a bipyridyl extractant, a preparation method thereof and application thereof as a nickel-cobalt extractant. The bipyridyl extractant has the following structure:
wherein R is C 12 ～C 25 Alkyl of (a); the preparation method comprises nucleophilic extraction of chloromethyl pyridine hydrochloride and primary amine compound through bilayerThe bipyridyl extractant is obtained by substitution reaction, has stable physical and chemical properties, large saturation capacity and good oil solubility of an extract, has good coordination complexing capability on nickel (cobalt) ions, can form a synergistic extraction system with DNNSA or P204 to selectively extract and separate nickel and cobalt in a complex metal ion solution system, can also be used as a single extraction system to efficiently extract and separate nickel and cobalt in a hydrochloric acid system, and has good industrial application prospect.
Description
Technical Field
The invention relates to a bipyridyl extractant, a preparation method of the bipyridyl extractant and application of the bipyridyl extractant in selective extraction and separation of nickel and cobalt, and belongs to the technical field of hydrometallurgy.
Background
Lithium ion batteries play a critical role in achieving a worldwide sustainable development goal, and therefore, their production and consumption have increased significantly in recent years. As a key raw material for battery anodes, the demand for high purity Ni (II) and Co (II) products (> 99.99%) is also increasing. Currently, high purity Ni (II) and Co (II) products are produced mainly by hydrometallurgical processes of laterite nickel ores. However, in view of the life of lithium ion batteries being about 10 years, the number of waste batteries will increase significantly over time. Therefore, it is important to recycle the waste batteries as secondary resources to avoid environmental pollution and resource waste caused by Ni (II) and Co (II) in the waste batteries. However, the bottleneck problem of preparing high purity Ni (II) and Co (II) products using laterite-nickel ore and secondary resources as raw materials is mainly the efficient low-cost separation of nickel, cobalt from metal impurities, and nickel from cobalt:
1. because the laterite-nickel ore and secondary resources have low grade and complex components, the hydrometallurgical process with low energy consumption and high recovery rate is a main method for extracting Ni (II) in the laterite-nickel ore and secondary resources. However, prior to solvent extraction, neutralization, precipitation and solid-liquid separation processes are generally employed to remove Fe (III) and Al (III) from laterite-nickel ore leachate and secondary resources, directly increasing acid-base consumption and production costs. In addition, the loss rate of Ni (II) and Co (II) in the neutralization and precipitation process is higher. Even after removal of Fe (III) and Al (III) from the filtrate, further precipitation, solid-liquid separation, secondary leaching and multistage extraction are required to separate Ni (ii), co (ii) and Ca (ii), mg (ii), mn (ii) and Zn (ii). Thereby bringing the problems of long process flow, high energy consumption, industrial wastewater production, high production cost and the like. To overcome these problems, many researchers have been struggling to find extractants and extraction systems that can selectively extract Ni (II) and Co (II) from laterite nickel ores and secondary resource leachates. Because the N atom has excellent coordination performance to Ni (II) and Co (II), the LIX solvent extractant and the pyridine derivative extractant can form an extract by combining the N atom with Ni (II) and Co (II). Thus, a variety of LIX-type extractants and pyridine-type derivative extractants were synthesized and tested. Representative extractants are: LIX63, DH2,3,4PIA, 3PC10,3PC-PrCl and 2,3,4PC. However, these extractants containing oxime groups (-c=noh) are susceptible to degradation in the presence of organic acids. Therefore, when the extractant and the acid extractant are used as a synergistic extraction system, the decomposition of the extractant is unavoidable, and the application range of the extractant is greatly limited. Thus, pyridine carboxylic acid ester extractants such as 2,3,4PC are of great interest because they can form synergistic extraction systems with acidic extractants. However, the widely used hydrochloric or sulfuric acid in the washing and stripping processes inevitably breaks down the ester bonds (-COOR) in the 2,3,4PC molecular structure, resulting in 2,3,4PC degradation, significantly reducing the cycle performance of 2,3,4PC. In addition, 2,3,4PC has insufficient selectivity to Ni (II) and Co (II), can not achieve the purpose of deep purification, and greatly limits the industrial application of the catalyst. Therefore, the design and synthesis of a high-efficiency stable nickel and cobalt extractant is urgently needed to solve the bottleneck problem faced in the existing laterite nickel ore and secondary resource hydrometallurgical process.
2. Since the ionic radii, oxidation states and coordination numbers of Ni (II) and Co (II) are similar, they cannot be separated in a clean and efficient manner. Currently, solvent extraction is a common method for separating Ni (II) and Co (II). Most previous studies on the extraction and separation of Ni (II) and Co (II) have been performed with organophosphorus extractants in acidic sulfate media and amine extractants in high concentration hydrochloric acid solutions. Cyanex 272, D2EHPA and PC-88A are commonly used organophosphorus extractants. However, the separation coefficient of Ni (II) and Co (II) is not more than 10, whether PC-88A, cyanex 272 or D2EHPA is used. In addition, the organophosphorus extractant needs to be saponified to improve the utilization of the extractant, and the high pH of the Ni (II) -Co (II) solution must be maintained during the extraction process. High concentrations of hydrochloric or sulfuric acid are also required in the stripping process. Thus, the extraction system has many disadvantages such as high consumption of acid and alkali, long extraction flow, and difficulty in recovering the extractant due to saponification of the organophosphorus extractant. As for the amine extractant, at least 5mol/L hydrochloric acid is needed in the solution to selectively separate Ni (II) and Co (II), because Co (II) forms a negatively charged cobalt chloride complex at high acidity and forms ion pairs with the cations of the amine extractant at the membrane solution interface. Thus, the extraction process consumes a large amount of hydrochloric acid and a large amount of alkaline stripping agent is consumed in the stripping process to regenerate the amine extractant. Although this process can effectively separate Ni (II) and Co (II), it has not been widely used because of severe corrosion of high concentration hydrochloric acid to extraction equipment, resulting in severe production conditions. In addition, most lithium ion batteries contain 15 to 30% Co (II) and 10% Ni (II), while laterite nickel ores contain 1.5 to 1.8% Ni (II) and 0.02 to 0.1% Co (II). At present, co (II) and Ni (II) are separated mainly by preferential extraction of Co (II), while Ni (II) remains in the raffinate. Although this method is suitable for laterite nickel ore, it is obviously unsuitable for waste batteries in view of extraction cost and extraction efficiency. However, single extractant systems that selectively extract Ni (II) from Ni (II) -Co (II) solutions have not been successfully developed.
Thus, the current separation of Ni (II), co (II) from metallic impurities and the separation of Ni (II), co (II) cannot be achieved in a low-cost, clean and efficient manner, especially with waste batteries and laterite-nickel ores as raw materials. Therefore, it is important to develop new extractants and breakthrough methods to efficiently separate Ni (II), co (II) and metal ion impurities and to achieve efficient separation of Ni (II) and Co (II).
Disclosure of Invention
Aiming at the technical defects that the prior method for recovering valuable metals in laterite-nickel ores and waste lithium ion batteries in the hydrometallurgical process has complex process flow, low recovery rate of nickel and cobalt, difficult separation of nickel and cobalt and the like.
The first object of the invention is to provide a bipyridyl extractant which has stable physicochemical property, large saturation capacity, good oil solubility of an extract and good coordination complexing ability for nickel (cobalt) ions.
The second purpose of the invention is to provide a preparation method of the bipyridyl extractant, which has the advantages of cheap and easily available raw materials, simple synthesis process, convenient operation, high yield and the like, and is beneficial to mass production.
A third object of the present invention is to provide the use of a bipyridyl extractant which can be used as a single extraction system or as a synergistic extraction system with P204 or DNNSA compositions. The dual-pyridyl extractant and DNNSA form a synergistic extraction system, which has a strong positive synergistic extraction effect on nickel and cobalt ions in complex metal ion solution systems containing nickel, cobalt, iron, aluminum, calcium, magnesium, manganese, zinc and the like, has an obvious reverse synergistic extraction effect on other metal ions, remarkably improves the separation coefficient between nickel, cobalt and other metal ions, is very suitable for the extraction and separation of nickel, cobalt and iron, aluminum, calcium, magnesium, manganese and zinc in laterite-nickel ore pickle liquor, and has a higher application prospect for the separation and recovery of valuable metals in laterite-nickel ore. Or, the dual-pyridyl extractant and P204 form a synergistic extraction system, which has a strong positive synergistic extraction effect on nickel and cobalt ions in complex metal ion solution systems containing nickel, cobalt, aluminum, calcium, magnesium, manganese, zinc and the like, and has an obvious reverse synergistic extraction effect on other metal ions, so that the separation coefficient between the nickel, cobalt and other metal ions is obviously improved, and the separation of nickel, cobalt, aluminum, calcium, magnesium, manganese and zinc in laterite-nickel ore pickle liquor can be realized by an extraction method after conventional iron removal is performed. Or taking the bipyridine-based extractant as a single extraction system, based on the strong coordination capability of the bipyridine-based extractant on nickel and cobalt, and Ni (II) -Co (II) solutions with different chloride ion concentrations and different pH values exist in different easy-to-extract forms, and the Ni (II) and Co (II) efficient separation is realized by utilizing the difference of association forms of nickel and cobalt ions. The method can selectively extract nickel and cobalt, and can remarkably shorten the extraction process flow by selectively extracting nickel or cobalt with low Ni (II) -Co (II) solution content, so that the method has a high application prospect in separation and recovery of nickel and cobalt.
In order to achieve the technical purpose, the invention provides a bipyridyl extractant, which has a structure shown in a formula 1:
wherein R is C 12 ～C 25 Is a hydrocarbon group.
The bipyridyl extractant provided by the invention has a unique molecular structure, takes tertiary amine as a molecular main body, and has two symmetrical pyridine groups and long-chain alkyl. The long-chain alkyl imparts good oil solubility and hydrophobicity to the whole extractant molecule, can improve the phase separation capability, has flexibility, can improve the solubility and dispersibility in organic solvents, and has coordination effect on nickel cobalt metal ions, especially when two symmetrical pyridine groups are introduced, a pair of chelating groups can be formed, and a stable chelating ring structure can be formed with nickel cobalt metal ions, so that the binding capability and selectivity of the long-chain alkyl to nickel cobalt metal ions are improved. In addition, the complexing ability of pyridine groups at different substitution positions on nickel cobalt metal ions is different, the pyridine groups are introduced in a 2-methyl pyridine form, electron donating groups are arranged at the 2-positions of the pyridine groups, the complexing ability of N atom lone pair electrons on pyridine on the nickel cobalt metal ions can be improved, meanwhile, a methylene capable of twisting exists between the two pyridine groups, and the two pyridine groups are symmetrically distributed and are easy to chelate the nickel cobalt metal ions to form a stable chelate ring structure, so that the selective complexing ability and saturation capacity of the bipyridine extractant on the nickel cobalt metal ions are greatly improved.
As a preferred embodiment, R in the bipyridyl extractant is C 12 ～C 25 Straight-chain alkyl or C 12 ～C 25 Branched alkanes of (2). Specifically, examples thereof include straight-chain alkyl groups such as n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl, and branched-chain alkyl groups such as isotetradecyl and isohexadecyl. The length of the alkyl chain affects its lipophilicity as well as hydrophobicity, and affects its extraction phase separation ability. Further preferably C 14 ～C 18 An alkyl group.
The invention also provides a preparation method of the bipyridyl extractant, which comprises the steps of carrying out a bimolecular nucleophilic substitution reaction on chloromethylpyridine hydrochloride and a primary amine compound with a structure shown in a formula 2 to obtain the bipyridyl extractant;
RNH 2
2, 2
Wherein R is C 12 ～C 25 Is a hydrocarbon group.
The invention takes commercial 2-chloromethylpyridine hydrochloride and primary amine as raw materials, and synthesizes the raw materials through one-step bimolecular nucleophilic substitution reaction, and the method has the advantages of simplicity, short steps, mild condition and easily obtained raw materials, and is beneficial to industrial production.
As a preferred embodiment, the molar ratio of chloromethylpyridine hydrochloride to primary amine compound is (2-2.2): 1.
As a preferred embodiment, the conditions for the nucleophilic substitution reaction of the bilayer are: under the action of alkali, the reaction is carried out for 48 to 60 hours at the temperature of 60 to 90 ℃. Bimolecular nucleophilic substitution reactions employ a base, such as potassium carbonate, as a neutralizing agent to facilitate the reaction. The bimolecular nucleophilic substitution reaction adopts at least one of acetonitrile, dimethylbenzene and methanol as a solvent, and the solvent dosage is 100-300% of the tertiary amine compound mass. Under the preferred reaction conditions, the reaction can be ensured to have higher yield.
The specific preparation method of the bipyridyl extractant provided by the invention (the following is a typical synthesis method of the bipyridyl extractant): to a round bottom flask was first added 2-chloromethylpyridine hydrochloride (2 mol,328.06 g) and acetonitrile and heated with stirring in an oil bath at 80 ℃. After 2- (chloromethyl) pyridine hydrochloride was completely dissolved in acetonitrile, potassium carbonate solution (2.4 mol,331.2 g) was added dropwise, tetradecylamine (0.9 mol,192.02 g) in a molten state was further added, and after stirring and refluxing at 90℃for 2 days, the reaction solution was filtered and the aqueous phase was separated by a separating funnel, and acetonitrile was removed by rotary evaporation at 85℃from the organic phase. Then, the oily complex was washed three times with ultrapure water to remove unreacted 2-chloromethylpyridine hydrochloride, and then dried with anhydrous sodium sulfate. The yield of the dark brown oily complex finally obtained is 90% and the purity exceeds 95%.
The synthesis process of the bipyridyl extractant mainly comprises a bimolecular nucleophilic substitution reaction, and the specific reaction formula is as follows (the description is given by taking decamine and 2-chloromethylpyridine hydrochloride as examples):
the invention also provides application of the bipyridyl extractant, which is applied as a nickel extractant and/or a cobalt extractant. The bipyridyl extractant has selective coordination or chelation on nickel ions and cobalt ions, has good solubility and dispersibility in an oil phase, and is particularly suitable for being used as a nickel-cobalt extractant.
As a preferred scheme, the bipyridyl extractant is applied to the separation of nickel and cobalt from other metal ions in a complex metal ion solution system or the separation of nickel ions and cobalt ions in a nickel cobalt solution system.
As a preferred embodiment, the bipyridyl extractant is used alone, or in combination with DNNSA, or in combination with P204.
As a preferable scheme, the bipyridyl extractant is independently applied to the separation of nickel ions and cobalt ions in a nickel-cobalt solution system, the concentration of the bipyridyl extractant in an organic phase is 0.1-0.4 mol/L, and the extraction conditions are as follows: the pH value is 0-6, the temperature is 15-40 ℃, and the chloride ion concentration in the nickel-cobalt solution system is 1-4 mol/L. The nickel cobalt solution system is a hydrochloric acid solution system, which contains nickel ions and cobalt ions. Sources of nickel and cobalt ion solution systems such as laterite nickel ores and spent batteries are hydrometallurgical purified nickel cobalt solutions. Based on the strong complexing ability of the bipyridyl extractant for Ni (II) and Co (II), and the existence of Ni (II) and Co (II) in different forms easy to extract in Ni (II) -Co (II) solutions with different chloride ion concentrations and different pH values, the bipyridyl extractant is not only suitable for selectively extracting Co (II) but also suitable for selectively extracting Ni (II) from Ni (II) -Co (II) solutions by utilizing the difference of association forms of nickel ions and cobalt ions. Experimental results prove that the separation coefficient of the bipyridine extractant on Ni (II) and Co (II) is obviously higher than that of the organophosphorus extractant and the amine extractant. In addition, the deionized water can achieve high stripping rate, and the deionized water can avoid the problem of degradation of the extractant caused by contact with acid or alkali in the stripping process. Therefore, the whole extraction-back extraction process greatly reduces the production cost, furthest reduces the influence on the environment, reduces the consumption of acid and alkali, and has good cycle performance. Further preferred pH is 0 to 2 to effect selective extraction of nickel, and pH is 5 to 6 to effect selective extraction of nickel.
As a preferred scheme, the bipyridyl extractant and DNNSA are applied in conjunction to separate nickel and cobalt from other metal ions in a complex metal ion solution system comprising nickel and/or cobalt and at least one of iron, aluminum, calcium, magnesium, zinc and manganese; the extraction conditions are as follows: the pH value is 0.25-2.5, and the temperature is 15-40 ℃; the concentration of the bipyridyl extractant in the organic phase is 0.1-0.4 mol/L; the molar ratio of the bipyridyl extractant to DNNSA is 1:1 to 4. Based on the strong coordination ability of the bipyridine extractant to Ni (II) and Co (II) and the low extraction ability of DNNSA to Fe (III), the DNNSA-bipyridine extractant is used as a synergistic extraction system, and Ni (II) and Co (II) can be directly extracted from Fe (III), al (III), ca (II), mg (II), mn (II) and Zn (II). The bipyridyl extractant and DNNSA form a synergistic extraction system according to a proper proportion, so that the complexation selectivity of nickel ions and cobalt ions, especially nickel ions, in the complex metal ion solution can be remarkably improved. With the increase of the proportion of bipyridyl extractant in the organic phase, the extraction capacity of the extractant to nickel ions and cobalt ions is further increased, the extraction rate of other metal ions is basically unchanged, and the separation effect is also better and better. The molar ratio of the bipyridyl extractant to DNNSA is 1:1-4; further preferably 1:2 to 4. Under the preferable condition, the coordination and chelation of the complex extractant to nickel ions and cobalt ions in the complex metal ion solution system can be improved, and the phase separation time is shortened, so that the extraction and separation efficiency is improved. Sources of complex metal ion solution systems such as sulfuric acid leach solutions of laterite nickel ores.
As a preferred embodiment, the bipyridyl extractant is used in conjunction with P204 for the separation of nickel and cobalt from other metal ions in a complex metal ion solution system comprising nickel and/or cobalt and at least one of aluminum, calcium, magnesium, zinc and manganese; the extraction conditions are as follows: the pH value is 0.25-2.5, and the temperature is 15-40 ℃; the concentration of the bipyridyl extractant in the organic phase is 0.1-0.4 mol/L; the molar ratio of the bipyridyl extractant to P204 is 1:1 to 4. The dual-pyridyl extractant and P204 form a synergistic extraction system, which has a very strong positive synergistic extraction effect on nickel and cobalt ions in complex metal ion solution systems containing nickel, cobalt, aluminum, calcium, magnesium, manganese, zinc and the like, has an obvious reverse synergistic extraction effect on other metal ions, remarkably improves the separation coefficient between nickel, cobalt and other metal ions, and has a higher application prospect in separating and recycling valuable metals in laterite nickel ores after conventional iron removal is performed on laterite nickel ore pickle liquor.
The organic phase related by the invention also contains a polar modifier and a diluent; the polar modifier is at least one of isooctyl alcohol, TBP, sec-octyl alcohol and n-octyl alcohol, and occupies 5-40% of the volume of the organic phase. The diluent in the organic phase is at least one of sulfonated kerosene, higher alcohol and n-heptane.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The bipyridyl extractant provided by the technical scheme of the invention is synthesized by taking amine compounds and 2-chloromethylpyridine as raw materials through a bilayer nucleophilic substitution reaction and a one-step classical reaction, has the advantages of short synthesis flow, simplicity in operation, environment friendliness, low production cost, high product yield and the like, and is convenient for large-scale production.
2) The bipyridyl extractant provided by the technical scheme of the invention takes the long-chain amine compound structure as a molecular main body, can ensure that the extractant has good oil solubility and hydrophobicity, has stable physical and chemical properties under the extraction process condition, has good metal ion complexing capacity, and has good application prospects in the fields of organic synthesis, hydrometallurgy and the like.
3) According to the bipyridyl extractant provided by the technical scheme of the invention, two pyridine groups or a pair of chelate groups are connected to primary amine formed by the nucleophilic addition reaction of the bilayer, and the coordination and chelation capability of the bipyridyl extractant to nickel ions and cobalt ions can be improved by utilizing the selective coordination and complexation of the ligand groups or the chelate groups and the nickel ions and cobalt ions.
4) The bipyridyl extractant and DNNSA provided by the technical scheme of the invention are cooperated to serve as the transition metal nickel cobalt extractant, and belong to an acidic-neutral mixed synergic extraction system. The bipyridyl extractant can coordinate or chelate nickel and cobalt, and nitrogen atoms coordinated with metal ions in pyridine functional groups belong to boundary alkali, so that the bipyridyl extractant has good complexation with nickel ions and cobalt ions of boundary acid according to the rule of soft and hard acid alkali, and in addition, N atoms in a carbon chain of the bipyridyl extractant can increase the electron density of N atoms in the pyridine groups, so that the coordination capacity with Ni (II) and Co (II) is enhanced. Thus, bipyridyl extractants have a large electrostatic interaction. The position of the N atom on the pyridine ring has a larger influence on the selectivity of the extractant, and when the N atom on the pyridine ring is in the ortho position, the steric hindrance of the extractant is larger than that when the N atom on the pyridine ring is in the para position. Therefore, the ortho bipyridyl extractant may have larger steric hindrance, and thus the selectivity to Ni (II) and Co (II) can be improved. In addition, two pyridine groups in the bipyridyl extractant can form eight-membered chelate rings with Ni (II) and Co (II). Thus, the bipyridyl extractant forms an extract that is more stable due to chelation. The DNNSA is a sulfonic acid extractant, the structure of which is shown in the formula 3, and the DNNSA has the main functions of improving the extraction capacity of a synergistic extraction system and reducing the extraction rate of iron. Therefore, the synergistic extraction system composed of the bipyridyl extractant and DNNSA has very good selectivity and strong extraction capacity for nickel ions and cobalt ions.
5) The double-pyridyl extractant and DNNSA are cooperatively matched to serve as the extractant of nickel ions and cobalt metal ions, the extraction process is carried out at room temperature, the phase separation performance of the extraction process is good, the oil-water interface is clear, the phase separation time is short, and the high-efficiency separation of nickel and cobalt from iron, aluminum, calcium, magnesium, manganese and zinc in the laterite-nickel ore sulfuric acid leaching solution can be realized.
6) The bipyridyl extractant provided by the technical scheme of the invention is cooperated with P204 to serve as the extractant of transition metal nickel cobalt, and belongs to an acidic-neutral mixed type cooperated extraction system. The bipyridyl extractant can coordinate or chelate nickel ions and cobalt ions. P204 is phosphoric acid extractant, and the structure is shown in formula 4, and the main function of P204 is to improve the extraction capacity of the synergistic extraction system. Therefore, the synergistic extraction system consisting of the bipyridyl extractant and P204 has very good selectivity and strong extraction capacity for nickel ions and cobalt ions.
7) The bipyridyl extractant and P204 provided by the technical scheme of the invention are cooperatively matched to serve as the extractant of nickel and cobalt metal ions, the extraction process is carried out at room temperature, the phase separation performance of the extraction process is good, the oil-water interface is clear, the phase separation time is short, and the high-efficiency separation of nickel, cobalt, aluminum, calcium, magnesium, manganese and zinc in the laterite-nickel ore sulfuric acid leaching solution after deironing can be realized.
8) The technical scheme of the invention is based on the strong coordination capability of bipyridine extractant to nickel and cobalt, and Ni (II) -Co (II) solutions with different chloride ion concentrations and different pH values exist in different easy-to-extract forms, and the Ni (II) and Co (II) are efficiently separated by utilizing the difference of nickel and cobalt ion association forms. The method can selectively extract nickel and cobalt.
9) The bipyridyl extractant provided by the technical scheme of the invention is used as an extractant for separating nickel ions from cobalt ions, the extraction process is carried out at room temperature, the phase separation performance of the extraction process is good, the oil-water interface is clear, the phase separation time is short, and the high-efficiency separation of nickel and cobalt in laterite nickel ore and sulfuric acid or hydrochloric acid leaching solution of secondary resources can be realized.
Drawings
FIG. 1 is a High Resolution Mass Spectrum (HRMS) plot of the bipyridyl extractant of example 1.
FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of the bipyridyl extractant of example 1 1 H-NMR)。
Fig. 3 shows DNNSA in example 2: the molar ratio of the bipyridyl extractant is 2:1 influence on Ni (II), co (II), fe (III), al (III), mg (II), zn (II) and Mn (II) extraction efficiency.
Fig. 4 shows DNNSA in example 3: the molar ratio of the bipyridyl extractant is 2:1.5 influence on Ni (II), co (II), fe (III), al (III), mg (II), zn (II) and Mn (II) extraction efficiency.
Fig. 5 shows DNNSA in example 4: the molar ratio of the bipyridyl extractant is 2:2 influence on Ni (II), co (II), fe (III), al (III), mg (II), zn (II) and Mn (II) extraction efficiency.
FIG. 6 is a graph of the Co (II) and Ni (II) extraction saturation curves and the McCabe-Thiele plot thereof in example 4.
FIG. 7 shows the concentration of chloride ions in example 5Effect on the extraction process (ph=6, temperature=20 ℃, O/a ratio=1:1, extraction time=10 minutes), (b) effect of pH on the extraction process (2 mol/L Cl - Temperature=20 ℃, O/a ratio=1:1, extraction time=10 minutes), (c) [ CoCl x ] 2-x The mole fraction of (c) is related to the chloride ion concentration. (c) [ CoCl ] x ] 2-x Molar fraction and chloride concentration ([ Co (II))] T ＝9g/L，logK 1 ＝-1.05，logK 2 ＝-2.69，logK 3 ＝-1.54，log K 4 -1.34. Chloride concentration [ Ni (II)] T ＝9g/L，log K 1 Effect of (e) extraction time on Co (II) extraction process (2 mol/L Cl) - Ph=6, temperature=20 ℃, O/a ratio=1:1). (f) Effect of extraction time on Ni (II) extraction procedure (2 mol/L Cl) - Ph=0, temperature=20 ℃, O/a ratio=1:1).
FIG. 8 is a comparison of the extraction behavior of bipyridyl extractant (NNPA) at pH <2 and pH >2 in example 5.
FIG. 9 is a graph showing the separation coefficient of bipyridyl extractant (NNPA) from Ni (II) and Co (II) for different extraction systems in example 5.
FIG. 10 is a view showing the McCabe-Thiele diagram showing the saturation curves of Co (II) (a) and Ni (II) (b) in example 6.
Fig. 11 is a diagram showing P204 in example 7: the molar ratio of the bipyridyl extractant is 2:2 influence on Ni (II), co (II), al (III), mg (II), zn (II) and Mn (II) extraction efficiency.
Detailed Description
The invention will be further illustrated by the following detailed description for a better understanding of the invention, but the examples set forth are not intended to limit the scope of the invention.
Example 1
Preparation of bipyridyl extractant:
to a round bottom flask was first added 2-chloromethylpyridine hydrochloride (2 mol,328.06 g) and 300mL acetonitrile and heated with stirring in an oil bath at 80 ℃. After 2- (chloromethyl) pyridine hydrochloride was completely dissolved in acetonitrile, potassium carbonate solution (2.4 mol,331.2 g) was added dropwise, followed by meltingTetradecylamine (0.9 mol,192.02 g) in a molten state was refluxed with stirring at 90℃for 2 days, and after the reaction solution was filtered and the aqueous phase was separated by a separating funnel, acetonitrile was removed by rotary evaporation of the organic phase at 85 ℃. Then, the oily complex was washed three times with ultrapure water to remove unreacted 2-chloromethylpyridine hydrochloride, and then dried with anhydrous sodium sulfate. The yield of the dark brown oily complex finally obtained is 90% and the purity exceeds 95%. The High Resolution Mass Spectrum (HRMS) diagram of the bipyridine extractant is shown in figure 1, and the nuclear magnetic resonance hydrogen spectrum of the bipyridine extractant is shown in the specification 1 H-NMR) chart is shown in FIG. 2.
Example 2
The configuration contains 3 g.L -1 Ni(II),0.3g·L -1 Co(II),3g·L -1 Fe(III),3g·L -1 Al(III),0.2g·L -1 Ca(II),1g·L -1 Mg(II),0.86g·L -1 Zn (II), and 0.4 g.L -1 20mL of sulfuric acid leaching solution of Mn (II) simulated laterite-nickel ore is used as a water phase to be extracted, and 2mol/L sulfuric acid and 1mol/L sodium hydroxide are used for dissolving and adjusting the initial pH of the feed liquid. Preparing an organic phase, wherein the organic phase contains DNNSA 0.2mol/L, bipyridyl extractant 0.1mol/L, diluent is sulfonated kerosene, polar modifier is isooctyl alcohol with the volume ratio of 30%, and the ratio (O/A) is 1:1, adjusting the extraction balance pH by saponifying the organic phase with 10mol/L sodium hydroxide solution. Adding the aqueous phase into the organic phase, oscillating in water bath at room temperature of 25deg.C for 10min, standing for layering, separating phase, and measuring metal ion concentration in the extractive solution by inductively coupled plasma emission spectrometry (ICP-OES), wherein the metal ion concentration in the organic phase is obtained by differential method.
As shown in fig. 3, as the equilibrium pH increases, the extraction efficiency of Ni (II) and Co (II) increases slowly, while the extraction efficiency of Fe (III), al (III), ca (II), mg (II), zn (II), and Mn (II) decreases significantly after a slight increase. However, the extraction rate of Co (II) is low, and the aqueous phase still contains more Co (II), and the aqueous phase needs further extraction treatment.
Example 3
The configuration contains 3 g.L -1 Ni(II),0.3g·L -1 Co(II),3g·L -1 Fe(III),3g·L -1 Al(III),0.2g·L -1 Ca(II),1g·L -1 Mg(II),0.86g·L -1 Zn (II), and0.4g·L -1 20mL of sulfuric acid leaching solution of Mn (II) simulated laterite-nickel ore is used as a water phase to be extracted, and 2mol/L sulfuric acid and 1mol/L sodium hydroxide are used for dissolving and adjusting the initial pH of the feed liquid. Preparing an organic phase, wherein the organic phase contains DNNSA 0.2mol/L, bipyridyl extractant 0.15mol/L, diluent is sulfonated kerosene, polar modifier is isooctyl alcohol with the volume ratio of 30%, and the ratio (O/A) is 1:1, adjusting the extraction balance pH by saponifying the organic phase with 10mol/L sodium hydroxide solution. Adding the aqueous phase into the organic phase, oscillating in water bath at room temperature of 25deg.C for 10min, standing for layering, separating phase, and measuring metal ion concentration in the extractive solution by inductively coupled plasma emission spectrometry (ICP-OES), wherein the metal ion concentration in the organic phase is obtained by differential method.
As shown in fig. 4, as the equilibrium pH increases, the extraction efficiency of Ni (II), co (II), and Zn (II) increases slowly, while the extraction efficiency of Fe (III), al (III), ca (II), mg (II), and Mn (II) decreases significantly after a slight increase. The extraction rate of Ni (II) is not significantly increased compared with that of example 2, but the extraction rate of Co (II) is increased, but the extraction rate of Co (II) is lower at this time, and more Co (II) is still contained in the aqueous phase, and the aqueous phase needs further extraction treatment.
Example 4
The configuration contains 3 g.L -1 Ni(II),0.3g·L -1 Co(II),3g·L -1 Fe(III),3g·L -1 Al(III),0.2g·L -1 Ca(II),1g·L -1 Mg(II),0.86g·L -1 Zn (II), and 0.4 g.L -1 20mL of sulfuric acid leaching solution of Mn (II) simulated laterite-nickel ore is used as a water phase to be extracted, and 2mol/L sulfuric acid and 1mol/L sodium hydroxide are used for dissolving and adjusting the initial pH of the feed liquid. Preparing an organic phase, wherein the organic phase contains DNNSA 0.2mol/L and bipyridyl extractant 0.2mol/L, the diluent is sulfonated kerosene, the polar modifier is isooctyl alcohol with the volume ratio of 30%, and the ratio (O/A) is 1:1, adjusting the extraction balance pH by saponifying the organic phase with 10mol/L sodium hydroxide solution. Adding the aqueous phase into the organic phase, oscillating in water bath at room temperature of 25deg.C for 10min, standing for layering, separating phase, and measuring metal ion concentration in the extractive solution by inductively coupled plasma emission spectrometry (ICP-OES), wherein the metal ion concentration in the organic phase is obtained by differential method.
As shown in fig. 5, as the equilibrium pH increases, the extraction efficiency of Ni (II), co (II), and Zn (II) increases slowly, while the extraction efficiency of Fe (III), al (III), ca (II), mg (II), and Mn (II) decreases significantly after a slight increase. The extraction rate of Ni (II) is reduced compared with examples 1 and 2, while the extraction rate of Co (II) is greatly improved, but the extraction rates of Ni (II) and Co (II) are lower at the moment, and the aqueous phase still contains more Ni (II) and Co (II), and the aqueous phase needs further extraction treatment. Because the bipyridyl extractant molecule contains two basic pyridine rings, the bipyridyl extractant molecule reacts with the acidic extractant DNNSA to generate a complex, so that the concentration of free DNNSA is reduced, the metal extraction rate is reduced, but the increase of the concentration of the bipyridyl extractant shows good impurity inhibition capability, which is probably caused by the competition effect of excessive bipyridyl extractant and impurity metal on the free DNNSA. Thus in high nickel low cobalt systems, a stronger driving force (higher concentration of bipyridyl extractant) is required to improve cobalt extraction efficiency.
Therefore, a 6-stage cascade extraction process is selected for further extraction and separation of nickel ions and cobalt ions, as shown in fig. 6. As shown in Table 1, after six-stage countercurrent cascade extraction, the impurities are not extracted basically, and the extraction rates of nickel ions and cobalt ions are above 99%. The synergistic extraction system of DNNSA-bipyridyl extractant under similar extraction conditions can realize direct extraction of Ni (II) and Co (II) from sulfuric acid leaching solution of laterite-nickel ore.
Table 1 shows six-stage countercurrent cascade extraction data for 0.2M DNNSA+0.1-0.2M bipyridine extractants to extract nickel and cobalt
Example 5
The configuration contains 9 g.L -1 Ni(II)，9g·L -1 20mL of sulfuric acid leaching solution of simulated laterite-nickel ore and secondary resources of Co (II) purified by hydrometallurgical process is used as water phase to be extracted, 2mol/L sulfuric acid and 1mol/L sodium hydroxide are used for dissolving and adjusting the initial pH value of feed liquid, and sodium chloride is used for adjusting solution chlorineIon concentration. Preparing an organic phase, wherein the organic phase contains 0.3mol/L bipyridyl extractant, the diluent is sulfonated kerosene, the polar modifier is isooctyl alcohol with the volume ratio of 30 percent, and the ratio (O/A) is 1:1. adding the aqueous phase into the organic phase, oscillating in water bath at room temperature of 25deg.C for 10min, standing for layering, separating phase, and measuring metal ion concentration in the extractive solution by inductively coupled plasma emission spectrometry (ICP-OES), wherein the metal ion concentration in the organic phase is obtained by differential method.
As shown in fig. 7 (a), ni (II) and Co (II) exhibit different extraction characteristics as the concentration of chloride ions increases, because Ni (II) and Co (II) form different complexes. FIGS. 7 (c) and 7 (d) depict [ CoCl ] in aqueous phase x ] 2-x And [ NiCl ] x ] 2-x The mole fraction of (c) is related to the chloride ion concentration. As the concentration of chloride ions increases, [ Co (H) 2 O) 6 ] 2 + forms four complexes with mainly chloride ions, [ CoCl ] 1 (H 2 O) 5 ] + ,[CoCl 2 (H 2 O) 4 ],[CoCl 3 (H 2 O) 3 ] - ,[CoCl 4 ] 2- And [ Ni (H) 2 O) 6 ] 2+ Mainly forms a complex, [ NiCl (H) 2 O) 5 ] + . This can be explained by that although Ni (II) and Co (II) both exist in the form of hydrated ions in an aqueous solution, the hydrated ions of Ni (II) are more stable than those of Co (II), and in particular, ni (II) is more difficult to be replaced with chloride ions than water molecules in the inner coordination sphere of Co (II). Because of the exchange rate (K) of Ni (II) with water H2O (s -1 )＝10 6 ) Exchange ratio of Co (II) to water (K) H2O (s -1 )＝10 4 ～10 5 ) An order of magnitude greater. Thus, when the chloride concentration exceeds 1mol/L, co (II) starts to form a four-coordinate structure instead of a six-coordinate structure, while Ni (II) maintains its six-coordinate structure. Co (II) forms a four-coordinate hexahedral coordination structure ([ CoCl) mainly with four chloride ions when the chloride ion concentration in the aqueous solution is 2mol/L 4 ] 2- ) While Ni (II) has mainly two hexacoordinated octahedral coordination structures [ NiCl (H) 2 O) 5 ] + And [ Ni (H) 2 O) 6 ] 2+ . While different forms of Co (II) and Ni (II) lead to the formation of different extracts. Thus, in experiments, it has been observed that Co (II) is preferentially extracted by NNPA. In addition, the high concentration of chloride ions also promotes the extraction of Ni (II), so once Co (II) extraction is complete, NNPA begins to extract Ni (II). Therefore, in order to selectively separate Ni (II) and Co (II), 2mol/L was selected as the optimum concentration of chloride ions for the subsequent experiments.
Both pink cobalt sulfate and light green nickel sulfate were present in the solution, resulting in a brown color of the solution. As shown in fig. 7, the color of the organic and aqueous phases changed significantly with the extraction process. Whereas when Ni (II) or Co (II) is selectively extracted, the colors of the two phases are significantly different. At a pH below 2, the organic phase changes from a reddish wine to a dark green color, while the aqueous phase changes from a brown to a pink color. At a pH above 2, the organic phase changes colour from reddish to dark purple and the aqueous phase changes colour from brown to light green. The dark green and dark purple organic phases represent the extracted Ni (II) complex and the extracted Co (II) complex, respectively. The pale green aqueous phase indicates that only nickel sulfate remains in the aqueous phase, while the pink aqueous phase indicates that Ni (II) is completely extracted into the organic phase.
From the data and experimental plot shown in FIG. 7 (b), it can be seen that Co (II) extraction efficiency increases rapidly and Ni (II) extraction efficiency decreases rapidly as pH increases from 0 to 6 when the concentration of chloride ions in the synthesis feed is 2 mol/L. As shown in fig. 8, since hydrogen ions are bound to the basic sites of bipyridyl extractant (hereinafter, abbreviated as NNPA), at a pH below 2, deprotonation treatment is required before the extraction process, and the extraction behavior of NNPA is mainly divided into deprotonation and extraction process. During deprotonation, ni (II) replaces the hydrogen ion to compete for the lone pair of electrons of the nitrogen atom. During the extraction process, the deprotonated nitrogen atom is complexed with Ni (II). However, ni (II) may replace a hydrogen ion on a pyridyl group, but cannot replace a hydrogen ion bonded to an N atom of a tertiary amine. Since there is a large pi bond in the pyridine group, it has electron-withdrawing effect, while the alkyl group on the tertiary amine has electron-donating effect, resulting in electrons of N atom on the tertiary amineThe cloud density is greater than the N atoms on the pyridine group. Thus, the nature of the N atom on the pyridyl group changes from "strong base" to "interface base", but the nature of the N atom on the tertiary amine remains "strong base". According to SHAB theory, ni (II) and Co (II) belong to the "interface acid" and are therefore more likely to replace protons on pyridyl groups than on tertiary amines. In addition, the N atom (pka=10.76) on the tertiary amine is more basic than the N atom (pka=5.17) on the pyridyl group, so the N atom on the tertiary amine binds hydrogen ions more strongly than the N atom on the pyridyl group. Thus, the tertiary amine on NNPA remains bound to the hydrogen ion ((R) 3NH+) after the deprotonation process. NNPA-H + Can be combined with [ NiCl (H) 2 O) 5 ] + Or [ Ni (H) 2 O) 6 ] 2+ Forming a complex of electroneutral and coordination saturation extraction (NNPANiHCl) 3 And a small portion of NNPANiHCl 3 H 2 O). Whereas NNPA-H + Can not be combined with [ CoCl ] 4 ] 2- Formation of complex of electroneutral and coordination saturation extraction ([ NNPAHCoCl) 2 ] + ). Because only N atoms on the pyridine group can replace Cl in the coordination sphere in Co (II) - While the tertiary amine on NNPA remains with H + And (5) combining.
However, at pH values above 2, the hydrogen ion concentration is too low to bind to the basic sites of NNPA, which results in another extracted Ni (II) complex (NNPANiCl 2 (H 2 O) 2 ) Is formed. Since no deprotonation process is required at pH values above 2, NNPA can be combined with [ CoCl ] 4 ] 2- Form an extraction complex ([ NNPACoCl) with neutrality and coordination saturation 2 ]). Thus, as the pH increases, the extraction selectivity of NNPA changes. This is one of the reasons why NNPA selectively extracts Ni (II) at pH values below 2, and Co (II) at pH values above 2. FIGS. 7 (e) and 7 (f) show the rapid extraction capacity of NNPA for Ni (II) and Co (II), and the extraction reaches equilibrium within 10 minutes.
As shown in fig. 9, NNPA has better separation performance for Ni (II) and Co (II) than the organophosphorus and amine extractants, and NNPA can selectively extract Ni (II) from Ni (II) -Co (II) solution, which cannot be done by the organophosphorus and amine extractants. The breakthrough method for separating Ni (II) and Co (II) by NNPA can reduce the consumption of extractant, shorten the extraction process flow, improve the efficiency and reduce the energy consumption.
Example 6
A Ni (II) -Co (II) solution containing 16.8g/L Ni (II) and 1.2g/L Co (II) was prepared to simulate a Ni (II) -Co (II) solution leached from laterite nickel ore and purified by a hydrometallurgical process. In addition, an actual spent lithium ion battery leach solution containing 3.5g/L Li (I), 23.6g/L Co (II), 1.2g/L Ni (II), 2.35g/L Mn (II) and 2.6g/LAl (III) was also prepared. To verify the extraction performance of NNPA, the Ni (II) -Co (II) solution leached from laterite nickel ore was adjusted to ph=6 to selectively extract Co (II), while the real spent lithium ion battery leachate was adjusted to ph=0 to selectively extract Ni (II), the diluent was sulfonated kerosene, the polar modifier was isooctanol with a volume ratio of 30%, and after shaking in a water bath at room temperature of 25 ℃ for 10min, standing for delamination, after phase separation, the metal ion concentration in the extract was measured by inductively coupled plasma emission spectroscopy (ICP-OES), and the metal ion concentration in the organic phase was determined by differential subtraction. FIGS. 10 (a) and 10 (b) show Co (II) and Ni (II) extraction saturation curves and their McCabe-Thiele plots, respectively, at 10vol% NNPA and 3mol/L chloride concentrations.
As can be seen from FIG. 10, a 5-stage countercurrent extraction experiment was performed with an A/O ratio of 9/1. About 98% of Co (II) or Ni (II) is extracted by 5 stages of countercurrent extraction. In the extracted organic phase of Co (II) or Ni (II), the mass concentration ratio of Co (II)/Ni (II) and Ni (II)/Co (II) reaches 836 and 891 respectively. As listed in table 2, the separation performance of NNPA on Ni (II) and Co (II) was not affected by impurities. According to the SHAB theory, li (I), al (III) and Mn (II) may not be coordinated with the pyridine group since they do not belong to "boundary acids". Even if these metal impurities are present in the Ni (II) -Co (II) solution, they do not affect the separation performance of NNPA for Ni (II) and Co (II). After the stripping process with deionized water, coCl in the raffinate and strip 2 Or NiCl 2 Precipitated by carbonate and sodium ions remain in the crude filtrate and in the stripping solution. These precipitates are subsequently converted into CoSO 4 Or NiSO 4 Further purified by hydrometallurgical process can be used as raw material for cathode of battery.
Table 25 raffinate after countercurrent extraction
Example 7
The configuration contains 3 g.L -1 Ni(II)，0.3g·L -1 Co(II)，3g·L -1 Al(III)，0.2g·L -1 Ca(II)，1g·L -1 Mg(II),0.86g·L -1 Zn (II), and 0.4 g.L -1 20mL of sulfuric acid leaching solution of Mn (II) simulated laterite-nickel ore is used as a water phase to be extracted, and 2mol/L sulfuric acid and 1mol/L sodium hydroxide are used for dissolving and adjusting the initial pH of the feed liquid. Preparing an organic phase, wherein the organic phase contains P204 of 0.2mol/L, a bipyridyl extractant of 0.2mol/L, a diluent of sulfonated kerosene, and a polar modifier of isooctyl alcohol accounting for 30% of the volume, and the ratio (O/A) is 1:1, adjusting the extraction balance pH by saponifying the organic phase with 10mol/L sodium hydroxide solution. Adding the aqueous phase into the organic phase, oscillating in water bath at room temperature of 25deg.C for 10min, standing for layering, separating phase, and measuring metal ion concentration in the extractive solution by inductively coupled plasma emission spectrometry (ICP-OES), wherein the metal ion concentration in the organic phase is obtained by differential method.
As shown in fig. 4, as the equilibrium pH increases, the extraction rates of Ni (II), co (II) significantly increase, while the extraction rates of Al (III), ca (II), mg (II), mn (II), and Zn (II) slightly increase as the equilibrium pH increases. The extraction tendencies of Ni (II) and Co (II) are similar to those of Ni (II) and Co (II) in example 4, but the synergistic extraction system consisting of a bipyridyl extractant and P204 needs to neutralize and remove Fe (III) in laterite nickel ore and secondary resource leaching solution so as to realize direct extraction separation of Ni (II) and Co (II) from Al (III), ca (II), mg (II), mn (II) and Zn (II). However, since DNNSA has a relatively high price and the extraction capacity and saturation capacity of DNNSA are not as high as those of P204, this example is very suitable for separating Ni (II) and Co (II) from a solution of laterite nickel ore with a low iron content and a secondary resource leachate by pre-removing Fe (III).
Claims (10)
1. A bipyridyl extractant, characterized in that: has a structure shown in formula 1:
wherein R is C 12 ～C 25 Is a hydrocarbon group.
2. A bipyridyl extractant as claimed in claim 1, wherein: r is C 12 ～C 25 Straight-chain alkyl or C 12 ～C 25 Branched alkanes of (2).
3. A process for the preparation of a bipyridyl extractant as claimed in claim 1 or claim 2, characterised in that: chloromethyl pyridine hydrochloride and primary amine compound with the structure of formula 2 are subjected to a bimolecular nucleophilic substitution reaction to obtain a bipyridyl extractant;
RNH 2
2, 2
Wherein,,
r is C 12 ～C 25 Is a hydrocarbon group.
4. A method for preparing a bipyridyl extractant according to claim 3, wherein:
the molar ratio of chloromethylpyridine hydrochloride to primary amine compound is (2-2.2): 1.
5. A process for the preparation of a bipyridyl extractant as claimed in claim 3 or 4, wherein: the conditions of the nucleophilic substitution reaction of the double molecules are as follows: under the action of alkali, the reaction is carried out for 48 to 60 hours at the temperature of 60 to 90 ℃.
6. Use of a bipyridyl extractant according to claim 1 or 2, characterized in that: as nickel extractant and/or cobalt extractant.
7. The use of a bipyridyl extractant as claimed in claim 6, wherein: the method is applied to the separation of nickel and cobalt from other metal ions in a complex metal ion solution system or the separation of nickel ions and cobalt ions in a nickel-cobalt solution system.
8. The use of a bipyridyl extractant as claimed in claim 6, wherein: the bipyridyl extractant is used alone, or in combination with DNNSA, or in combination with P204.
9. Use of a bipyridyl extractant according to any one of claims 6 to 8, characterized in that: the bipyridyl extractant is independently applied to the separation of nickel ions and cobalt ions in a nickel-cobalt solution system, the concentration of the bipyridyl extractant in an organic phase is 0.1-0.4 mol/L, and the extraction conditions are as follows: the pH value is 0-6, the temperature is 15-40 ℃, and the concentration of chloride ions in the nickel-cobalt solution system is 1-4 mol/L.
10. Use of a bipyridyl extractant according to any one of claims 6 to 8, characterized in that: the bipyridyl extractant and DNNSA are cooperatively applied to the separation of nickel and cobalt from other metal ions in a complex metal ion solution system, wherein the complex metal ion solution system comprises nickel and/or cobalt and at least one of iron, aluminum, calcium, magnesium, zinc and manganese; the extraction conditions are as follows: the pH value is 0.25-2.5, and the temperature is 15-40 ℃; the concentration of the bipyridyl extractant in the organic phase is 0.1-0.4 mol/L; the molar ratio of the bipyridyl extractant to DNNSA is 1:1 to 4;
or,
the bipyridyl extractant and P204 are cooperatively applied to the separation of nickel and cobalt from other metal ions in a complex metal ion solution system, wherein the complex metal ion solution system comprises nickel and/or cobalt and at least one of aluminum, calcium, magnesium, zinc and manganese; the extraction conditions are as follows: the pH value is 0.25-2.5, and the temperature is 15-40 ℃; the concentration of the bipyridyl extractant in the organic phase is 0.1-0.4 mol/L; the molar ratio of the bipyridyl extractant to P204 is 1:1 to 4.
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