CN115433832B - Nickel and cobalt synergistic extractant and application thereof - Google Patents
Nickel and cobalt synergistic extractant and application thereof Download PDFInfo
- Publication number
- CN115433832B CN115433832B CN202110615247.4A CN202110615247A CN115433832B CN 115433832 B CN115433832 B CN 115433832B CN 202110615247 A CN202110615247 A CN 202110615247A CN 115433832 B CN115433832 B CN 115433832B
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- Prior art keywords
- acid
- nickel
- cobalt
- extractant
- extraction
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 298
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 148
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 129
- 239000010941 cobalt Substances 0.000 title claims abstract description 129
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 78
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 73
- 239000012535 impurity Substances 0.000 claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 41
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 claims abstract description 31
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 31
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 5
- 239000011504 laterite Substances 0.000 claims abstract description 5
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 14
- DZGWZDVJPZBWGS-UHFFFAOYSA-N 3-pentyldecanoic acid Chemical compound C(CCCC)C(CC(=O)O)CCCCCCC DZGWZDVJPZBWGS-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- FYSUCIRARGQXCJ-UHFFFAOYSA-N 2-hexylnonanoic acid Chemical compound CCCCCCCC(C(O)=O)CCCCCC FYSUCIRARGQXCJ-UHFFFAOYSA-N 0.000 claims description 7
- JMOLZNNXZPAGBH-UHFFFAOYSA-N hexyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCC JMOLZNNXZPAGBH-UHFFFAOYSA-N 0.000 claims description 7
- 229950004531 hexyldecanoic acid Drugs 0.000 claims description 7
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 6
- YHYRSCXMQFIFNC-UHFFFAOYSA-N 4-decylpyridine Chemical compound CCCCCCCCCCC1=CC=NC=C1 YHYRSCXMQFIFNC-UHFFFAOYSA-N 0.000 claims description 5
- FQWJTYWHQOIMFL-UHFFFAOYSA-N 8-methylnonyl pyridine-3-carboxylate Chemical compound CC(C)CCCCCCCOC(=O)c1cccnc1 FQWJTYWHQOIMFL-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- RXSDLZMEACISEK-UHFFFAOYSA-N n-decylpyridine-4-carboxamide Chemical compound CCCCCCCCCCNC(=O)C1=CC=NC=C1 RXSDLZMEACISEK-UHFFFAOYSA-N 0.000 claims description 5
- YDJUCGMWHYJPIS-UHFFFAOYSA-N 3-propyltridecanoic acid Chemical compound CCCCCCCCCCC(CCC)CC(O)=O YDJUCGMWHYJPIS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- HHBIYJMJDKRUCS-UHFFFAOYSA-N 2-Propyl-tridecanoic acid Chemical compound CCCCCCCCCCCC(C(O)=O)CCC HHBIYJMJDKRUCS-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- FAXUIYJKGGUCBO-UHFFFAOYSA-N 1-(2,5-dimethoxyphenyl)ethanone Chemical compound COC1=CC=C(OC)C(C(C)=O)=C1 FAXUIYJKGGUCBO-UHFFFAOYSA-N 0.000 claims description 2
- KUQRQSRKUXHMPX-UHFFFAOYSA-N 1-decylbenzimidazole Chemical compound C1=CC=C2N(CCCCCCCCCC)C=NC2=C1 KUQRQSRKUXHMPX-UHFFFAOYSA-N 0.000 claims description 2
- UTTOFKUHMSIKMG-UHFFFAOYSA-N 2-(3-methylbutyl)decanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCC(C)C UTTOFKUHMSIKMG-UHFFFAOYSA-N 0.000 claims description 2
- BDWTUWFDMGJTOD-UHFFFAOYSA-N 2-butylnonanoic acid Chemical compound CCCCCCCC(C(O)=O)CCCC BDWTUWFDMGJTOD-UHFFFAOYSA-N 0.000 claims description 2
- QWKKIWGATLDTLF-UHFFFAOYSA-N 2-decylpyridine Chemical compound CCCCCCCCCCC1=CC=CC=N1 QWKKIWGATLDTLF-UHFFFAOYSA-N 0.000 claims description 2
- UWORJOUXMWXRPU-UHFFFAOYSA-N 2-heptyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCCC UWORJOUXMWXRPU-UHFFFAOYSA-N 0.000 claims description 2
- YLZIMEJTDZWVJG-UHFFFAOYSA-N 2-heptylundecanoic acid Chemical compound CCCCCCCCCC(C(O)=O)CCCCCCC YLZIMEJTDZWVJG-UHFFFAOYSA-N 0.000 claims description 2
- NJUGDERYCCDBMJ-UHFFFAOYSA-N 2-propyldodecanoic acid Chemical compound CCCCCCCCCCC(C(O)=O)CCC NJUGDERYCCDBMJ-UHFFFAOYSA-N 0.000 claims description 2
- NKVGNUVTQDNTBZ-UHFFFAOYSA-N 3-butyldecanoic acid Chemical compound CCCCCCCC(CC(O)=O)CCCC NKVGNUVTQDNTBZ-UHFFFAOYSA-N 0.000 claims description 2
- SBOFSIAVDBUXHM-UHFFFAOYSA-N 3-butylnonanoic acid Chemical compound CCCCCCC(CC(O)=O)CCCC SBOFSIAVDBUXHM-UHFFFAOYSA-N 0.000 claims description 2
- NNEYEQMCIJZAOS-UHFFFAOYSA-N 3-decylpyridine Chemical compound CCCCCCCCCCC1=CC=CN=C1 NNEYEQMCIJZAOS-UHFFFAOYSA-N 0.000 claims description 2
- NLMPTHDIKIOXAG-UHFFFAOYSA-N 3-heptyldecanoic acid Chemical compound CCCCCCCC(CC(O)=O)CCCCCCC NLMPTHDIKIOXAG-UHFFFAOYSA-N 0.000 claims description 2
- KFTONPAKWUUXSN-UHFFFAOYSA-N 3-hexyldecanoic acid Chemical compound C(CCCCC)C(CC(=O)O)CCCCCCC KFTONPAKWUUXSN-UHFFFAOYSA-N 0.000 claims description 2
- YAAMJAVIZRNQDL-UHFFFAOYSA-N 3-hexylnonanoic acid Chemical compound CCCCCCC(CC(O)=O)CCCCCC YAAMJAVIZRNQDL-UHFFFAOYSA-N 0.000 claims description 2
- DCVMHYMVLVTZLU-UHFFFAOYSA-N 3-propyldecanoic acid Chemical compound CCCCCCCC(CCC)CC(O)=O DCVMHYMVLVTZLU-UHFFFAOYSA-N 0.000 claims description 2
- NODDIWRUBZSFCP-UHFFFAOYSA-N 3-propylpentadecanoic acid Chemical compound CCCCCCCCCCCCC(CCC)CC(O)=O NODDIWRUBZSFCP-UHFFFAOYSA-N 0.000 claims description 2
- GVPDJTFWPBOKGK-UHFFFAOYSA-N 3-propyltetradecanoic acid Chemical compound CCCCCCCCCCCC(CCC)CC(O)=O GVPDJTFWPBOKGK-UHFFFAOYSA-N 0.000 claims description 2
- WQZSUIUJDNVCAB-UHFFFAOYSA-N 3-propylundecanoic acid Chemical compound CCCCCCCCC(CCC)CC(O)=O WQZSUIUJDNVCAB-UHFFFAOYSA-N 0.000 claims description 2
- OSLWKVZCPYBKCZ-UHFFFAOYSA-N 4-methyl-2-propyldecanoic acid Chemical compound CCCCCCC(C)CC(CCC)C(=O)O OSLWKVZCPYBKCZ-UHFFFAOYSA-N 0.000 claims description 2
- TZZQXAGNOAGLQM-UHFFFAOYSA-N N1=C(C=CC=C1)C(=O)OCCCCCCCC(C)C Chemical compound N1=C(C=CC=C1)C(=O)OCCCCCCCC(C)C TZZQXAGNOAGLQM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- LNSLZFGNVRHPJG-UHFFFAOYSA-N nonyl pyridine-4-carboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=NC=C1 LNSLZFGNVRHPJG-UHFFFAOYSA-N 0.000 claims description 2
- JNPKZDAETFQNEL-UHFFFAOYSA-N 2-butylundecanoic acid Chemical compound CCCCCCCCCC(C(O)=O)CCCC JNPKZDAETFQNEL-UHFFFAOYSA-N 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 176
- 239000007788 liquid Substances 0.000 abstract description 44
- 239000011777 magnesium Substances 0.000 abstract description 39
- 239000011575 calcium Substances 0.000 abstract description 37
- 229910052749 magnesium Inorganic materials 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 14
- 238000005191 phase separation Methods 0.000 abstract description 14
- 239000000284 extract Substances 0.000 abstract description 7
- 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 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 70
- 239000000243 solution Substances 0.000 description 52
- 239000012074 organic phase Substances 0.000 description 38
- 239000011572 manganese Substances 0.000 description 37
- 238000005406 washing Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003350 kerosene Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 239000003085 diluting agent Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 11
- OUXLCIKYUJAYJF-UHFFFAOYSA-N 8-methylnonyl pyridine-4-carboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=NC=C1 OUXLCIKYUJAYJF-UHFFFAOYSA-N 0.000 description 8
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
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- TVBCCWGVCZSXFD-UHFFFAOYSA-N 4-amino-3-butyl-1h-1,2,4-triazole-5-thione Chemical compound CCCCC1=NNC(=S)N1N TVBCCWGVCZSXFD-UHFFFAOYSA-N 0.000 description 2
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- 239000012527 feed solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VPFMEXRVUOPYRG-UHFFFAOYSA-N hex-5-ynoic acid Chemical compound OC(=O)CCCC#C VPFMEXRVUOPYRG-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Chemical group 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical group C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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
Abstract
The invention discloses a nickel and cobalt synergistic extractant and application thereof. The extractant comprises long-chain monobasic fatty acid with more than 12 carbon atoms and nitrogen-containing heterocyclic compound with more than 9 branched carbon atoms, wherein the long-chain monobasic fatty acid has a branched chain on beta-carbon or alpha-carbon. The synergistic extraction system can efficiently extract nickel and cobalt, has a good removal effect on common coexisting impurities such as manganese, magnesium and calcium, and overcomes the defects of high water solubility and difficult phase separation of the traditional extractant. The extraction system formed by the extractant can be used for extracting nickel and cobalt from the leaching solution of the nickel laterite, extracting nickel and cobalt from the leaching solution of the secondary ternary battery waste, extracting nickel and cobalt from the electroplating waste liquid and other nickel and cobalt-containing feed liquid, and the application of the extractant can simplify the flow, improve the yield and purity of the nickel and cobalt, reduce the consumption of acid-base reagents and greatly reduce the extraction cost of the nickel and cobalt.
Description
Technical Field
The invention relates to the technical field of extractants, and relates to a nickel and cobalt synergistic extractant and application thereof.
Background
Nickel cobalt is widely used in the fields of energy materials, alloys, stainless steel and the like, and commonly coexists with impurity elements such as Mn, mg, ca and the like in the process of recycling primary resources or secondary resources, and the impurity elements are required to be separated in the extraction of Ni and Co. At present, the solvent extraction method is commonly used in industry for extraction and separation, but the commonly used extracting agents in industry are phosphine extracting agents, including 2-ethylhexyl phosphoric acid (P204), 2-ethylhexyl mono-2-ethylhexyl ester (P507) and di (2, 4-trimethyl amyl) phosphinic acid (Cyanex 272), and the phosphine extracting agents have strong extraction capacity to impurity elements Mn, mg and Ca and even are better than Ni and Co extraction, so that the extracting agents are difficult to extract Ni and Co, a plurality of extraction cycles are required to be completed, the number of required extraction stages is large, the consumption of reagents is large, and the produced waste liquid is large and pollution is large.
CN103421952a discloses a synergistic extractant and a method for selectively extracting nickel from an acidic nickel-containing solution, wherein the synergistic extractant is naphthalene sulfonic acid or a compound of naphthalene sulfonate and pyridine carboxylate, the method is to selectively extract nickel ions from an acidic nickel-containing aqueous solution by using the synergistic extractant, and a loaded organic phase is back-extracted by using inorganic acid to obtain a high-purity nickel-containing solution, so that effective separation of nickel ions from impurity ions such as iron ions, aluminum ions, manganese ions, magnesium ions, calcium ions and chromium ions is realized. However, the extraction system is used for selectively extracting nickel and cobalt under the condition of pH <2, more than 1.0M sulfuric acid is needed to completely strip nickel and cobalt loaded by an organic phase, strip liquor residual acid is high, post-treatment is complex, and the system has poor stability, phase separation difficulty and large industrial application limitation.
CN108822147a discloses a pyridylphosphamide compound, a preparation method thereof and application thereof as a nickel cobalt extractant. The pyridine-4-formaldehyde and alkyl primary ammonia are subjected to an aldol condensation reaction to generate a Schiff base intermediate, and the Schiff base intermediate and dialkyl phosphite are subjected to an addition reaction to obtain the pyridyl phosphoramide compound. The pyridyl phosphoramide compound is matched with P204 to serve as a nickel-cobalt synergistic extractant for extracting and separating nickel, cobalt, magnesium, manganese and other cations, and has the characteristics of higher extraction capacity, short phase separation time, excellent extraction and back extraction performance and the like. However, the extraction capacity of the system for impurity Mn is better than that of cobalt, and if a solution contains a large amount of Mn ions, the application of the system is greatly limited. And the phosphorus extractant also has stronger extraction capacity to Ca and Mg, so the selectivity of the extraction system for extracting Ni and Co to separate Ca and Mg is also poor, and the practical application is difficult.
There are also studies reporting the combination of aliphatic carboxylic acids (Versatic-10 and Versatic-911) and naphthenic acids (cyclohexenecarboxylic acid) with pyridyl ester nitrogen heterocyclesThe synergistic extraction system composed of the substances extracts nickel and cobalt, but has poor nickel-cobalt extraction performance and poor separation effect of impurity elements. In addition, certain pyridine ester compounds are reported for the extraction of nickel and cobalt at acidity of nickel cobalt stripping (0.5-2M H 2 SO 4 ) In addition, the reagent is almost completely dissolved in the water phase, which makes practical use impossible. Therefore, such synergistic extraction systems are not reported for industrial use.
Therefore, it is necessary to provide a synergistic extractant for nickel and cobalt, which not only ensures the efficient extraction of nickel and/or cobalt, but also solves the problems of large water solubility, difficult phase separation, poor impurity ion separation effect and the like of an extraction system so as to meet the application requirements in the practical industrial production of Ni and Co.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a nickel and cobalt synergistic extractant and a method for extracting nickel and/or cobalt by adopting the same. The nickel-cobalt synergistic extractant provided by the invention comprises long-chain monobasic fatty acid with more than 12 carbon atoms and nitrogen-containing heterocyclic compound with more than 9 carbon atoms in a side chain, wherein the long-chain monobasic fatty acid has a branched chain on beta-carbon or alpha-carbon. The synergistic extractant is used for extracting nickel and/or cobalt, so that the problems of large water solubility, difficult phase separation, poor impurity ion separation effect and the like of an extraction system are effectively solved, and the synergistic extractant can be applied to the actual industrial production of Ni and Co, thereby greatly simplifying the extraction flow, reducing the reagent consumption and lowering the production cost.
In the invention, the "nickel and cobalt synergistic extractant" refers to: the extractant can be used for extracting one of nickel or cobalt, can also be used for simultaneously extracting nickel and cobalt, and has good extraction effect on nickel and cobalt when simultaneously extracting nickel and cobalt.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention aims to provide a nickel and cobalt synergistic extractant, which comprises long-chain monobasic fatty acid with more than 12 carbon atoms and a nitrogen-containing heterocyclic compound with more than 9 carbon atoms in a side chain, wherein the long-chain monobasic fatty acid has a branched chain on beta-carbon or alpha-carbon.
In the long chain monobasic fatty acid, the number of carbon atoms is 12 or more, for example, 12, 13, 14, 15, 16, 17 or 18. In the nitrogen-containing heterocyclic compound, the number of carbon atoms in the side chain is 9 or more, for example, 9, 10, 11 or 12. In the nitrogen-containing heterocyclic compound of the present invention, the number of side chains may be one or more, and if a plurality of side chains are used, it is necessary to ensure that the number of carbon atoms of at least one side chain is 9 or more.
Through a great deal of experimental researches of the inventor, the number of carbon atoms of the side chain of the nitrogen-containing heterocyclic compound can influence the water solubility of the compound and the stability of the compound to an acid solution, the length of the side chain of the heterocyclic compound is increased, the water solubility of the compound is reduced, and the stability of the compound to the acid solution is increased. Molecular design and modification and experiments prove that: the side chain contains 8-carbon aminopyridine, the water solubility is about 1.5g/L at normal temperature, the length of the side chain is increased to 9 carbon atoms, the water solubility is greatly reduced to 0.15g/L, the requirement of the metallurgical process can be met, and the experimental result is also supported by theoretical calculation of a de novo calculation method. Aminopyridine having 8 carbon branches in the side chain forms a soluble salt with acid and is completely dissolved in water phase when back-extracted with sulfuric acid of 0.5M or more, and 1M H when the number of carbon atoms is 9 or more 2 SO 4 The solution can still exist in the organic phase stably during back extraction, thereby meeting the metallurgical requirement. The same results are found for pyridine ester compounds of another class of aza heterocyclic compounds.
The extraction system comprises long-chain monobasic fatty acid and a nitrogen-containing heterocyclic compound, wherein the number of carbon atoms of a side chain of the nitrogen-containing heterocyclic compound is more than 9, the length of the side chain of the heterocyclic compound is increased, the water solubility of the compound is reduced, the stability of the compound in an acid solution is greatly increased, the reported serious defects that the side chain is short-chain and the water solubility of the nitrogen-containing heterocyclic compound is high, and acid salt formed by a reagent enters a water phase during acid back extraction are overcome, and the recycling of an extractant is facilitated. The long-chain fatty acid has more than 12 carbon atoms and branched chains at beta or alpha positions, so that the water solubility of the compound is greatly reduced, and the phase separation effect and the extraction separation effect in the extraction process are improved.
Meanwhile, N atoms in the nitrogen-containing heterocyclic compound are strong electron donors, the nitrogen-containing heterocyclic compound can participate in coordination of Ni and Co, carboxylic acid in long-chain fatty acid, the nitrogen-containing heterocyclic compound and metal ions form a stable cyclic complex, the extraction selectivity of a synergistic extraction system to nickel and cobalt is greatly improved, impurity ions Ca, mg and Mn and the synergistic extraction system do not form a ligand or have weak coordination capacity, and the extraction rate of the extraction system to impurity ions is very low.
Therefore, the synergistic extractant is used for extracting nickel and/or cobalt, effectively solves the problems of large water solubility, difficult phase separation, poor impurity ion separation effect and the like of an extraction system, can be applied to the actual industrial production of Ni and Co, can efficiently extract nickel and/or cobalt, has easy phase separation, and has good removal and separation effects on common coexisting impurity ions Mn, mg, ca and the like.
In the extractant, two substances, namely long-chain monobasic fatty acid and nitrogen-containing heterocyclic compound, are indispensable, and if only long-chain monobasic fatty acid is adopted, the extraction rate of nickel and cobalt is reduced, for example, the long-chain fatty carboxylic acid compound has weak extraction capacity to impurity ions Mn, mg and Ca, the extraction rate of Mg and Ca is about 5% below pH 6.5, the extraction rate of Mn is less than 20%, and the extraction rate of Ni and Co is lower and is less than 50%.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, the long chain monobasic fatty acid has a carbon number greater than 12, preferably 15 to 17. With the increase of the number of carbon atoms, the separation effect on impurities is better, but the extraction effect on nickel and cobalt tends to be poor at the same mass concentration. In the preferred range of 15 to 17 carbon atoms, the extraction effect on nickel and cobalt and the separation effect on impurities can be better considered. Not only avoids the environmental problem caused by the unqualified wastewater, but also is beneficial to the recycling of the extractant.
Preferably, the beta-carbon or the alpha-carbon is provided with only one branched chain, and the carbon number of the branched chain is more than 3, so that the phase separation effect in the extraction process can be improved, the steric hindrance of the compound is reduced, and the extraction separation effect is enhanced.
More preferably, the branched chain has a carbon number of 3 to 10, for example 3,4, 5, 6, 8 or 10.
Preferably, the branches are alkyl branches. Preferably, the long chain monobasic fatty acids include, but are not limited to, at least one of 3-propyl nonanoic acid, 2-propyl nonanoic acid, 3-hexyl nonanoic acid, 2-hexyl nonanoic acid, 3-butyl nonanoic acid, 2-butyl nonanoic acid, 3-butyl-4-methyl nonanoic acid, 3-propyl decanoic acid, 2-propyl decanoic acid, 3-amyl decanoic acid, 2-amyl decanoic acid, 3-hexyl decanoic acid, 2-hexyl decanoic acid, 3-butyl decanoic acid, 3-heptyl decanoic acid, 2-heptyl decanoic acid, 4-methyl-2-propyl decanoic acid, 3-propyl undecanoic acid, 2-pentyl undecanoic acid, 2-heptyl undecanoic acid, 3-propyl dodecanoic acid, 2-propyl dodecanoic acid, 3-butyl dodecanoic acid, 2-amyl dodecanoic acid, 2- (3-methyl butyl) -decanoic acid, 2-propyl tridecanoic acid, 2-propyl tetradecanoic acid, 3-propyl tetradecanoic acid, isostearic acid, 3-propyl pentadecanoic acid, 2-octyl dodecanoic acid, and 3-octyl dodecanoic acid, preferably 3-amyl decanoic acid, 2-hexyl nonanoic acid, 3-propyl tridecanoic acid, 2-hexyl decanoic acid, 3-butyl-4-methyl nonanoic acid.
It should be noted that isostearic acid exists in a plurality of isomers, and that isostearic acid having a branch on the β -carbon or the α -carbon is not used in the present invention.
Part of long-chain monobasic fatty acid can be directly purchased from the market, the rest part of long-chain monobasic fatty acid can be obtained by oxidizing corresponding alcohol compounds, and the oxidant can be hydrogen peroxide, peroxosulfuric acid, cerium oxide, chromium trioxide, vanadium pentoxide, potassium permanganate and the like, and related documents are as follows:
document 1: just G, luthe C, oh H.4-Pentynoc and 5-Hexynoic Acid from Jones Oxidation of-Hexynol [ J ]. Synthetic Communications,1980,9 (7): 613-617.
Document 2: sun B, hong W, aziz H, et al Diketopropyrrrole-based semiconducting polymer bearing thermocleavable side chains [ J ]. Journal of Materials Chemistry,2012,22 (36): 18950-18955.
Document 3: liu Zongyong test for oxidizing hydrogen peroxide to synthesize glyceric acid [ J ]. Salt industry and chemical industry 2015,44 (05): 26-28.
Document 4: chen Jun, long Jilan alcohol oxidation reaction research progress [ J ]. Industrial catalysis, 2017 (8): 1-6. In the present invention, the long-chain monobasic fatty acid may be a single compound, or may be a mixture or complex of two or more.
Preferably, the nitrogen-containing heterocyclic compound is selected from at least one of a substituted imidazole compound and a substituted pyridine compound.
In the present invention, the nitrogen-containing heterocyclic compound may be a single compound, or may be a mixture or a complex of two or more.
Preferably, the substituents in the substituted imidazole compound and the substituted pyridine compound independently include any one of alkyl groups, amine groups, amide groups, ester groups, or ether linkages, but are not limited to the above-listed types, and other hydrophobic functional groups that can achieve the same effect may be suitable for the present invention. The term "independently" means: the substituent of the imidazole compound and the substituent of the pyridine compound can be the same or different, and the types of the substituent and the substituent are selected independently.
In the present invention, the position of the substituent in the substituted imidazole compound is not limited.
In the substituted pyridine compound, the substituent may be located in the ortho-position, meta-position or para-position of the N atom on the benzene ring. Preferably, the nitrogen-containing heterocyclic compound includes, but is not limited to, at least one of N-decyl 3-picolinate, N-decyl 4-picolinate, isodecyl 3-picolinate, isodecyl 2-picolinate, 2-propylheptyl 4-picolinate, 2-propylheptyl 3-picolinate, nonyl 4-picolinate, N-decyl bipyridylamine, N- (2-propylheptyl) -4-pyridinecarboxamide, N- (1-decyl) -4-pyridinecarboxamide, bis- (1-decylbenzimidazole) amine, 2- (5-N-octylpyrazolyl) pyridine, 4-decylpyridine, 3-decylpyridine, and 2-decylpyridine.
Some nitrogen-containing heterocyclic compounds having 9 or more side chain carbon atoms can be obtained by direct purchase from related reagent companies, and the remainder can be obtained by reacting raw materials such as nicotinic acid, isonicotinic acid, 2-chloromethylpyridine, pyridylaldehyde, etc., with n-decanol, isodecanol, etc., through esterification, acid-amine condensation, ammonolysis, aldol condensation, etc., and the related documents are as follows:
document 5: ge Chunhua, zhang Xiangdong, fan Ping, et al, phase transfer catalytic synthesis of ethyl isonicotinate [ J ]. Chemical world, 2003,44 (2): 81-82.
Document 6: jiang Darong the equation for the preparation of amines by reaction of haloalkanes with ammonia [ J ]. Inward river university school, 2002,017 (004): 67-69.
Document 7: tang Lin, peiling substituted 4-pyridone-2-carboxaldehyde and amino compound condensation products, J. Hua Xiyao J.1988 (01): 5-9.
Document 8: borowiak-research, a.. Extraction of copper from acid chloride solutions by n-alkyl-and n, n-dialkylyl-3-pyridinecarboxamides, solvent Extraction and Ion Exchange,2007,12 (3), 557-569. Preferably, the molar ratio of the long chain monobasic fatty acid to the nitrogen-containing heterocyclic compound is from 5:1 to 1:5, for example, from 5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:4 or 1:5, etc., preferably from (1.5 to 3.5): 1.
The molar ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound can influence the extraction saturation capacity and the phase separation effect of a synergistic system and the effect of separating impurity ions Mn, mg and Ca, and if the molar ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound is too large, the excessive long-chain monobasic fatty acid can cause the small saturation capacity of the system and the poor effect of separating impurities; if the molar ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound is too small, too little of the long-chain monobasic fatty acid can cause the extraction system to emulsify or phase-separate slowly.
It should be noted that the nickel and cobalt synergistic extraction system of the present invention is not limited to the above listed components, but may also include other functional components, for example, additives may be added, and the types of additives include, but are not limited to, long-chain phenol compounds, long-chain alcohol compounds, and the like, such as nonylphenol, dodecylphenol, isooctanol, isotridecanol, and the like, and the additives also form a part of the nickel and cobalt synergistic extraction agent.
It is another object of the present invention to provide a use of the nickel-cobalt synergistic extractant for extracting nickel and/or cobalt in a nickel-and/or cobalt-containing solution and capable of separating impurity elements Mn, mg and Ca as described in one of the objects.
The specific type of the nickel and/or cobalt-containing solution is not limited in the present invention, and may be any of, for example, a nickel laterite leaching solution, a secondary ternary battery waste leaching solution, an electroplating waste solution, or a nickel sulfide ore leaching solution, or may be other nickel and/or cobalt-containing feed solutions.
Illustratively, nickel and cobalt may be extracted from a secondary ternary battery waste leachate comprising nickel, cobalt and manganese while separating manganese; nickel may also be extracted from the electroplating effluent.
The application of the extractant can simplify the process, improve the yield and purity of nickel and cobalt, reduce the consumption of acid-base reagents and greatly reduce the extraction cost of nickel and cobalt.
The extractant can be used together with phase modifier in the extraction process, so as to further improve the phase separation effect of two phases. The type of the modifier is not particularly limited, and may include, for example, a long-chain alcohol having 8 or more carbon atoms and/or tributyl phosphate (TBP).
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts molecular structure analysis and carries out a great amount of experimental study, successfully provides a nickel and cobalt synergistic extraction system, effectively solves the problems of large water solubility of the extraction system, poor impurity separation capability and the like of an acid stripping extractant entering a water phase, and greatly improves the phase separation effect in the extraction process.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
This example provides a nickel and cobalt synergistic extractant consisting of 3-amyl decanoic acid and isodecyl 4-picolinate, wherein 3-amyl decanoic acid is purchased from TCI reagent company and isodecyl 4-picolinate is obtained from isonicotinic acid and isodecyl alcohol by esterification (preparation method reference 5). The molar ratio of 3-amyl decanoic acid to isodecyl 4-picolinate was 2:1.
The embodiment also provides a method for separating and recovering nickel and cobalt in the waste NCM battery by adopting the nickel and cobalt synergistic extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel and cobalt reaches more than 99%, the extraction rate of manganese is 10%, and the extraction rate of calcium and magnesium is less than 1%.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed by 5g/L sulfuric acid solution, and compared with O/A=1:20, the removal rate of impurity metal manganese, calcium and magnesium is more than 99% after 3-stage washing.
(3) Back extraction operation: the washed organic phase is back-extracted by 200g/L sulfuric acid, and compared with O/A=1:25, the back-extraction rate of nickel and cobalt is more than 99% after 3-level back-extraction, and the back-extraction solution comprises 50g/L nickel, 48g/L cobalt and 0.003g/L manganese.
After the back extraction operation in this embodiment, the extractant can be reused.
Example 2
This example provides a nickel and cobalt synergistic extractant consisting of 2-hexyl nonanoic acid and 4-picolinic acid-2-propylheptanoate, wherein 2-hexyl nonanoic acid is purchased from milin reagent company and 4-picolinic acid-2-propylheptanoate is obtained from isonicotinic acid and 2-propylheptanol by esterification reaction (preparation method reference 5). The molar ratio of 2-hexyl nonanoic acid to 4-picolinic acid-2-propylheptyl ester was 3:1.
The embodiment also provides a method for separating, recovering and precipitating nickel and cobalt in the laterite-nickel ore leaching solution after impurity removal by adopting the nickel and cobalt synergistic extractant, which comprises the following steps:
(1) Extraction operation:
taking leaching liquid for standby after precipitation and impurity removal of laterite nickel ore, wherein the leaching liquid comprises 2.79g/L Ni 2+ ，0.33g/L Co 2+ ，1.58g/L Mn 2+ ，0.61g/L Ca 2+ ，42g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water, the saponification rate is 30%, and then the saponified organic phase and the feed liquid (i.e. the leaching liquid obtained after precipitation and impurity removal of laterite nickel ore) are mixed and stirred under the condition of O/A=1:3, and extraction of nickel and cobalt is carried out. ,
the leaching solution is subjected to 3-stage countercurrent extraction, the extraction rate of nickel and cobalt reaches more than 99%, the extraction rate of manganese is 12%, and the extraction rate of calcium and magnesium is less than 1%.
(2) Washing operation: the loaded organic phase is washed with 2g/L nickel sulfate solution, and compared with O/A=1:20, the washing operation is subjected to 3-stage washing, and the removal rate of impurity metal manganese, calcium and magnesium is more than 99%.
(3) Back extraction operation: the washed organic phase is back-extracted by 100g/L sulfuric acid, and compared with O/A=1:25, the back-extraction operation is 3-stage back-extraction, the back-extraction rate of nickel and cobalt is more than 99%, and the back-extraction solution comprises 20g/L nickel, 22g/L cobalt and 0.004g/L manganese, and hardly contains impurity ions such as calcium and magnesium.
After the back extraction operation in this embodiment, the extractant can be reused.
Example 3
This example provides a nickel and cobalt synergistic extractant consisting of 3-propyltridecanoic acid and N- (1-decyl) -4-pyridinecarboxamide, wherein 2-propyltridecanoic acid is purchased from Nanjia chemical Co., ltd. And N- (1-decyl) -4-pyridinecarboxamide is obtained from isonicotinic acid and N-decylamine by an acid amine condensation reaction (preparation method reference 8). The molar ratio of 3-propyltridecanoic acid to N- (1-decyl) -4-pyridinecarboxamide is 2.5:1.
The embodiment also provides a method for separating and recovering nickel and cobalt in nickel-containing wastewater by adopting the nickel and cobalt synergistic extractant, which comprises the following steps:
(1) Extraction operation:
taking nickel-containing wastewater for standby, wherein the nickel-containing wastewater comprises 0.33g/L Ni 2+ ，0.10g/L Co 2+ ，1.55g/L Mg 2+ . Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water, the saponification rate is 20%, and then the saponified organic phase and the feed liquid (namely nickel-containing wastewater) are mixed and stirred under the condition of O/A=12:1, and extraction of nickel and cobalt is carried out.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel reaches more than 99%, the extraction rate of cobalt is 92%, and the extraction rate of magnesium is less than 1%.
(2) Washing impurities: the loaded organic phase is washed by pure water, and compared with O/A=1:20, the washing operation has the impurity magnesium removal rate of more than 99.5 percent after 3-stage washing.
(3) Back extraction operation: the washed organic phase is back-extracted by 50g/L sulfuric acid, and compared with O/A=1:10, the back-extraction operation is 3-stage back-extraction, the back-extraction rate of nickel and cobalt is more than 99%, the back-extraction liquid composition is 22g/L nickel, and the back-extraction liquid almost contains no impurity magnesium ions.
After the back extraction operation in this embodiment, the extractant can be reused.
Example 4
This example provides a nickel and cobalt synergistic extractant consisting of 2-hexyldecanoic acid and 4-decylpyridine, wherein 2-hexyldecanoic acid is obtained by oxidation of 2-hexyldecanol (preparation method reference 1), and 4-decylpyridine is purchased from milin reagent company. The molar ratio of 2-hexyl decanoic acid to 4-decyl pyridine was 1.5:1.
The embodiment also provides a method for separating and recovering nickel and cobalt in the extracted liquid after extracting cobalt by a traditional system in a nickel-cobalt production flow by adopting the nickel-cobalt synergistic extractant, which comprises the following steps:
(1) Extraction operation:
in the production flow of nickel and cobalt, the extract liquid obtained after extracting cobalt by the traditional system is used for standby, and the composition of the extract liquid is 1.29g/L Ni 2+ ，0.015g/L Co 2+ ，10.55g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at normal temperature to obtain a synergistic system with the concentration of the synergistic extractant of 20 vol%; the synergistic system is saponified by ammonia water, the saponification rate is 20%, and then the saponified organic phase and the feed liquid (namely the extract liquid after cobalt extraction by the traditional system in the nickel cobalt production flow) are mixed and stirred under the condition of O/A=1:2, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel reaches more than 99%, the extraction rate of cobalt is 92.17%, and the extraction rate of magnesium is less than 1%.
(2) Washing impurities: the loaded organic phase is washed with pure water, and the Mg removal rate is greater than 99.5% after 3-stage washing compared with O/a=1:20 in the washing operation.
(3) Back extraction operation: the washed organic phase is back-extracted by 50g/L sulfuric acid, and compared with O/A=1:20, the back-extraction operation is 3-stage back-extraction, the back-extraction rate of nickel and cobalt is more than 99%, the back-extraction solution composition is 50g/L nickel and 0.5g/L cobalt, and the back-extraction solution hardly contains magnesium ions as impurities.
After the back extraction operation in this embodiment, the extractant can be reused.
Example 5
This example provides a nickel and cobalt synergistic extractant consisting of 3-butyl-4-methylnonanoic acid and isodecyl 3-picolinate, wherein 3-butyl-4-methylnonanoic acid was purchased from Hangzhou Shang Jie chemical company, and isodecyl 3-picolinate was obtained from nicotinic acid and isodecyl alcohol by esterification (preparation method reference 5). The molar ratio of 3-butyl-4-methyl nonanoic acid to isodecyl 3-picolinate was 3:1.
The embodiment also provides a method for separating and recovering nickel and cobalt in the nickel sulfide ore leaching solution after impurity removal by adopting the nickel and cobalt synergistic extractant, which comprises the following steps:
(1) Extraction operation:
taking nickel sulfide ore leaching solution for standby after removing impurities, wherein the leaching solution comprises 5.3g/L Ni 2+ ，0.52g/L Co 2+ ，2.12g/L Mn 2+ ，12.15g/L Mg 2+ ，0.5g/L Ca 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 20 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water, the saponification rate is 30%, and then the saponified organic phase and the feed liquid (namely the nickel sulfide ore leaching liquid after impurity removal of the nickel sulfide ore leaching liquid) are mixed and stirred under the condition of O/A=1:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel reaches more than 99%, the extraction rate of cobalt is 98.17%, the extraction rate of manganese is about 15%, and the extraction rates of calcium and magnesium are less than 1%.
(2) Washing impurities: the organic phase is loaded with 5g/L sulfuric acid for washing, and compared with O/A=1:20, the washing operation has the 3-level washing, and the calcium and magnesium removal rate is more than 99 percent.
(3) Back extraction operation: the washed organic phase is back-extracted by 50g/L sulfuric acid, and compared with O/A=1:20, the back-extraction operation is 3-stage back-extraction, the back-extraction rate of nickel and cobalt is more than 99%, and the back-extraction solution comprises 50g/L nickel and 5g/L cobalt, and almost contains no impurity calcium, magnesium and manganese ions.
After the back extraction operation in this embodiment, the extractant can be reused.
Example 6
The extractant of this example differs from example 1 in that the molar ratio of 3-amyl decanoic acid to isodecyl 4-picolinate is 5:1.
The embodiment also provides another method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-level countercurrent extraction, the extraction rates of nickel and cobalt reach 71% and 63% respectively, the extraction rate of manganese reaches 15%, and the extraction rates of calcium and magnesium are less than 1%.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed by 5g/L sulfuric acid solution, and compared with O/A=1:20, the removal rate of impurity metal manganese, calcium and magnesium is more than 99% after 3-stage washing.
(3) Back extraction operation: the washed organic phase is back-extracted by 200g/L sulfuric acid, the operation ratio is O/A=1:25, the back extraction rate of nickel and cobalt is more than 99% by 3-level back extraction, and the back extraction solution comprises 25g/L nickel, 22g/L cobalt and 0.004g/L manganese.
After the back extraction operation in this embodiment, the extractant can be reused.
The extraction yield of nickel and cobalt was significantly reduced and the extraction capacity was also significantly reduced compared to example 1.
Example 7
The extractant of this example differs from example 1 in that the molar ratio of 3-amyl decanoic acid to isodecyl 4-picolinate is 1:5.
The embodiment also provides another method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel and cobalt reaches more than 99%, the extraction rate of manganese is 10%, and the extraction rate of calcium and magnesium is less than 1%.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed by 5g/L sulfuric acid solution, and compared with O/A=1:20, the removal rate of impurity metal manganese, calcium and magnesium is more than 99% after 3-stage washing.
(3) Back extraction operation: the washed organic phase is back-extracted by 200g/L sulfuric acid, and compared with O/A=1:25, the organic phase is emulsified, oil and water cannot be separated, and the back-extraction operation cannot be normally performed.
As is evident from the comparison of example 1 with examples 6 to 7, the preferred range of mass ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound exists, and the molar ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound is in the range of (1.5 to 3.5): 1, which is more advantageous for increasing the extractant ratio of nickel and cobalt and improving the phase separation effect. The reason is that when the content of the nitrogen-containing heterocyclic compound is too small, the synergistic effect with the aliphatic carboxylic acid is weak, and the extraction rate of nickel and cobalt is low. When the content of the nitrogen-containing heterocyclic compound is too large, the nitrogen-containing heterocyclic compound is combined with sulfuric acid to form sulfate compounds in the back extraction process, and the sulfate compounds can be dissolved in long-chain organic acid, but the solubility in the diluent kerosene is small, and the excessive sulfate compounds can be separated out in the kerosene to generate an emulsification phenomenon.
Example 8
The extractant of this example differs from example 1 in that 3-amyl decanoic acid was replaced with 2-amyl decanoic acid, 2-amyl decanoic acid was purchased from TCI reagent company, and the amount of extractant was the same as in example 1.
The embodiment also provides a method for separating and recovering nickel and cobalt in the waste NCM battery by adopting the extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel and cobalt reaches more than 99%, the extraction rate of manganese is 11%, and the extraction rate of calcium and magnesium is less than 1%.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed by 5g/L sulfuric acid solution, and compared with O/A=1:20, the removal rate of impurity metal manganese, calcium and magnesium is more than 99% after 3-stage washing.
(3) Back extraction operation: the washed organic phase is back extracted by 200g/L sulfuric acid, the operation ratio is O/A=1:25, the back extraction rate of nickel and cobalt is more than 99% by 3-level back extraction, and the back extraction liquid comprises 49.2g/L nickel, 48g/L cobalt and 0.003g/L manganese.
From a comparison of example 1 with example 8, it is clear that the position of the branching on the long-chain monobasic fatty acid on the β -carbon or on the α -carbon hardly influences its ability to extract nickel and cobalt.
Comparative example 1
The extractant of this comparative example is different from example 1 in that 3-amyl decanoic acid is used as the extractant, and the amount of extractant used is the same as that of example 1.
The comparative example also provides a method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the independent 3-amyl capric acid with the diluent kerosene at 50 ℃ to obtain an extractant with the concentration of the extractant of 30 vol%; the extractant is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-level countercurrent extraction, the extraction rates of nickel and cobalt are respectively 51% and 43%, the extraction rate of manganese is 25%, and the extraction rates of calcium and magnesium are less than 1%.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed with 5g/L sulfuric acid solution, and compared with O/A=1:20, the washing operation has 3-stage washing, the impurity calcium and magnesium removal rate is more than 99%, and the manganese removal rate is about 20%.
(3) Back extraction operation: the washed organic phase is back-extracted by 200g/L sulfuric acid, and compared with O/A=1:25, the back-extraction rate of nickel and cobalt is more than 99% after 3-level back-extraction, and the back-extraction solution comprises 24g/L nickel, 18g/L cobalt and 14g/L manganese.
As is clear from the comparison between the example 1 and the comparative example 1, the extraction of the 3-amyl capric acid nickel and cobalt is not complete, the separation capability of the impurity manganese ions is poor, further more extraction stages are needed, the consumption of the reagent is large, and the purity of the nickel cobalt product does not reach the standard.
Comparative example 2
The extractant of this comparative example is different from example 1 in that isodecyl 4-picolinate is used as the extractant, and the amount of extractant used is the same as that of example 1.
The comparative example also provides a method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the independent isodecyl 4-picolinate with the diluent kerosene at 50 ℃ to obtain an extractant with the concentration of the extractant of 30 vol%; the extractant is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-level countercurrent extraction, the extraction rates of nickel and cobalt are respectively 0.2 percent and 0.1 percent, the extraction rate of manganese is 0.1 percent, and the extraction rates of calcium and magnesium are 0.2 percent.
(2) Washing impurities: the loaded organic phase after the extraction operation is washed with 5g/L sulfuric acid solution, and the organic phase is emulsified after 3-stage washing in comparison with O/A=1:20, so that the next operation cannot be performed.
As is evident from the comparison of example 1 and comparative example 2, the extraction of nickel and cobalt was not completed by isodecyl 4-picolinate alone, and emulsification occurred.
Comparative example 3
The extractant of this comparative example differs from example 1 in that 3-amyl decanoic acid was replaced with 2-propyl nonanoic acid, which was purchased from the michel reagent company, and the amount of extractant was the same as in example 1.
The comparative example also provides a method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
(1) Extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid (i.e. NCM battery sulfuric acid leaching liquid) are mixed and stirred under the condition of O/A=10:1, so as to extract nickel and cobalt.
The feed liquid is subjected to 3-stage countercurrent extraction, the extraction rate of nickel and cobalt reaches more than 99%, the extraction rate of manganese is 10%, and the extraction rate of calcium and magnesium is less than 1%. However, during the extraction process, it is obviously found that the raffinate produced by the system is cloudy, and a certain amount of floating oil is produced after the raffinate is treated by sulfuric acid.
As is clear from the comparison between example 1 and comparative example 3, the monovalent fatty acid has too small carbon number, and the compound has poor hydrophobicity, which results in large water solubility of the saponified organic phase, and further causes problems such as large loss of extractant, non-standard wastewater, and the like, and the extractant cannot be reused.
Comparative example 4
The difference from example 1 is that 3-amyl decanoic acid is replaced with isostearic acid, which is available from milin reagent company, and the amount of extractant is the same as in example 1.
In this comparative example, the structure of isostearic acid is as follows:
the comparative example also provides a method for separating and recovering nickel and cobalt in waste NCM batteries by adopting the extractant, which comprises the following steps:
extraction operation:
taking sulfuric acid leaching solution of NCM battery for standby, wherein the leaching solution comprises 19.05g/L Ni 2+ ，14.33g/L Co 2+ ，15.17g/L Mn 2+ ，0.61g/L Ca 2+ ，0.72g/L Mg 2+ 。
Mixing the nickel and cobalt synergistic extractant with diluent kerosene at 50 ℃ to obtain a synergistic system with the concentration of the synergistic extractant of 30 vol%; the synergistic system is saponified by ammonia water with the saponification rate of 30%, and then the saponified organic phase and the feed liquid are mixed and stirred under the condition of O/A=10:1, and extraction of nickel and cobalt is carried out.
But during the extraction process, the phase separation effect of the system is obviously slow, and the emulsification phenomenon gradually occurs along with the increase of the running time.
As is clear from the comparison of example 1 and comparative example 4, the use of isostearic acid having the structure shown in this comparative example resulted in a significant decrease in the solubility of the saponified organic phase in kerosene, and further an emulsification phenomenon occurred, failing to complete the extraction operation.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (13)
1. The nickel and cobalt synergistic extractant is characterized by comprising long-chain monobasic fatty acid with 13-18 carbon atoms and nitrogen-containing heterocyclic compound with more than 9 carbon atoms in side chain, wherein beta-carbon or alpha-carbon in the long-chain monobasic fatty acid is provided with a branched chain;
the molar ratio of the long-chain monobasic fatty acid to the nitrogen-containing heterocyclic compound is (1.5-3.5): 1.
2. The extractant according to claim 1, wherein the long-chain monobasic fatty acid has 15 to 17 carbon atoms.
3. The extractant according to claim 1, wherein the β -carbon or α -carbon has only one branched chain, and the number of carbon atoms in the branched chain is 3 or more.
4. The extractant according to claim 3, wherein the branched chain has 3 to 10 carbon atoms.
5. An extractant according to claim 3 wherein the branches are alkyl branches.
6. The extractant of claim 1 wherein the long chain monobasic fatty acid comprises at least one of 3-hexylnonanoic acid, 2-hexylnonanoic acid, 3-butylnonanoic acid, 2-butylnonanoic acid, 3-butyl-4-methylnonanoic acid, 3-propyldecanoic acid, 2-propyldecanoic acid, 3-pentylsecanoic acid, 2-pentylsecanoic acid, 3-hexyldecanoic acid, 2-hexyldecanoic acid, 3-butyldecanoic acid, 3-heptyldecanoic acid, 2-heptyldecanoic acid, 4-methyl-2-propyldecanoic acid, 3-propylundecanoic acid, 2-butylundecanoic acid, 2-pentylshenic acid, 2-heptylundecanoic acid, 3-propyldodecanoic acid, 2-propyldodecanoic acid, 3-butyldodecanoic acid, 2-pentylsodenoic acid, 2- (3-methylbutyl) -decanoic acid, 2-propyltridecanoic acid, 3-propyltetradecanoic acid, 3-propylpentadecanoic acid.
7. The extractant of claim 6 wherein the long chain monobasic fatty acid is 3-amyl decanoic acid, 2-hexyl nonanoic acid, 3-propyl tridecanoic acid, 2-hexyl decanoic acid, 3-butyl-4-methyl nonanoic acid.
8. The extractant according to claim 1, wherein the nitrogen-containing heterocyclic compound is selected from at least one of a substituted imidazole compound and a substituted pyridine compound.
9. The extractant of claim 8, wherein the substituents in the substituted imidazoles and substituted pyridines independently comprise any one of an alkyl group, an amine group, an amide group, an ester group, or an ether linkage.
10. The extractant of claim 1, wherein the nitrogen-containing heterocyclic compound comprises at least one of N-decyl 3-picolinate, N-decyl 4-picolinate, isodecyl 3-picolinate, isodecyl 2-picolinate, 2-propylheptyl 4-picolinate, 2-propylheptyl 3-picolinate, nonyl 4-picolinate, N-decyldipyridylamine, N- (2-propylheptyl) -4-pyridinecarboxamide, N- (1-decyl) -4-pyridinecarboxamide, bis- (1-decylbenzimidazole) amine, bis- (5-N-octylpyrazolyl) pyridine, 4-decylpyridine, 3-decylpyridine, and 2-decylpyridine.
11. Use of an extractant according to any one of claims 1 to 10, wherein the nickel and cobalt co-extractant is used to extract nickel and/or cobalt from nickel and/or cobalt containing solutions and is capable of separating the impurity elements Mn, mg and Ca.
12. Use according to claim 11, wherein the nickel and/or cobalt containing solution comprises any one of nickel laterite leaching solution, secondary ternary battery waste leaching solution, electroplating effluent or nickel sulphide ore leaching solution.
13. The use according to claim 11, wherein the extractant is used in combination with a phase modifier comprising a long chain alcohol having 8 or more carbon atoms and/or tributyl phosphate TBP.
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| US20200384451A1 (en) * | 2017-09-05 | 2020-12-10 | Council Of Scientific And Industrial Research | Phosphine free cobalt based catalyst, process for preparation and use thereof |
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| JP2000247956A (en) * | 1999-02-26 | 2000-09-12 | Japan Energy Corp | Tricyclic phenylpyridine derivative and liquid crystal composition containing the same |
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