CN116479237A - Extractant, preparation method and application thereof - Google Patents
Extractant, preparation method and application thereof Download PDFInfo
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- CN116479237A CN116479237A CN202210043674.4A CN202210043674A CN116479237A CN 116479237 A CN116479237 A CN 116479237A CN 202210043674 A CN202210043674 A CN 202210043674A CN 116479237 A CN116479237 A CN 116479237A
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- China
- Prior art keywords
- carboxamide
- extractant
- nickel
- cobalt
- pyrrole
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 nitrogen-containing heterocyclic amide compound Chemical class 0.000 claims abstract description 134
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000000605 extraction Methods 0.000 claims abstract description 64
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 38
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 239000003085 diluting agent Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 39
- 239000003607 modifier Substances 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 10
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012527 feed solution Substances 0.000 claims description 6
- VFIYYYJRSKJECJ-UHFFFAOYSA-N n-octylpyridine-4-carboxamide Chemical compound CCCCCCCCNC(=O)C1=CC=NC=C1 VFIYYYJRSKJECJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- XVQJYCJZQVBVTL-UHFFFAOYSA-N n-dodecylpyridine-3-carboxamide Chemical compound CCCCCCCCCCCCNC(=O)C1=CC=CN=C1 XVQJYCJZQVBVTL-UHFFFAOYSA-N 0.000 claims description 4
- JSIDBRSPTZXMGO-UHFFFAOYSA-N n-octylpyridine-3-carboxamide Chemical compound CCCCCCCCNC(=O)C1=CC=CN=C1 JSIDBRSPTZXMGO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- APGIDZYILREERN-UHFFFAOYSA-N n-dodecylpyridine-4-carboxamide Chemical compound CCCCCCCCCCCCNC(=O)C1=CC=NC=C1 APGIDZYILREERN-UHFFFAOYSA-N 0.000 claims description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims 1
- 125000004076 pyridyl group Chemical group 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 12
- 239000011777 magnesium Substances 0.000 abstract description 11
- 239000011575 calcium Substances 0.000 abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052791 calcium Inorganic materials 0.000 abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 abstract description 9
- 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 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000284 extract Substances 0.000 abstract description 6
- 239000004480 active ingredient Substances 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000002386 leaching Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 4
- 229910001710 laterite Inorganic materials 0.000 description 4
- 239000011504 laterite Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- DOYOPBSXEIZLRE-UHFFFAOYSA-N pyrrole-3-carboxylic acid Natural products OC(=O)C=1C=CNC=1 DOYOPBSXEIZLRE-UHFFFAOYSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- QRDZFPUVLYEQTA-UHFFFAOYSA-N quinoline-8-carboxylic acid Chemical compound C1=CN=C2C(C(=O)O)=CC=CC2=C1 QRDZFPUVLYEQTA-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical group N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 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
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HPQRQAOVNXWEEQ-UHFFFAOYSA-N quinoline-8-carboxamide Chemical compound C1=CN=C2C(C(=O)N)=CC=CC2=C1 HPQRQAOVNXWEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention provides an extractant, a preparation method and application thereof, wherein the extractant comprises a combination of a diluent and a nitrogen-containing heterocyclic amide compound, and the nitrogen-containing heterocyclic amide compound has a structure shown in a formula I. The extractant takes the nitrogen-containing heterocyclic amide compound as an active ingredient, is particularly suitable for metal separation in a chloride or nitrate system, can efficiently separate impurities such as manganese, magnesium, calcium and the like, and can purify nickel and cobalt. The extractant preferentially extracts nickel and separates cobalt, fills the blank of selectively extracting nickel and separating cobalt in nickel/cobalt separation, separates impurities such as iron, copper, zinc, manganese, calcium, magnesium and the like through a single extractant, and simplifies the flow. The extractant is particularly suitable for being used as a nickel-cobalt extractant for separating metals in nickel-cobalt feed liquid, has the advantages of large extraction capacity, good separation effect, low reagent consumption, simple process, no acid-base consumption in the extraction process, low operation cost, no complex wastewater treatment problem and environmental protection.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to an extractant, a preparation method and application thereof.
Background
Along with the high-speed development of new energy technology, the requirement for lithium batteries is increasingly increased, and the nickel-cobalt-manganese ternary positive electrode material is good in cycle performance and high in cost performance, and is one of common lithium battery positive electrode materials. Nickel and cobalt are important elements in battery components, and separation and extraction technologies thereof are key research subjects in the chemical industry field. On one hand, the development of the nickel-cobalt separation technology can improve the exploitation efficiency of low-grade nickel-cobalt ore, and obtain a high-purity nickel-cobalt product, thereby reducing the exploitation cost of the low-grade nickel-cobalt ore; on the other hand, nickel and cobalt in the anode material of the waste lithium battery can be recovered, so that the recycling of metals is realized, and the method has important significance for environmental protection and sustainable development of resources.
Nickel cobalt extraction and separation is typically carried out in a sulphate system, for example CN112430733a discloses a method of treating laterite nickel ores comprising the steps of: leaching the laterite nickel ore by sulfuric acid to obtain a laterite nickel ore leaching solution; carrying out precipitation treatment on the laterite-nickel ore leaching solution to obtain nickel-cobalt solution, and carrying out impurity removal treatment and extraction treatment on the nickel-cobalt sulfate solution to obtain battery-grade nickel sulfate and cobalt sulfate; the impurity-removing extractant in the impurity-removing treatment is P204, and the extractant adopted in the extraction treatment is CPH88, so that the method can realize the cooperative recovery of nickel and cobalt. CN112941338A discloses a method for co-extracting and enriching nickel and cobalt in a mixed solution, which comprises the following steps: (1) Performing homogeneous saponification on the P507 extractant by adopting alkali to obtain a saponified extractant; (2) Co-extracting, standing and separating cobalt-nickel solution containing impurities by adopting a saponified extractant to obtain a nickel-cobalt loaded organic phase; (3) Pickling the organic phase with sulfuric acid to obtain a nickel-cobalt loaded organic phase after pickling; (4) And (3) carrying out back extraction on the acid-washed organic phase by adopting a sulfuric acid back extractant to obtain a water phase containing nickel and cobalt. The existing nickel-cobalt extractant is mainly P204 and P507, which are acidic extractants, and the process of reacting with nickel-cobalt is a cation exchange process. In the use of the extractant, alkali is generally required to be added for saponification of the extractant, or the pH value is regulated to be proper in the extraction process, so that the consumption of acid and alkali is high, the salt content in the wastewater generated by extraction treatment exceeds the standard, and the wastewater treatment problem is caused; if ammonia water is adopted for saponification of the extractant or the pH value of the extraction balance is adjusted, the ammonia nitrogen content in the wastewater can be increased, and the wastewater treatment cost can be increased.
Another system for nickel cobalt extraction separation is the chloride system, which uses amine extractants (e.g., N235) to form CoCl by Co (II) 4 2- Co is subjected to anion exchange extraction, while Ni (II) is not extracted, thereby realizing nickel/cobalt separation. However, for the solution separation of a small amount of Ni in a large amount of Co, the saturation capacity of the amine extractant is small, the Ni is separated by completely extracting Co, the workload is large, and the operation cost is high. In addition, nickel and cobalt are often accompanied with impurities such as pig iron, zinc, copper, manganese, magnesium, calcium and the like, and pure nickel and cobalt are required to be removed in the extraction production, so that a plurality of extraction systems are adopted to separate and remove the impurities in a plurality of extraction cycles at present, and the process flow is long, the consumption of reagents is large, and the cost is high.
Therefore, development of an extractant with better separation effect and larger capacity is an important research point in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an extractant, a preparation method and application thereof, wherein the extractant takes a nitrogen-containing heterocyclic amide compound as an effective component, is particularly suitable for a chloride or nitrate system, can efficiently separate impurities such as manganese, magnesium, calcium and the like, and is used for purifying nickel and cobalt, and has the advantages of large extraction capacity, good separation effect, low reagent consumption and simple process.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an extractant comprising a combination of a diluent and a nitrogen-containing heterocyclic amide compound having a structure as shown in formula I:
in the formula I, R 1 Selected from C4-C20 (e.g., C4, C5, C6, C7, C8, C9, C10, C11, C12, C14, C16, C18, etc.) contentAny one of the aza aryl groups.
In the formula I, R 2 Any one selected from hydrogen, C8-C12 (e.g., C8, C9, C10, C11, or C12) straight or branched alkyl;
in the formula I, R 3 Selected from any of C8-C12 (e.g., C8, C9, C10, C11, or C12) straight or branched chain alkyl groups.
In the extractant provided by the invention, the nitrogen-containing heterocyclic amide compound with the structure shown in the formula I is used as a main active ingredient, is used for separating nickel and cobalt of a chloride and/or nitrate system, does not need acid-base regulation, preferentially extracts Ni (II) and separates Co (II), and the extractant is used for extracting Fe (III), cu (II) and Zn (II) more strongly than Ni (II) and hardly extracting Mn (II), ca (II) and Mg (II). The extractant is particularly suitable for being used as a nickel-cobalt extractant, can preferentially extract nickel and cobalt from nickel-cobalt feed liquid and separate impurity elements such as manganese, magnesium, calcium and the like, has large extraction capacity and good separation effect, adopts water back extraction, and has low reagent consumption.
Preferably, said R 1 Selected from the group consisting of pyrrolylPyridyl->Quinolinyl radicalsOr isoquinolinyl->Any one of them; the dotted line represents the attachment site of the group.
Preferably, said R 2 Selected from any one of hydrogen, octyl, isooctyl, decyl, isodecyl or dodecyl.
Preferably, said R 3 Selected from any one of octyl, isooctyl, decyl, isodecyl or dodecyl.
Preferably, the nitrogen-containing heterocyclic amide compound includes N-octylquinoline-8-carboxamide, N-isooctylquinoline-8-carboxamide, N, N-di (octylquinoline-8-carboxamide, N, N-di (isooctyl) quinoline-8-carboxamide, N-octylisoquinoline-8-carboxamide, N-isooctyl isoquinoline-8-carboxamide, N, N-di (octyl) isoquinoline-8-carboxamide, N, N-di (isooctyl) isoquinoline-2-carboxamide, N-dodecylquinoline-8-carboxamide, N, N-bis (dodecyl) quinoline-8-carboxamide, N-dodecylisoquinoline-8-carboxamide, N, N-bis (dodecyl) isoquinoline-8-carboxamide, N-octyl-1H-pyrrole-2-carboxamide, N-isooctyl-1H-pyrrole-2-carboxamide, N, N-di (isooctyl) -1H-pyrrole-2-carboxamide, N, N-dodecyl-quinoline-8-carboxamide, N-dodecylisoquinoline-8-carboxamide, N, N-bis (dodecyl) isoquinoline-2-carboxamide, N-octyl-2-carboxamide, N-pyrrole-carboxamide, N-2-carboxamide, N-octyl-1H-pyrrole-carboxamide, N-octyl-1H-pyrrole-3-carboxamide, N-isooctyl-1H-pyrrole-3-carboxamide, N-di (octyl) -1H-pyrrole-3-carboxamide, N-di (isooctyl) -1H-pyrrole-3-carboxamide, N-dodecyl-1H-pyrrole-3-carboxamide, N-bis (dodecyl) -1H-pyrrole-3-carboxamide, N-octylpyridine-3-carboxamide, N-isooctylpyridine-3-carboxamide, N-di (octyl) pyridine-3-carboxamide, N, any one or a combination of at least two of N-di (isooctyl) pyridine-3-carboxamide, N-octylpyridine-4-carboxamide, N-isooctylpyridine-4-carboxamide, N-di (octyl) pyridine-4-carboxamide, N-di (isooctyl) pyridine-4-carboxamide, N-dodecylpyridine-3-carboxamide, N-dodecylpyridine-4-carboxamide, N-bis (dodecyl) pyridine-3-carboxamide or N, N-bis (dodecyl) pyridine-4-carboxamide.
As a preferred technical scheme of the invention, the nitrogen-containing heterocyclic amide compound with the structure shown in the formula I can be purchased through a market approach, and can also be prepared through an amide reaction. Illustratively, the preparation routes for the nitrogen-containing heterocyclic amide compounds and related references are as follows:
route one: the R is 2 Is a hydrogen gas which is used as a hydrogen gas,
route two: the R is 2 Is any one of C8-C12 straight chain or branched alkyl,
wherein R is 1 And R is 3 Has the same defined range as in formula I.
The nitrogen-containing heterocyclic amide compound can also be synthesized by referring to the following documents: "Extraction of copper from acid chloride solutions by N-alkyl-and N, N-dialkylyl-3-pyridinecarboxamides", borowiak-research A., solvent Extraction and Ion Exchange,2007, 12 (3), 557-569; "Synthesis of N- (2-ethylhexyl) -pyridine-4-carboxamide and its synergistic behaviors with dinonylnaphthalene sulfonic acid for the selective extraction of nickel and cobalt", liu W. Et al Separation and Purification Technology,2022, 286:p.120385.
Preferably, the volume percentage of the nitrogen-containing heterocyclic amide compound in the extractant is 5-50%, for example, may be 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and specific point values between the above point values, limited in space and for brevity, the invention is not exhaustive list of specific point values included in the range, and more preferably 10-40%.
Preferably, the diluent comprises any one or a combination of at least two of sulfonated kerosene, kerosene or aliphatic hydrocarbon solvent oils.
Preferably, the aliphatic hydrocarbon solvent oil is solvent oil DT100 and/or D110.
Preferably, the extractant further comprises a phase modifier.
As a preferred embodiment of the present invention, the extractant includes a phase modifier which helps to adjust the polarity of the nitrogen-containing heterocyclic amide compound, and to increase the solubility of the nitrogen-containing heterocyclic amide compound in the diluent, thereby avoiding the occurrence of "three phases" during the extraction process.
Preferably, the phase modifier comprises a neutral phosphate and/or a fatty alkanol.
Preferably, the phase modifier comprises any one or a combination of at least two of isooctanol, sec-octanol, dodecanol, isotridecanol or tributyl phosphate.
Preferably, the extractant comprises 1-30% by volume of the phase modifier, for example, 2%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 20%, 22%, 25% or 28%, and specific values between the above values, and the invention is not intended to be exhaustive or to limit the invention to the specific values included in the ranges.
Preferably, the extractant comprises, in volume percent: 10-40% of nitrogen-containing heterocyclic amide compound, 1-30% of phase modifier and the balance of diluent.
In a second aspect, the present invention provides a process for the preparation of an extractant as described in the first aspect, the process comprising: mixing the nitrogen-containing heterocyclic amide compound with a diluent to obtain the extractant.
In a third aspect, the present invention provides the use of an extractant as described in the first aspect in the separation, extraction or purification of metals.
Preferably, the metal comprises any one or a combination of at least two of Cu, zn, ni, co, mn, ca, mg or Fe.
As a preferred technical scheme of the invention, the extractant is used for separating, extracting or purifying metals in a chloride and/or nitrate system, is particularly suitable for the chloride system, preferentially extracts nickel and further extracts cobalt, and the extraction sequence is as follows: cu (Zn) Fe (III) > Ni > Co > Mn Ca Mg. The extraction agent provided by the invention has important significance in the separation of nickel and cobalt because the technology for separating iron, copper and zinc is mature, can be used as a nickel-cobalt extraction agent, can fully remove impurity elements such as calcium, magnesium and manganese, purify nickel and cobalt, and realize the effective separation of nickel and cobalt through the back extraction of water, and is suitable for the separation of nickel and cobalt in nickel ore leaching solution, the removal of a small amount of nickel in cobalt, the direct co-extraction of nickel and cobalt in ternary battery leaching solution and the like.
In a fourth aspect, the present invention providesA method for separating metals in a nickel-cobalt feed liquid, comprising: extracting the nickel cobalt feed solution with the extractant of the first aspect to obtain a loaded organic phase and a raffinate phase; the anions in the nickel cobalt feed liquid comprise Cl - And/or NO 3 - 。
Preferably, the anions in the nickel cobalt feed solution comprise Cl - Namely, the nickel cobalt feed liquid is a chloride system, the extraction agent provided by the invention is adopted for extraction and separation treatment, and the extraction and separation can be carried out through anions (MCl) x n- ) Exchange or solvation of neutral molecular forms occurs without pH adjustment; the loaded organic phase is back extracted by water, no acid and alkali is consumed, and the medium is easy to circulate (mother liquor is circulated after HCl is volatilized and recycled or temperature change is crystallized).
Preferably, the nickel cobalt feed liquid is hydrochloric acid leaching liquid of nickel ore.
Preferably, the pH of the nickel cobalt solution is 2-7, for example, the pH may be 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 or 6.5, and specific values between the above values, which are limited in space and for brevity, the present invention is not intended to be exhaustive.
Preferably, the concentration of the anions in the nickel cobalt feed solution is 2-7mol/L, for example, may be 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L or 6.5mol/L, and specific point values between the above point values, which are limited in length and for brevity, the present invention is not exhaustive.
Preferably, anions (Cl) in the nickel cobalt feed solution - ) The concentration of (2) may be adjusted by adding hydrochloride (e.g. sodium chloride and/or ammonium chloride) to a concentration of 2-7mol/L.
Preferably, the volume ratio (O/A) of the extractant to the nickel cobalt feed liquid is 1 (0.1-10), for example, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9, etc.
Preferably, the extraction is a multistage countercurrent extraction.
Preferably, the multistage countercurrent extraction has a number of stages of 2-10 stages, for example 3, 4, 5, 6, 7, 8 or 9 stages.
Preferably, the loaded organic is back-extracted with water to yield nickel and cobalt, respectively.
Preferably, the volume ratio (O/A) of the loaded organic to water is (1-50): 1, which may be, for example, 2:1, 5:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, etc.
Preferably, the stripping is multistage countercurrent stripping.
Preferably, the multistage countercurrent stripping has a stage number of 2-10 stages, for example, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages or 9 stages.
Preferably, the loaded organic phase further comprises a washing step prior to stripping.
Preferably, the washed reagent is a hydrochloride solution and/or a nitrate solution.
Preferably, the anions in the nickel cobalt feed liquid are Cl - The washed reagent is a hydrochloride salt (e.g., sodium chloride) solution.
Preferably, the concentration of the hydrochloride solution is 2-7mol/L, for example, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L or 6.5mol/L, and the specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the volume ratio (O/A) of the loaded organic phase to the washed reagent is (1-30): 1, for example, it may be 3:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 19:1, 20:1, 23:1, 25:1, 27:1 or 29:1, etc.
Preferably, the separation method comprises the steps of:
(1) Extracting the nickel-cobalt feed liquid by adopting the extractant to obtain a loaded organic phase and a raffinate water phase; the anions in the nickel cobalt feed liquid comprise Cl - The method comprises the steps of carrying out a first treatment on the surface of the The pH value of the nickel-cobalt feed liquid is 2-7, and Cl in the nickel-cobalt feed liquid - The concentration of (2) is 2-7mol/L; the volume ratio of the extractant to the nickel cobalt feed liquid is 1 (0.1-10);
(2) Washing the loaded organic phase obtained in the step (1) by using a hydrochloride solution to obtain a washed loaded organic phase; the concentration of the hydrochloride solution is 2-7mol/L; the volume ratio of the loaded organic phase to the hydrochloride solution in the washing is (1-30): 1;
(3) Carrying out back extraction on the washed loaded organic phase obtained in the step (2) by using water to obtain nickel and cobalt; the volume ratio of the washed loaded organic phase to the water is (1-50): 1.
Compared with the prior art, the invention has the following beneficial effects:
the extractant provided by the invention takes the nitrogen-containing heterocyclic amide compound as an active ingredient, is especially suitable for metal separation in a chloride or nitrate system, can efficiently separate impurities such as manganese, magnesium, calcium and the like, and can purify nickel and cobalt. The extractant preferentially extracts nickel and separates cobalt, fills the blank of selectively extracting nickel and separating cobalt in nickel/cobalt separation, separates impurities such as iron, copper, zinc, manganese, calcium, magnesium and the like through a single extractant, and simplifies the flow. The extractant is particularly suitable for being used as a nickel-cobalt extractant for separating metals in nickel-cobalt feed liquid, the extraction rate of nickel and cobalt can reach more than 90%, the extraction rate of nickel can even reach 99%, the extraction capacity is large, the separation effect is good, the extraction efficiency is high, the phase separation time is less than or equal to 15min, the reagent consumption is low, the process is simple, the acid-base consumption is not needed in the extraction process, the operation cost is low, the complex wastewater treatment problem is not brought, and the environment is protected.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The materials used in the following embodiments of the present invention are obtained by the following means:
(1) Nitrogen-containing heterocyclic amide compounds: obtained by market purchase or by amide reaction. The preparation route of the nitrogen-containing heterocyclic amide compound and related references are as follows:
route one: by a means ofThe R is 2 Is a hydrogen gas which is used as a hydrogen gas,
route two: the R is 2 Is any one of C8-C12 straight chain or branched alkyl,
wherein R is 1 And R is 3 Has the same defined range as in formula I.
Illustratively, the nitrogen-containing heterocyclic amide compounds may also be synthesized with reference to the following references: document 1: "Extraction of copper from acid chloride solutions by N-alkyl-and N, N-dialkylyl-3-pyridinecarboxamides", borowiak-research A., solvent Extraction and Ion Exchange,2007, 12 (3), 557-569; document 2: "Synthesis of N- (2-ethylhexyl) -pyridine-4-carboxamide and its synergistic behaviors with dinonylnaphthalene sulfonic acid for the selective extraction of nickel and cobalt", liu W. Et al Separation and Purification Technology,2022, 286:p.120385.
Specifically, the N-isooctylpyridine-4-carboxamide is obtained by reacting 4-picolinic acid with isooctylamine; n-octyl pyridine-4-formamide is obtained by reacting 4-picolinic acid with N-octylamine; n-isooctyl quinoline-8-formamide is obtained by reacting 8-quinoline carboxylic acid with isooctylamine; n, N-di (isooctyl) quinoline-8-carboxamide is obtained from the reaction of 8-quinolinecarboxylic acid with diisooctylamine; N-octyl-1H-pyrrole-2-carboxamide is obtained by reacting pyrrole-2-carboxylic acid with N-octylamine; N-isooctyl-1H-pyrrole-2-carboxamide is obtained by reacting pyrrole-2-carboxylic acid with isooctylamine; n, N-bis (dodecyl) -1H-pyrrole-2-carboxamide is obtained by reacting pyrrole-2-carboxylic acid with didodecyl amine; the synthesis process parameters can be found in reference 2.
(2) Phase modifier: tributyl phosphate (TBP), isotridecyl alcohol, available from Chongqing Kangpu chemical industries, inc.
(3) A diluent: kerosene, aliphatic hydrocarbon solvent oil DT100, available from Chongqing Kangpu chemical industries, inc.
Example 1
An extractant comprising, in volume percent: 30% of nitrogen-containing heterocyclic amide compound (N-isooctylpyridine-4-carboxamide), 5% of phase modifier (tributyl phosphate, TBP), and the balance of diluent (kerosene).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 2
An extractant comprising, in volume percent: 10% of nitrogen-containing heterocyclic amide compound (N-isooctylpyridine-4-carboxamide), 1% of phase modifier (TBP), and the balance of diluent (kerosene).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 3
An extractant comprising, in volume percent: 40% of nitrogen-containing heterocyclic amide compound (N-isooctylpyridine-4-carboxamide), 20% of phase modifier (TBP), and the balance of diluent (kerosene).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 4
An extractant comprising, in volume percent: 30% of nitrogen-containing heterocyclic amide compound (N-octyl pyridine-4-carboxamide), 5% of phase modifier (TBP) and the balance of diluent (kerosene).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 5
The nickel cobalt extractant comprises the following components in percentage by volume: 30% of nitrogen-containing heterocyclic amide compound (N-isooctyl quinoline-8-formamide), 5% of phase modifier (isotridecyl alcohol) and the balance of diluent (DT 100).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 6
The nickel cobalt extractant comprises the following components in percentage by volume: nitrogen-containing heterocyclic amide compound (N, N-di (isooctyl) quinoline-8-carboxamide) 30%, phase modifier (isotridecyl alcohol) 5%, balance of diluent (DT 100).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 7
The nickel cobalt extractant comprises the following components in percentage by volume: 30% of nitrogen-containing heterocyclic amide compound (N-octyl-1H-pyrrole-2-carboxamide), 5% of phase modifier (isotridecyl alcohol) and the balance of diluent (DT 100).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 8
The nickel cobalt extractant comprises the following components in percentage by volume: 30% of nitrogen-containing heterocyclic amide compound (N-isooctyl-1H-pyrrole-2-carboxamide), 5% of phase modifier (isotridecyl alcohol) and the balance of diluent (DT 100).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Example 9
The nickel cobalt extractant comprises the following components in percentage by volume: 30% of nitrogen-containing heterocyclic amide compound (N, N-bis (dodecyl) -1H-pyrrole-2-carboxamide), 5% of phase modifier (isotridecyl alcohol) and the balance of diluent (DT 100).
The preparation method of the extractant comprises the following steps: and uniformly mixing the nitrogen-containing heterocyclic amide compound, the phase modifier and the diluent at room temperature to obtain the extractant.
Application example
The method for separating metals in the nickel-cobalt feed liquid comprises the steps of respectively adopting the extracting agents provided in the embodiments 1-9 for extraction treatment; the nickel cobalt feed liquid is hydrochloric acid leaching liquid of laterite nickel ore, the initial pH value is 4.0, and the composition is as follows: 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+ 。
The separation method specifically comprises the following steps:
(1) Mixing and stirring the extractant and the nickel-cobalt feed liquid, and adding a proper amount of solid sodium chloride to regulate Cl - Concentration, extracting to obtain a loaded organic phase and a raffinate phase; after the extraction balance, the pH value of the nickel cobalt feed liquid is 4, and Cl - The concentration of (2) is 6mol/L; the volume ratio (O/A) of the extractant to the nickel cobalt feed liquid is 1:1; the extraction is 4-stage countercurrent extraction;
(2) Washing the loaded organic phase obtained in the step (1) by using a 6mol/L sodium chloride solution, wherein the volume ratio (O/A) of the loaded organic phase to the sodium chloride solution in the washing is 10:1, and the washing is 3-stage countercurrent washing to obtain a washed loaded organic phase;
(3) And (3) carrying out back extraction on the washed loaded organic phase obtained in the step (2) by using deionized water, wherein the volume ratio (O/A) of the washed loaded organic phase in the back extraction operation is 20:1, and the back extraction is 3-stage countercurrent back extraction, so that metal separation is completed.
And (3) separation effect evaluation:
the concentration of metal ions in the raffinate is quantified by adopting an ICP-OES (inductively coupled plasma emission spectrometer); the content of metal ions in the organic phase is subjected to back extraction by deionized water and is also analyzed by ICP-OES; the metal extraction (Ex) was calculated using the following formula:
wherein C is org And C aq Respectively represent the concentration of metal ions in the aqueous phase of the organic phase, V org And V aq Representing the volumes of the organic and aqueous phases, respectively.
The specific test results are shown in table 1:
TABLE 1
According to the test results shown in Table 1, the extractant provided by the invention takes the nitrogen-containing heterocyclic amide compound as an active ingredient, has good selectivity on nickel and cobalt, the extraction rate of nickel and cobalt can reach more than 90% and even 99%, the impurity ions such as manganese, calcium and magnesium are hardly extracted, the phase separation time is less than or equal to 15min and even less than 5min, the extraction efficiency is high, the capacity is large, the process is simple, and the acid and alkali consumption is not needed in the extraction process.
The components of the extractants according to examples 1 to 9 and the test results in Table 1 show that the extraction of nickel and cobalt with different nitrogen-containing heterocyclic amide compounds as active ingredients also has the following rule: (1) TBP or isotridecyl alcohol and other modifier are added, so that three phases generated in the extraction process can be effectively avoided; for example, the phase modifier content in example 2 is relatively low, resulting in "three phases" in the phase separation. (2) In the nitrogen-containing heterocyclic amide compound, when the carbon chain connected to the amide N is branched, the nitrogen-containing heterocyclic amide compound has better phase separation effect than a linear system. (3) The extraction rate of nickel and cobalt is improved along with the increase of the concentration of the extractant, but the corresponding phase separation time is also increased, and the proper concentration can be selected in practical application; (4) At the same volume concentration, the three types of nitrogen heterocycles are different (i.e. R 1 Different) nitrogen-containing heterocyclic amide compound extractants have the following extraction capacities for nickel and cobalt: pyrrole-containing amide compound > pyridine-containing amide compound > quinoline-containing amide compound. (5) At the same volume concentration, the nitrogen-containing heterocyclic secondary amide compound (i.e., R 2 Is hydrogen) has obviously better extraction capacity to nickel and cobalt than that of the nitrogen-containing heterocyclic tertiary amide compound (namely R 2 A C8-C12 linear or branched alkyl group).
The applicant states that the invention is illustrated by the above examples as an extractant and a method for its preparation and use, but the invention is not limited to, i.e. it is not meant that the invention must be practiced in dependence on the above examples. 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 (10)
1. An extractant comprising a combination of a diluent and a nitrogen-containing heterocyclic amide compound having a structure according to formula I:
wherein R is 1 Any one selected from C4-C20 nitrogen-containing heteroaryl;
R 2 any one selected from hydrogen and C8-C12 straight-chain or branched-chain alkyl;
R 3 is selected from any one of C8-C12 straight chain or branched chain alkyl.
2. The extractant of claim 1 wherein R 1 Any one selected from pyrrolyl, pyridyl, quinolinyl or isoquinolinyl;
preferably, said R 2 Any one selected from hydrogen, octyl, isooctyl, decyl, isodecyl or dodecyl;
preferably, said R 3 Selected from any one of octyl, isooctyl, decyl, isodecyl or dodecyl.
3. The extractant according to claim 1 or 2, wherein the nitrogen-containing heterocyclic amide compound comprises N-octylquinoline-8-carboxamide, N-isooctylquinoline-8-carboxamide, N-di (octylquinoline-8-carboxamide, N-di (isooctyl) quinoline-8-carboxamide, N-octylisoquinoline-8-carboxamide, N-isooctylisoquinoline-8-carboxamide, N-di (octylisoquinoline-8-carboxamide, N-di (isooctyl) isoquinoline-2-carboxamide, N-dodecylquinoline-8-carboxamide, N, N-bis (dodecyl) quinoline-8-carboxamide, N-dodecyl isoquinoline-8-carboxamide, N, N-bis (dodecyl) isoquinoline-8-carboxamide, N-octyl-1H-pyrrole-2-carboxamide, N-isooctyl-1H-pyrrole-2-carboxamide, N, N-di (octyl) -1H-pyrrole-2-carboxamide, N, N-di (isooctyl) -1H-pyrrole-2-carboxamide, N-dodecyl-1H-pyrrole-2-carboxamide, N, N-bis (dodecyl) -1H-pyrrole-2-carboxamide, N-octyl-1H-pyrrole-3-carboxamide, N-isooctyl-1H-pyrrole-3-carboxamide, N-di (octyl) -1H-pyrrole-3-carboxamide, N-di (isooctyl) -1H-pyrrole-3-carboxamide, N-dodecyl-1H-pyrrole-3-carboxamide, N-bis (dodecyl) -1H-pyrrole-3-carboxamide, N-octylpyridine-3-carboxamide, N-isooctylpyridine-3-carboxamide, N-di (octyl) pyridine-3-carboxamide, N, any one or a combination of at least two of N-di (isooctyl) pyridine-3-carboxamide, N-octylpyridine-4-carboxamide, N-isooctylpyridine-4-carboxamide, N-di (octyl) pyridine-4-carboxamide, N-di (isooctyl) pyridine-4-carboxamide, N-dodecylpyridine-3-carboxamide, N-dodecylpyridine-4-carboxamide, N-bis (dodecyl) pyridine-3-carboxamide or N, N-bis (dodecyl) pyridine-4-carboxamide.
4. An extractant according to any one of claims 1 to 3, wherein the volume percentage of nitrogen containing heterocyclic amide compounds in the extractant is from 5 to 50%, preferably from 10 to 40%;
preferably, the diluent comprises any one or a combination of at least two of sulfonated kerosene, kerosene or aliphatic hydrocarbon solvent oils.
5. The extractant according to any one of claims 1 to 4, further comprising a phase modifier;
preferably, the phase modifier comprises a neutral phosphate and/or a fatty alkanol;
preferably, the phase modifier comprises any one or a combination of at least two of isooctanol, sec-octanol, dodecanol, isotridecanol or tributyl phosphate;
preferably, the volume percentage of the phase modifier in the extractant is 1-30%;
preferably, the extractant comprises, in volume percent: 10-40% of nitrogen-containing heterocyclic amide compound, 1-30% of phase modifier and the balance of diluent.
6. A process for the preparation of an extractant according to any one of claims 1 to 5, comprising: mixing the nitrogen-containing heterocyclic amide compound with a diluent to obtain the extractant.
7. Use of an extractant according to any one of claims 1 to 5 for the separation, extraction or purification of metals;
preferably, the metal comprises any one or a combination of at least two of Cu, zn, ni, co, mn, ca, mg or Fe.
8. A method for separating metals in a nickel-cobalt feed liquid, which is characterized by comprising the following steps: extracting the nickel cobalt feed solution with the extractant of any one of claims 1-5 to obtain a loaded organic phase and a raffinate phase; the anions in the nickel cobalt feed liquid comprise Cl - And/or NO 3 - 。
9. The separation method according to claim 8, wherein the pH value of the nickel cobalt feed solution is 2-7;
preferably, the concentration of anions in the nickel cobalt feed liquid is 2-7mol/L;
preferably, the volume ratio of the extractant to the nickel cobalt feed liquid is 1 (0.1-10);
preferably, the extraction is a multistage countercurrent extraction;
preferably, the multistage countercurrent extraction has a stage number of 2-10 stages.
10. The separation process according to claim 8 or 9, characterized in that the loaded organic phase is back-extracted with water to obtain nickel and cobalt, respectively;
preferably, the volume ratio of the loaded organic phase to water is (1-50): 1;
preferably, the back extraction is multistage countercurrent back extraction;
preferably, the multistage countercurrent stripping has a stage number of 2-10 stages;
preferably, the loaded organic phase further comprises a washing step prior to stripping;
preferably, the washed reagent is a hydrochloride solution and/or a nitrate solution;
preferably, the volume ratio of the loaded organic phase to the washed reagent is (1-30): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210043674.4A CN116479237A (en) | 2022-01-14 | 2022-01-14 | Extractant, preparation method and application thereof |
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| CN117004830A (en) * | 2023-09-28 | 2023-11-07 | 上海稀固科技有限公司 | Method for recovering nickel from nickel-containing iron material liquid |
| CN117004830B (en) * | 2023-09-28 | 2023-12-08 | 上海稀固科技有限公司 | Method for recovering nickel from nickel-containing iron material liquid |
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