CN1109913A - A process for the extraction and separation of nickel and/or cobalt - Google Patents
A process for the extraction and separation of nickel and/or cobalt Download PDFInfo
- Publication number
- CN1109913A CN1109913A CN95102797A CN95102797A CN1109913A CN 1109913 A CN1109913 A CN 1109913A CN 95102797 A CN95102797 A CN 95102797A CN 95102797 A CN95102797 A CN 95102797A CN 1109913 A CN1109913 A CN 1109913A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- metal
- ion
- organic phase
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 275
- 239000010941 cobalt Substances 0.000 title claims abstract description 105
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 105
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 102
- 238000000926 separation method Methods 0.000 title claims abstract description 13
- 238000000605 extraction Methods 0.000 title claims description 162
- 238000000034 method Methods 0.000 title claims description 114
- 230000008569 process Effects 0.000 title claims description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 112
- 239000002184 metal Substances 0.000 claims abstract description 112
- 239000012074 organic phase Substances 0.000 claims abstract description 96
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 59
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 43
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 41
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 119
- 239000003795 chemical substances by application Substances 0.000 claims description 95
- 239000002994 raw material Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000000638 solvent extraction Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000011575 calcium Substances 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 19
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 19
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 16
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 229910001710 laterite Inorganic materials 0.000 claims description 4
- 239000011504 laterite Substances 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 238000001149 thermolysis Methods 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims 10
- 150000002738 metalloids Chemical class 0.000 claims 9
- 229910052728 basic metal Inorganic materials 0.000 claims 5
- 150000003818 basic metals Chemical class 0.000 claims 5
- 239000011260 aqueous acid Substances 0.000 claims 3
- 238000005272 metallurgy Methods 0.000 claims 3
- 150000002815 nickel Chemical group 0.000 claims 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- 229910001436 Cr3+ Inorganic materials 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 46
- 238000009854 hydrometallurgy Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000012527 feed solution Substances 0.000 abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 150000008427 organic disulfides Chemical class 0.000 description 19
- 150000003009 phosphonic acids Chemical class 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 13
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 12
- YOCZZJWFWDUAAR-UHFFFAOYSA-N sulfanyl-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(S)(=S)CC(C)CC(C)(C)C YOCZZJWFWDUAAR-UHFFFAOYSA-N 0.000 description 12
- 239000003978 infusion fluid Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 229910000906 Bronze Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 10
- 239000010974 bronze Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 150000002923 oximes Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000000658 coextraction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 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 3
- 239000000284 extract Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical group CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000009852 extractive metallurgy Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 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
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical compound OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 201000008827 tuberculosis Diseases 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/381—Phosphines, e.g. compounds with the formula PRnH3-n, with n = 0-3
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/385—Thiophosphoric acids, or esters thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a hydrometallurgical process for the recovery of metals. In particular, an aqueous feed solution derived from acid leaching is provided. The aqueous feed solution contains nickel and/or cobalt ions. The pH of the solution is maintained at a level between about 2 and 6. The aqueous feed solution is contacted with a water-immiscible organic phase containing an extractant to load the nickel and/or cobalt metal ions to form a metal-bearing organic phase. The metal-bearing organic phase is then separated from the metal-containing aqueous feed solution. Finally, after separation from the aqueous feed solution, the metal-bearing organic phase is contacted with an aqueous strip solution to recover the loaded nickel and/or cobalt from the metal-bearing organic phase.
Description
The present invention relates to hydrometallurgy, more particularly, relate to the aqueous solution recovery and separating nickel and/or the cobalt that go out to obtain by the acidleach of ore by liquid-liquid extraction.
In solvent extraction method, the organic phase of forming by organic extractant, organic thinner and organic soluble compounds of optional being commonly referred to " phase modifier " with adverse current, cross-flow or and stream mode contact one or more stages with the water that is loaded with metal ingredient.Should select organic phase by this way so that organic phase and water unmixing.Water shows and does not contain these metal ingredients thereby the metal ion exchanged of the hydrogen ion of organic phase and water makes organic phase be loaded with metal ingredient.Usually the pH by the control water keeps exchange efficiency, and regulates the selectivity of metal in the exchange process.After the extraction, the organic phase that is loaded with metal with adverse current, cross-flow or and stream mode contact one or more stages with sour, thereby metal ingredient is converted into the aqueous solution.Then, can in all sorts of ways electrowinning for example reclaims metal ingredient in this aqueous solution.
Known can be by from the acid infusion solution of dilution for example leaches the solution of laterite, reclaiming nickel and cobalt effectively with hydrogen sulfide precipitation.When precipitating with hydrogen sulfide, the precipitation that is mixed with nickelous sulfide/cobalt of gained can comprise the further refining of solvent-extracted operation by choosing wantonly.Preferably, solvent extraction is directly carried out in infusion solution and without the sulfide precipitation step.This direct solvent extraction routes exempted with hydrogen sulfide be difficult to produce and handle relevant expense, and have the possibility of direct production market product effectively.
Be used to reclaim to the industrialization of direct solvent extracting process copper existing many years.For cobalt and nickel, solvent extraction almost only is confined to the refining (Bautista of intermediate nickel-cobalt product, R., " The Solvent Extraction of Nickel; Cobalt; and their Associated Metals. " Extractive Metallurgy of Copper, Nickel and Cobalt, vol.I; Fundamental Aspects, R.Reddy ﹠amp; R.Weizenbach(Editors), The Minerals, Metals and Materials Society, 1993, pp.827-852).It is directly to reclaim nickel/cobalt from the ammonia leach liquor that an exception is only arranged, for example at United States Patent (USP) 3,907, and 966 and 3,981, described in 968.
Attempt to transform existing solvent extraction agent with from using for example direct acidleach of sulfuric acid to go out to reclaim nickel the solution of ore or concentrate gained and cobalt is unsuccessful basically.A major cause is that these solution generally contain a large amount of dissolved manganese, magnesium and/or calcium, and these metals usually are extracted with nickel and cobalt.Organophosphorus and carboxylic acid extraction agent extraction cobalt and nickel for example, but also usually even preferred coextraction manganese (and more a spot of calcium and magnesium).The coextraction of these metal ions has consumed the loading capacity of most of extraction agent, and makes it to obtain pure strip liquor.It is unacceptable to make that at last this extraction agent becomes industry.In addition, excessive water-soluble also is a problem usually for extraction agent such as carboxylic acid.
Contain the selectivity that the extraction agent of carboxylic acid and non-chelating oxime mixture has been proved for nickel and cobalt and be higher than manganese, magnesium and calcium.Yet non-chelating oxime has highly water-soluble usually, therefore helps hydrolysis.Chelated hydroxy oxime extraction agent such as ketoxime class and salicylic aldehyde oximes, its most of industrial being used for from sulfuric acid infusion solution extracting copper (II), the selectivity that also has been proved for nickel and cobalt (II) is higher than manganese, calcium and magnesium.Yet in case add in these chelating oximes, cobalt (II) tends to be oxidized to cobalt (III), and this is unfavorable for stripping and the oxime reagent of may degrading.In addition, existing report: when using chelating oxime extraction agent the percentage extraction of nickel very low (Szymanowski, J., Hydroxyoximes and Copper Hydrometallurgy, CRC Press, 1993, P.281).The mixture of chelated hydroxy oximes and dinonylnaphthalene sulfonic acid (DNNS) has been proved and can have improved the nickel extraction, yet DNNS has quickened degraded (Oliver, the A.J. ， ﹠amp of oxime; Ettel, V.A., " LIX 65N and Dowfax 2AO Interaction in Copper Solvent Extraction and Electrolysis ", and CIM 14 th Annual Conf, Edmonton, in August, 1975, PP.383-88).
People such as Brown are at United States Patent (USP) 4,721, disclose in 605 to use the dithiophosphinic acids class can be with the metal that is selected from zinc, silver, cadmium, mercury, nickel, cobalt and copper and calcium and/or the isolating method of magnesium that is present in the aqueous solution by solvent extraction.In addition, B.T.Tait " Cobalt-Nickel Separation:The Extraction of Cobalt(II) and Nickel (II) by Cyanex 301; Cyanex 302 and Cyanex 272; " Hydrometallurgy, 32(1993) having reported Cyanex301 extraction agent (Cyanex is the trade mark that Cytec Canada Inc. gives the organophosphorus extraction agent) among the PP.365-372 can extraction of nickel and cobalt and can be used for optionally removing cobalt from solution containing nickel.Yet, the difference of extraction 50% cobalt pH value during with 50% nickel relative less only be 1.1 units.In this piece article, Tait has also illustrated the shortcoming that needs with strong acid reextraction cobalt when using Cyanex 301 extraction agents.Tait at " The Extraction of Some Base Metal Ions by Cyanex 301; Cyanex 302 and Binary Extractant Mixtures with Aliquat 336; " Solv.Extr.Ion Exth., 10(5) point out among (1992) pp.799-809, when being higher than the pH value of nickel and cobalt, also can extract manganese with Cyanex 301.People such as Sole at " Solvent Extraction Characteristics of Thiosubstituted Organophosphinic Acid Extractants; " Hydrometallurgy, 30(1992) having illustrated among the pp.345-65 almost can not separating nickel and cobalt with Cyanex 301.Opposite with Tait, people such as Sole point out that Cyanex 301 is preferable over cobalt slightly for nickel.In addition, Cote and Bauer at " Metal Complexes with organothiophosphorus Ligands and Extraction phenomena; " Reviews in Inorganic Chemistry, Vol.10, Nos, 1-3, (1989) the Fe(III that the organic thiophosphorous acid of a class (organothiophosphorus acid) extraction agent can be existed in the solution has been described among the pp.121-144) and by the Co(III) be oxidized to disulphide, described Co(III) by atmosphericoxygen oxidation Co(II) thereby in organic phase, form.Cote and Bauer further point out can avoid the Co(II in organic phase such as trioctylphosphine oxide (TOPO) (TOPO), tributyl phosphate (TBP) or octanol (ROH) in the presence of oxygenate (oxygen donor reagents)) be oxidized to the Co(III).
None discloses the industrial feasible method that optionally reclaims metal such as nickel and/or cobalt from the acidic solution of metal such as manganese, calcium and magnesium in the above-mentioned document.For example, the acidleach of nickeliferous laterite goes out the infusion solution that for example obtains containing nickel and cobalt, a large amount of impurity such as manganese and the magnesium of normal mixing in this solution.Therefore, best method is only optionally solvent extraction nickel and a cobalt from the aqueous solution that contains nickel and cobalt and manganese, magnesium etc. concerning this area.By solvent extraction with nickel and cobalt and other metal initial gross separations after, often need nickel is separated with cobalt with other solvent extraction agent.Can and nickel and the isolating single extraction agent of cobalt more can be helped the recovery of nickel and cobalt with nickel and cobalt and other metal separation.
The purpose of this invention is to provide a kind of method that optionally reclaims nickel and/or cobalt composition from acidic aqueous solution, this method is used solvent extraction and has been avoided being present in for example coextraction of (but being not limited to) manganese, calcium and magnesium of other metal ingredients in the same solution.
Consistent with above-mentioned purpose, further aim of the present invention provides a kind of simple and economic method.
Consistent with above-mentioned one or two purposes, further aim of the present invention provides the organic phase of reusable back extraction.
Consistent with above-mentioned one or two purposes, further aim of the present invention provides by the organic mutual-assistance nickel of load of optionally stripping separates with cobalt.
Consistent with above-mentioned one or more purposes, further aim of the present invention provides by optionally being written into organic mutual-assistance nickel separates with cobalt.
The invention provides the hydrometallurgical that reclaims metal.Specifically, the invention provides the aqueous solution of raw material that goes out to produce by acidleach.Aqueous solution of raw material contains nickel and/or cobalt ion.The pH of solution remains on about 2 to 6.Aqueous solution of raw material with contain contacting of extraction agent with the immiscible organic phase of water, thereby carry to go up nickel and/or the cobalt metal ion forms the organic phase that has metal.Extraction agent contains at least a organic soluble dithiophosphinic acids, its an alkali metal salt, alkaline earth salt or ammonium salt.Chromium (VI) ion, iron (III) ion and the cupric ion that aqueous solution of raw material contains enough low amount makes reusable extraction agent.Then, the organic phase that will have metal is separated from the aqueous solution of raw material that contains metal.At last, after from aqueous solution of raw material, separating, the organic phase that has metal is contacted with stripping aqueous solution, from the organic phase that has metal, to reclaim contained nickel and/or cobalt.
The present invention has found by chromium (VI), iron (III) and cupric ion are remained on the amount of reusable extraction agent that makes, thereby has made organic disulfide generation phosphonic acids extraction agent can be used for isolating effectively nickel and/or cobalt from acid leach solution.
The present invention has further found, by using organic disulfide generation phosphonic acids extraction agent extraction of nickel and cobalt together, optionally strip from organic disulfide generation phosphonic acids extraction agent with the water soluble acid solution of dilution then and be total to the cobalt that carries, and then with the more strong solution reextraction nickel of identical or different water soluble acid, thereby the separation of realization nickel/cobalt.
The present invention has further found, by optionally only nickel being written into organic disulfide generation phosphonic acids extraction agent, cobalt is stayed in the moisture raffinate basically, uses then that identical or other extraction agent extracts this cobalt by cyclical operation separately.After optionally being written into,, thereby can realize the separation of nickel/cobalt with the water soluble acid solution of identical or different kind reextraction nickel and cobalt from each have the organic extractant that carries.
The present invention also found, organic disulfide generation phosphonic acids extraction agent can be used for separating with manganese (II) by nickel and/or cobalt that solvent extraction will be present in the acid leaching solution of oxide compound ore effectively.Organic disulfide generation phosphonic acids extraction agent nickel and cobalt ion easy and in the organic phase combine, and mn ion is stayed in the moisture raffinate.
Method of the present invention uses the dithiophosphinic acids extraction agent to isolate nickel and/or cobalt from acid leaching liquor.The specific examples that is suitable for the ore that acidleach goes out comprises and contains nickel and/or cobalt.The specific examples that is suitable for the ore that acidleach goes out comprises oxide compound ore, sulfide ore and manganese or marine products tuberculosis ore deposit (the sea nodules) that contains nickel and/or cobalt.Most preferably, method of the present invention is used for laterite.
Before nickel and/or cobalt ion were written into extraction agent, infusion solution must be remained on pH was about 2 to 6.Preferably, before being written into, making infusion solution remain on pH is about 3 to 6.Most preferably, before being written into, making infusion solution remain on pH is about 3 to 5.5.Preferably, before extraction step, infusion solution is partly neutralized to remove free acid.Remove in the part N-process that free acid can extremely reduce or even the solvent extraction operation having avoided following in need to add alkali.In the part N-process, most of iron (III), chromium (III), aluminium and cupric ion precipitation, and most of nickel and cobalt ion are stayed in the solution.Post precipitation, in the solid/liquid separation step, these ions are easy to separate from aqueous solution of raw material.In some cases, before the part neutralization procedure, may need with Fe(II) ionic oxide formation is the Fe(III) ion.Preferably, by contact II with the gas that contains aerobic with Fe() ionic oxide formation is the Fe(III) ion.In some cases, when manganese (IV) ion was present in the infusion solution, manganese (IV) ion also precipitated in the part N-process.The part neutralization can use any suitable alkali reagent to finish.Most preferably, regulate the pH of infusion solution with lime carbonate.
Preferably, removing the Fe(III) behind the ion, remaining iron (III) ion is reduced to the Fe(II) ion to be to prevent the unnecessary degraded of extraction agent.Can use chemical reducing agent such as SO
2, reduction Fe(III such as sulphite, hydrosulphite, soluble sulfide) ion.
For extraction of nickel from infusion solution and/or cobalt, make solution and organic soluble dithiophosphinic acids, its an alkali metal salt, alkaline earth salt or ammonium salt contact.The dithiophosphinic acids extraction agent is preferably represented with following formula:
R wherein
1And R
2Can be identical or different and be alkyl, cycloalkyl, alkoxyalkyl, alkyl-cycloalkyl, aryl, alkylaryl, aralkyl or the cycloalkyl aryl of replacement with 2 to 24 carbon atoms.Most preferably, R
1And R
2Respectively do for oneself (2,4, the 4-tri-methyl-amyl); This pair (2,4, the 4-tri-methyl-amyl) dithiophosphinic acids can be bought from Cytec Canada Inc., and trade mark is Cyanex 301 extraction agents.When extraction agent used with its sour form, M can be hydrogen.In addition, when extraction agent used with its salt, M can be alkalimetal ion, alkaline-earth metal ions or ammonium ion.Most preferably, M is a hydrogen.In solvent extraction, nickel and/or cobalt ion replace M, therefore make extraction agent carry these metal ions.Extraction agent is loaded.
In metal reextraction process, water miscible acid solution provides the necessary hydrogen of the metal that is extracted of the M position that is used to be substituted in extraction agent.Then by as this method reextraction, extraction agent is capable of circulation to be used to repeat to load nickel and/or cobalt ion.
Have now found that if in aqueous solution of raw material, exist chromium (VI) ion will greatly and promptly reduce the metal extraction ability of organic disulfide generation phosphonic acids extraction agent.Industrial feasible manipulation require is reused extraction agent.Preferably, extracting power only reduce about 10% or still less the time extraction agent can be used at least 10 times.Therefore; in order to protect extraction agent and to make it repeatedly bring into play optimum performance in the metal extraction and the operation of stripping; unhydrolyzable oxidation composition such as chromium (VI) ion in the part neutralization procedure are preferably in organic disulfide generation phosphonic acids extraction agent and carry out removing before the solvent extraction.People can recognize, when chromium (VI) concentration is very low, can carries out chromium (VI) and remove step.Can in all sorts of ways and remove chromium (VI).For example, in the part neutralization procedure, chromium (VI) is reduced to chromium (III) thereby also precipitates can be at an easy rate except that dechromising (VI).Preferably, being used to reduce chromium (VI) ionic reductive agent is sulphur class reductive agent such as metabisulphite, sulfur dioxide gas or water-soluble sulfide.In addition, hydrogen peroxide can be used for chromium (VI) reduction.Most preferably, sulfur dioxide gas is used for chromium (VI) reduction.
If also find in addition to have cupric ion in aqueous solution of raw material, cupric ion will combine with organic disulfide generation phosphonic acids extraction agent very securely.The key that forms between dithiophosphinic acids extraction agent and cupric ion so firmly in fact can not reextraction copper with the mineral acid commonly used of applying.Therefore, in order to bring into play the optimum performance of extraction agent, before carrying out solvent extraction, preferably remove cupric ion with organic disulfide generation phosphonic acids extraction agent.People can recognize, when copper concentration is very low, can carries out copper and remove step.Can in all sorts of ways and remove copper.For example, spent ion exchange resin can be removed cupric ion.Most preferably, ion exchange resin is the chelating resin with iminodiacetic acid (salt) acid functional group.Other method that can be used for removing copper for example comprises the cementation and the precipitator method with the cupric sulfide form.
Can use undiluted organic disulfide generation phosphonic acids extraction agent.Yet, preferably use and the immiscible organic thinner of water.This thinner can be the organic extractant/diluent mixture of 1 to 99 part of volume.Randomly, organic extractant/diluent mixture can contain 1 to 20 part of volume one or more other organic soluble and with the immiscible compound of water, this compound is commonly referred to as " phase modifier ", and its effect particularly improves separating of water and organic phase.In addition, for example when solution contacted with oxidizing atmosphere such as air, these compounds are written into organic phase can help to prevent the Co(II) be oxidized to the Co(III).
Various and the immiscible organic liquid of water can be used as thinner.Suitable diluent is including, but not limited to kerosene, toluene, dimethylbenzene, petroleum naphtha, hexane, decane, hexanaphthene etc.Preferably, thinner is aliphatic series or aromatics petroleum products.Most preferably, thinner is aliphatic petroleum liquid.The aliphatic series petroleum liquid can be chosen wantonly and contain cycloalkanes and/or aromatic substance.The example of suitable phase modifier is including, but not limited to isodecyl alcohol, tridecyl alcohol, nonyl phenol, tributyl phosphate, trioctyl-phosphine oxide etc.
Solvent extraction method can carry out under air atmosphere.Yet, when in air, operating, in solvent extraction process, (carry the step that organic phase contacts with back extraction (stipper) solution to having) and can take place some degraded of extraction agent from material solution and organic contacted step.Therefore, solvent extraction method is preferably under rare gas element or the reducing gas atmosphere and carries out, thereby avoids or limit detrimental action or oxydised component such as Fe(III) and the Co(III) formation.Specifically, rare gas element is defined in the gas that cobalt (II) can not be oxidized to cobalt (III) in the aqueous solution and/or the organic phase or iron (II) be oxidized to iron (III).The example of suitable gas is including, but not limited to carbonic acid gas, nitrogen, argon gas, sulfurous gas etc.Preferably, if oxydised component such as Fe(III) be present in the aqueous solution of raw material, so preferably add chemical reducing agent such as, but be not limited to SO
2, sulphite, hydrosulphite, water-soluble sulfide etc., with the reduction-oxidation composition.Chemical reducing agent can before the metal extraction or among add.
In order to implement solvent extraction method of the present invention, can use mixer-settlers, column extractor such as pulse column, use teeter column, reciprocating plate extraction column in the rotary blade, have the tubular reactor of line mixer etc.
Be less than approximately 4 in stable p H value, preferably be less than at about 3 o'clock, cobalt and nickel are written in the organic disulfide generation phosphonic acids extraction agent.Most preferably, be less than at about 2.5 o'clock, cobalt and nickel are written in the organic disulfide generation phosphonic acids extraction agent to guarantee that manganese is not written in the coextraction agent altogether in stable p H value.If it is about 2.5 that the pH value of aqueous solution of raw material is higher than, then in extraction process, need not add the hydrogen ion that the alkali neutralization discharges.Exempt and add the process cost that alkali can greatly help to reduce solvent extraction method.Preferably, the pH of extraction is higher than about 1.0 to guarantee effective extraction of nickel and/or cobalt.Preferably, about at least 60% nickel ion is written in the extraction agent.Most preferably, about at least 95% nickel ion is written in the extraction agent.Had now found that when about at least 60% nickel is extracted the contained ratio that obtains nickel and manganese easily is at least about 100.In fact, generally can obtain at least 400 to 700 separation ratio with method of the present invention.This preferred ratio makes can be effectively separates nickel and/or cobalt and manganese and calcium, magnesium etc.
The metal extraction reaction is very rapidly, therefore operation is carried out at ambient temperature.Yet extraction also can at high temperature be carried out.Preferably, in extraction process, organic/water mixture remained under the temperature of freezing point to 85 ℃.In extraction process, water preferably remains on 10 to 0.1 with the ratio of organic phase, and more preferably 5 to 0.5, most preferably 3 to 1.
After loading organic dithiophosphinic acids extraction agent with nickel and cobalt, can be separately or together with water soluble acid reextraction nickel and cobalt metal.Preferred available to have acidity be about 0.1 to 2.0N, and the aqueous solution that most preferably is less than the HCl of 1N or its other suitable acid or the sour mixtures cobalt ion of stripping respectively.After removing cobalt, can preferably be at least HCl or its other suitable acid or sour mixture reextraction nickel of 1.0N with the promptly sour concentration of the water soluble acid of identical or different kind.Most preferably, the acid concentration that is used to remove nickel is about 2.0N to 8.0N.Can use mineral acid for example commonly used such as sulfuric acid or hydrochloric acid etc. or its mixture to carry out metal strips.Preferred hydrochloric acid or the sulfuric acid of using.Most preferably, using hydrochloric acid to carry out metal strips.Preferably, with organic phase and the acidic aqueous solution nickel of under 45 ℃ to 85 ℃ temperature, stripping.In the operation of stripping, the preferred internal recycle of sour stripping solution is so that obtain denseer nickel and/or the cobalt stripping solution.
In addition, be written into separable nickel and cobalt by optionally making nickel have precedence over cobalt.Under the condition of the maximum metal load capacity that approaches organic disulfide generation phosphonic acids extraction agent, the nickel ion that is present in the aqueous solution of raw material can be written in the extraction agent by cobalt being replaced aqueous phase.Therefore, organic extractant only is loaded with nickel basically.Use identical or other extraction agents cobalt in the extraction water solution easily in the separating and extracting step.When adopting isolating cobalt extraction step, for improving its efficient, the cobalt extraction step of back can need heightening pH value.Can reach nickel/cobalt with nickel displacement cobalt and separate in extraction process, this is much higher than under the situation of cobalt concentration with the acid of the different concns nickel/cobalt of optionally stripping favourable than the nickel concentration in initial feed.
In addition, be the water soluble acid of 1.0N at least from the dithiophosphinic acids extraction agent that carries is arranged, can strip together nickel and cobalt with acid concentration.Preferably, acid is that hydrochloric acid and the concentration used are 2.0N to 8.0N.Then then with known solvent extraction method separating nickel and cobalt.Preferably, thus by optionally extracting cobalt separating nickel and cobalt with the amine solvent extraction agent.Most preferably, amine extractant is a tri-iso-octylamine.
Because economically, recovered acid is favourable from nickel and/or cobalt stripping solution.For example, the thermolysis separately of the nickel of stripping solution and/or cobalt salt can be used for producing nickel oxide and/or cobalt, and recovered acid, and this acid preferred cycle ground is used for the reextraction of further nickel and/or cobalt.
The following example only is used for explanation, and should not be construed as limitation of the present invention by any way, because under the situation of the marrow of appended claims of the present invention and scope, the present invention can improve.
Embodiment 1:
This implementation is with organic disulfide generation phosphonic acids extraction agent fully extraction of nickel (II) and cobalt (II) and not extract manganese (II), calcium (II), magnesium (II) or chromium (III) be possible under low pH condition.
Be to contact 5 minutes with sulfate liquor under 2 the condition with the liquor sample of Cyanex 301 extraction agents in Isopar M thinner (the aliphatic organic solvent of Imperial Oil) of 15vol% at 23 ℃ temperature and various pH values (regulating) and water and the ratio of organic phase (A/O) with sodium hydroxide solution, sulfate liquor contains (unit is g/L) 0.045 bronze medal (II), 3.86 nickel (II), 0.35 cobalt (II), 0.002 iron (III), 2.24 manganese (II), 0.54 calcium (II), 1.54 magnesium (II), 0.094 zinc (II), 0.004 chromium (III) and 0.005 aluminium (III).The contact 5 minutes after, from each mutually the extraction sample.The metal concentration of analysis gained aqueous phase is listed in the table below among the 1a.
The Cr(III), Al(III), Ca(II) with the Mg(II) concentration is still identical with concentration in the aqueous solution of raw material.The Ni(II), Co(II) and the Mn(II) the per-cent of extraction separately be listed in the table below among the 1b.
Embodiment 2
Present embodiment explanation other method, it optionally with nickel (II) thus being written into organic disulfide generation phosphonic acids extraction agent reaches effective separating nickel/cobalt.
I) selectivity of nickel is written into
With the sample of 15vol%Cyanex 301 extraction agents in Isopar M thinner 23 ℃ temperature, A/O ratio be 2 and pH2.5(regulate with sodium hydroxide solution) condition under contact 5 minutes with the raw material sulphuric acid salts solution, sulfate liquor contain (unit is g/L) 0.002 bronze medal (II), 2.15 nickel (II), 0.25 cobalt (II),＜0.001 iron (III), 1.18 manganese (II), 0.51 calcium (II), 0.58 magnesium (II), 0.037 zinc (II), 0.020 chromium (III) and 0.007 aluminium (III).After separating two-phase, the water raffinate contain (unit is g/L)＜0.001 bronze medal (II),＜0.001 nickel (II),＜0.001 cobalt (II),＜0.001 iron (III), 1.09 manganese (II), 0.51 calcium (II), 0.56 magnesium (II),＜0.001 zinc (II), 0.028 chromium (III) and 0.004 aluminium (III).
Make then the identical raw material sulphuric acid salts solution that carries organic phase and another part the ratio of A/O be 3 and the identical situation of other conditions under contact for the second time.Contact after 5 minutes, then be separated, the water raffinate contain mutually (unit is g/L)＜0.001 bronze medal (II), 0.78 nickel (II), 0.36 cobalt (II),＜0.001 iron (III), 1.2 manganese (II), 0.51 calcium (II), 0.58 magnesium (II),＜0.001 zinc (II), 0.021 chromium (III) and 0.006 aluminium (III).
Make then the identical raw material sulphuric acid salts solution that carries organic phase and another part the ratio of A/O be 3 and the identical situation of other conditions under contact for the third time.Contact after 5 minutes, then be separated, the water raffinate contain mutually (unit is g/L)＜0.001 bronze medal (II), 2.30 nickel (II), 0.31 cobalt (II),＜0.001 iron (III), 1.2 manganese (II), 0.52 calcium (II), 0.59 magnesium (II), 0.005 zinc (II), 0.022 chromium (III) and 0.004 aluminium (III).
The identical raw material sulphuric acid salts solution that identical organic phase and part are fresh contacts after above-mentioned 3 times successively, analyze gained have the organic phase of carrying find to contain (unit is g/L) 0.023 bronze medal, 9.33 nickel, 0.038 cobalt, 0.004 iron,＜0.005 manganese and 0.272 zinc.
ⅱ) the reextraction of nickel
There is the organic phase of carrying under 55 ℃ temperature, to contact 40 minutes equally a part with the 5N hydrochloric acid soln, after being separated, find strip liquor contain (g/L)＜0.001 bronze medal (II), 5.99 nickel (II), 0.03 cobalt (II),＜0.001 iron (III), 0.003 manganese (II), 0.002 calcium (II), 0.003 magnesium (II), 0.51 zinc (II), 0.002 chromium (III) and 0.004 aluminium (III).
Embodiment 3
Present embodiment illustrates with sulfuric acid reextraction nickel and cobalt from the organic disulfide generation phosphonic acids extraction agent that carries is arranged.
To be loaded with about 7.6g/L Ni(II), 0.5g/L Co(II) with 0.12g/L Zn(II) the sample of 15vol%Cyanex 301 extraction agents in Isopar M thinner and 3.0N sulphuric acid soln be that 1 temperature is to contact 50 minutes under 55 ℃ the condition at the ratio of A/O.The back extraction of gained water intaking liquid contains 3.7g/L Ni(II), 0.5g/L Co(II) and 0.02g/L Zn(II), its be equivalent to strip 49% nickel,＞99.9% cobalt and 15% zinc.
Embodiment 4
Present embodiment has illustrated with organic disulfide generation complete extraction of nickel of phosphonic acids extraction agent (II) and cobalt (II), has got rid of manganese (II), calcium (II), magnesium (II) and chromium (III) simultaneously fully.Present embodiment further illustrates with the continuous multi-stage countercurrent solvent extraction and operates optionally strip organic disulfide generation phosphonic acids extraction agent separating nickel (II) and cobalt (II).
With pH be 3.66 temperature be 22 ℃ contain (g/L) 5.05 nickel (II), 0.53 cobalt (II),＜sulfate solution of 0.001 iron (III), 2.93 manganese (II), 0.48 calcium (II), 1.03 magnesium (II), 0.074 zinc (II), 0.044 chromium (III) and 0.005 aluminium (III) with reflux type three extraction stages (L1, L2 and L3 stages in turn; The aqueous solution enters operation in the L3 stage, contacts with the solution of 15vol%Cyanex 301 extraction agents in Isopar M thinner down for 41 ℃ with flow velocity 10mL/min and in temperature and break away from operation (as raffinate) in the L1 stage.Organic solution entered operation and has identical flow velocity 10mL/min by the L1 stage, thereby the ratio that obtains A/O is 1, and be 6 minutes the dead time in each stage.Do not need to add alkali for carrying out pH regulator or control to any extraction stages.Break away from having of L3 stage and be loaded with machine solution and contact with the 1N hydrochloric acid soln with flow velocity 0.8mL/min under 33 ℃ temperature two reextraction stages (C1 and C2 stage) successively with reflux type, to be the 12.5(1N hydrochloric acid soln in the C2 stage enter the ratio that obtains organic phase and water (O/A) operates and break away from operation (as the stripping solution of cobalt) in the C1 stage.Remove organic solution and contact with water under 32 ℃ temperature in a washing stage (W1 stage) by the C2 stage, thereby the ratio that obtains O/A is 20 with 0.5mL/min flow velocity with reflux type.After breaking away from the washing stage, part is stripped and is contacted with the 6N hydrochloric acid soln with 2.3mL/min flow velocity four reextraction stages (N1, N2, N3 and N4 stage) successively with reflux type with the organic phase of washing, obtains O/A than breaking away from operation in the N1 stage as the nickel stripping solution for the 4.3(6N hydrochloric acid soln enters operation by the N4 stage).It is 60 ℃ that the reextraction stage keeps temperature.The organic phase of removing the reextraction metal in the N4 stage, and under 34 ℃ temperature, contact with the water with 0.4mL/min flow velocity in a washing stage (W2 stage) with reflux type, be 25 thereby obtain the O/A ratio.Metal and the washed organic phase of stripping then is circulated back to extraction stages (L1 stage).
After each stage, typical aqueous solution composition and its pH value in case of necessity are summarized in the table 2.
* under corresponding temperature, measure
Embodiment 5
Present embodiment explanation contains the treatment process of the acidic solution of nickel and cobalt, comprises with sulfur dioxide gas reducing chromium (VI) and part neutralization.
To have that pH is about 1.0, redox-potential 800mV(measures with saturated calomel electrode) the sulfate solution that contains (g/L) 0.017 bronze medal, 3.29 nickel, 0.33 cobalt, 0.24 iron (III), 2.45 manganese, 0.5 chromium (VI), 0.18 calcium, 0.89 aluminium, 0.079 zinc and 2.44 magnesium contact with sulfur dioxide gas down at about 60 ℃, make redox electric heating be reduced to about 550mV(and measure with saturated calomel electrode).After so handling, under 60 ℃, lime carbonate is added to and makes pH rise to 4.5 in the solution.After removing the solid that is settled out, solution contain (g/L)＜0.008 bronze medal, 3.18 nickel, 0.31 cobalt,＜0.01 iron, 2.18 manganese, 0.074 chromium (III) (do not find chromium (VI), 0.89 calcium, 0.01 aluminium, 0.077 zinc and 2.18 magnesium.
Embodiment 6
The present embodiment explanation may be present in the copper (II) of the relatively small amount in the aqueous solution of raw material and can optionally remove before solvent extraction by the ion exchange resin that uses chelating.
The raw material sulphuric acid salt brine solution that will contain (g/L) 0.20 bronze medal (II), 3.5 nickel (II), 0.33 cobalt (II), 2.2 manganese (II), 0.5 calcium (II), 1.5 magnesium (II) and 0.087 zinc (II) with the upper reaches speed of 1.2m/h under 23 ℃ temperature by contain the Resin Tech SIR-300 resin that 100ml has the iminodiacetic acid (salt) acid functional group (from ResinTech, post Inc.).Behind the solution by 80 column volumes, handle persulfate solution and still contain the copper (II) that is less than 0.001g/L, and identical in the maintenance of the concentration of nickel (II) and cobalt (II) and the material solution.
Method of the present invention has several advantages.The invention provides the method for using the solvent extraction of avoiding manganese, calcium and magnesium coextraction from acidic aqueous solution, optionally to reclaim nickel and/or cobalt composition.Method of the present invention helps the method for simple economy ground selective recovery nickel and/or cobalt composition.Method of the present invention helps simple economy ground selective recovery nickel and/or cobalt.Organic phase generally can be recycled and reused for repeatedly extraction/reextraction circulation.Method of the present invention further provides by optionally stripping or optionally being written into processing separates nickel effectively with cobalt.At last, be written in the step when using the part neutralization to remove impurity at metal and needn't add alkali often.
Although clause according to rules, this paper illustrates and has described specific embodiments of the present invention, yet those skilled in the art will understand, form of the present invention can change in the scope of claims, and to use some feature of the present invention sometimes and correspondingly do not use other features also be favourable.
Claims (58)
1, a kind of Wet-process metallurgy method that reclaims metal, this method comprises the following steps:
A) provide a kind of aqueous solution of raw material, this aqueous solution of raw material goes out from acidleach, and this aqueous solution of raw material contains at least a metal that is selected from nickel and cobalt ion,
B) keeping the pH of the above-mentioned aqueous solution is about level of 2 to 6,
C) with the above-mentioned raw materials aqueous solution with contain contacting of extraction agent with the immiscible organic phase of water, make the metal of this aqueous solution of raw material be written into above-mentioned extraction agent and form the organic phase that has metal, above-mentioned extraction agent has at least a organic soluble dithiophosphinic acids or its an alkali metal salt or alkaline earth salt or ammonium salt, the above-mentioned raw materials aqueous solution has enough chromium (VI) ion, iron (III) ion and the cupric ion of low amount, make reusable above-mentioned extraction agent
D) the above-mentioned organic phase that has metal is separated with the above-mentioned aqueous solution of raw material that contains metal and
E) the above-mentioned organic phase that has metal is contacted with aqueous solution of back extraction have and reclaim contained metal the organic phase of metal from this.
2, the method for claim 1, this method are included in described with before the immiscible organic phase of water contacts, the other step of removing cupric ion from the above-mentioned raw materials aqueous solution.
3, the process of claim 1 wherein with described with before the immiscible organic phase of water contacts, by removing (VI) ion that dechromises with the reductive agent reduction.
4, the process of claim 1 wherein that described organic soluble dithiophosphinic acids or its an alkali metal salt or alkaline earth salt or ammonium salt represent with following formula:
R wherein
1And R
2Be selected from alkyl, cycloalkyl, alkoxyalkyl, alkyl-cycloalkyl, aryl, alkylaryl, aralkyl or the cycloalkyl aryl of replacement, and M wherein is hydrogen or basic metal or alkaline-earth metal ions or ammonium ion with 2 to 24 carbon atoms.
5, the process of claim 1 wherein that described extraction agent is two (2,4, the 4-tri-methyl-amyl) dithiophosphinic acidss.
6, the process of claim 1 wherein that described and the immiscible organic phase of water comprise organic thinner.
7, the process of claim 1 wherein that described aqueous solution of raw material and described and the immiscible organic phase of water contact being higher than under the temperature of freezing point to 85 ℃.
8, the process of claim 1 wherein that described aqueous solution of back extraction contains at least a hydrochloric acid and the vitriolic mineral acid of being selected from.
9, the process of claim 1 wherein that the described organic phase that has metal contains nickel and cobalt; And the described organic phase that has a metal and described pH are less than 2.5 aqueous solution of back extraction and contact.
10, the method of claim 1, wherein make described extraction agent carry nickel ion and cobalt ion, and described contact that makes the described organic phase that has a metal and aqueous solution of back extraction comprises the following steps: to make the organic phase that has metal contact with the recovery cobalt ion with aqueous solution of back extraction for the first time, with the first time aqueous solution of back extraction separate with the organic phase that has metal, after separation of cobalt, the organic phase that has metal is contacted with aqueous solution of back extraction for the second time, to reclaim nickel ion and obtain not having the organic phase of cobalt/nickel from the organic phase that has metal, making for the second time then, aqueous solution of back extraction separates with no cobalt/nickel organic phase.
11, the method for claim 10 is about 0.1 to 2.0N the aqueous solution of back extraction first time described cobalt ion of stripping with having acid concentration wherein, with having the aqueous solution of back extraction second time that acid concentration the is at least about 1.0N described nickel ion of stripping.
12, the method for claim 1, wherein said aqueous solution of raw material contains nickel and cobalt ion, make described extraction agent carry nickel and cobalt ion, be written into the contained cobalt ion of displacement again, form the organic phase and the aqueous solution that is rich in cobalt that are loaded with nickel and do not contain cobalt by the nickel ion that makes aqueous solution of raw material.
13, the process of claim 1 wherein that described aqueous solution of raw material contains nickel and cobalt ion, make described extraction agent carry nickel and cobalt ion, in described aqueous solution of back extraction contact process, reclaiming nickel and cobalt ion.
14, the method for claim 13 is wherein pressed solvent extraction method separating nickel and cobalt ion with amine extractant.
15, the process of claim 1 wherein by thermolysis with the metal in the form recovery aqueous solution of back extraction of oxide compound, the restored acid step (e) that is used for capable of circulation from the reextraction aqueous acid of no metal thus.
16, the process of claim 1 wherein that described aqueous solution of raw material contains mn ion, most of mn ion is not written into described extraction agent.
17, the method for claim 1, this method be included in before the step c) or among with the Fe(III) ion is reduced to the Fe(II) the other step of ionic.
18, the process of claim 1 wherein that step c) is to e) operate under the atmosphere of ionic oxide formation in restriction aqueous solution of raw material or organic phase, described ion is selected from the Co(II) ion and Fe(II) ion.
19, a kind of Wet-process metallurgy method that reclaims metal, it comprises the following steps:
A) provide a kind of aqueous solution of raw material, this aqueous solution of raw material goes out from the acidleach of ore, aqueous solution of raw material contains the first kind metal and second metalloid, first kind metal has at least a metal that is selected from nickel and cobalt ion, second metalloid has the metal of at least a chosen from Fe (III), chromium, aluminium and cupric ion
B) in the part and aqueous solution of raw material to make pH be about 2 to 6, thereby remove the free acid in the aqueous solution of raw material, and be settled out the metal in described second metalloid, this neutralization is stayed in the aqueous solution of raw material most of first kind metal ion,
C) sedimentary metal is separated with aqueous solution of raw material,
D) with the above-mentioned raw materials aqueous solution with contain contacting of extraction agent with the immiscible organic phase of water, make the metal in the first kind metal be written into above-mentioned extraction agent, and formation has the organic phase of metal, above-mentioned extraction agent has the salt of at least a organic soluble dithiophosphinic acids or its basic metal or alkaline-earth metal or ammonium, the above-mentioned raw materials aqueous solution has enough chromium (VI) ion, iron (III) ion and the cupric ion of low amount, make reusable above-mentioned extraction agent
E) the above-mentioned organic phase that has metal is separated with the above-mentioned aqueous solution of raw material that contains metal and
F) the above-mentioned organic phase that has metal is contacted with aqueous solution of back extraction, to reclaim the metal in the first kind metal the organic phase that has metal from this.
20, the method for claim 19, this method are included in described with before the immiscible organic phase of water contacts, the other step of removing cupric ion from described aqueous solution of raw material.
21, the method for claim 19, wherein with described with before the immiscible organic phase of water contacts, by removing (VI) ion that dechromises with the reductive agent reduction.
22, the method for claim 19, the salt of wherein said organic soluble dithiophosphinic acids or its basic metal or alkaline-earth metal or ammonium is represented with following formula:
R wherein
1And R
2Be selected from alkyl, cycloalkyl, alkoxyalkyl, alkyl-cycloalkyl, aryl, alkylaryl, aralkyl or the cycloalkyl aryl of replacement, and M wherein is hydrogen or basic metal or alkaline-earth metal ions or ammonium ion with 2 to 24 carbon atoms.
23, the method for claim 19, wherein said extraction agent are two (2,4, the 4-tri-methyl-amyl) dithiophosphinic acidss.
24, the method for claim 19, the wherein said and immiscible organic phase of water comprises organic thinner.
25, the method for claim 19, wherein said aqueous solution of raw material and described and the immiscible organic phase of water contact being higher than under the temperature of freezing point to 85 ℃.
26, the method for claim 19, wherein said aqueous solution of back extraction contain at least a hydrochloric acid and the vitriolic mineral acid of being selected from.
27, the method for claim 19, the wherein said organic phase that has metal contains nickel and cobalt; And this organic phase that has a metal and described pH contact less than 2.5 aqueous solution of back extraction.
28, the method of claim 19, wherein make described extraction agent carry nickel ion and cobalt ion, and described contact that makes the described organic phase that has a metal and aqueous solution of back extraction comprises the following steps: to make the described organic phase of metal that has to contact with aqueous solution of back extraction for the first time, to reclaim cobalt ion, with the first time aqueous solution of back extraction separate with the organic phase that has metal, after separation of cobalt, the organic phase that has metal and aqueous solution of back extraction are for the second time contacted from the organic phase that has metal reclaim nickel ion, and obtain not having the organic phase of cobalt/nickel, and make for the second time that aqueous solution of back extraction separates with no cobalt/nickel organic phase.
29, the method for claim 28 is about 0.1 to 2.0N the aqueous solution of back extraction first time described cobalt ion of stripping with having acid concentration wherein, with having the aqueous solution of back extraction reextraction second time nickel ion that acid concentration is at least about 1.0N.
30, the method for claim 19, wherein said aqueous solution of raw material contains nickel and cobalt ion, make described extraction agent carry nickel and cobalt ion, be written into the contained cobalt ion of displacement again, form the organic phase and the aqueous solution that is rich in cobalt that are loaded with nickel and do not contain cobalt by the nickel ion that makes aqueous solution of raw material.
31, the method for claim 19, wherein said aqueous solution of raw material contains nickel and cobalt ion, makes described extraction agent carry nickel and cobalt ion, is reclaiming nickel and cobalt ion in described aqueous solution of back extraction contact process.
32, the method for claim 31 is wherein separated described nickel and cobalt ion with amine extractant by solvent extraction method.
33, the method for claim 19 wherein reclaims described metal in the aqueous solution of back extraction, the restored acid step f) that is used for capable of circulation from the reextraction aqueous acid of no metal thus by thermolysis with the form of oxide compound.
34, the method for claim 19, wherein said aqueous solution of raw material contains mn ion, and most of described mn ion is not written into described extraction agent.
35, it is about 3 to 6 that the method for claim 19, wherein said aqueous solution of raw material are neutralized to pH.
36, the method for claim 19 is wherein with the lime carbonate described aqueous solution of raw material that partly neutralizes.
37, the method for claim 19, this method be included in after the step c) and before the step d) or among with the Fe(III) ion is reduced to the Fe(II) the other step of ionic.
38, the method for claim 19, wherein step d) is to f) to operate under the atmosphere of ionic oxide formation in described aqueous solution of raw material of restriction or described organic phase, ion is selected from cobalt (II) ion and iron (II) ion.
39, a kind of Wet-process metallurgy method that reclaims metal, this method comprises the following steps:
A) provide a kind of aqueous solution of raw material, this aqueous solution of raw material goes out from the acidleach of laterite, described aqueous solution of raw material contains chromium (VI) ion and first kind metal, second metalloid and the 3rd metalloid, described first kind metal has at least a metal that is selected from nickel and cobalt ion, described second metalloid has the metal of at least a chosen from Fe (III), chromium (III), aluminium and cupric ion, and described the 3rd metalloid has at least a metal that is selected from manganese, calcium and magnesium
B) chromium in the above-mentioned raw materials aqueous solution (VI) ion is reduced to chromium (III) ion, and the part neutralize the above-mentioned leaching aqueous solution to pH be about 3 to 6, thereby remove the free acid in the described aqueous solution of raw material, and be settled out metal in described second metalloid, described neutralization is stayed in the described aqueous solution of raw material ion of most of first kind metal
C) described sedimentary metal is separated with described aqueous solution of raw material,
D) with the above-mentioned raw materials aqueous solution with contain contacting with the immiscible organic phase of water of extractant; Make the metal in the first kind metal be written into above-mentioned extractant; And formation is with the organic phase of metal; Described extractant has dithiophosphinic acid or its alkali metal salt or alkali salt or the ammonium salt of at least a Identification of Soluble Organic; Above-mentioned contact is stayed in the raffinate of gained described the 3rd metalloid ion; The above-mentioned raw materials aqueous solution has chromium (VI) ion, iron (III) ion and the copper ion of enough low contents; So that reusable above-mentioned extractant
E) with the above-mentioned organic phase that has a metal with contain that the described raffinate of described the 3rd metalloid ionic separates and
F) the above-mentioned organic phase that has metal is contacted with aqueous solution of back extraction, to reclaim the metal in the described first kind metal the organic phase that has metal from this.
40, the method for claim 39, this method are included in described with before the immiscible organic phase of water contacts, the other step of removing cupric ion from described aqueous solution of raw material.
41, the method for claim 39 is wherein reduced described chromium (VI) ion with the sulfur dioxide gas reductive agent.
42, the method for claim 39, wherein said organic soluble dithiophosphinic acids or its an alkali metal salt or alkaline earth salt or ammonium salt are represented with following formula:
R wherein
1And R
2Be selected from alkyl, cycloalkyl, alkoxyalkyl, alkyl-cycloalkyl, aryl, alkylaryl, aralkyl or the cycloalkyl aryl of replacement, and M wherein is hydrogen or basic metal or alkaline-earth metal ions or ammonium ion with 2 to 24 carbon atoms.
43, the method for claim 39, wherein said extraction agent are two (2,4, the 4-tri-methyl-amyl) dithiophosphinic acidss.
44, the method for claim 39, the wherein said and immiscible organic phase of water comprises organic thinner.
45, the method for claim 39, wherein said aqueous solution of raw material and described and the immiscible organic phase of water contact being higher than under the temperature of freezing point to 85 ℃.
46, the method for claim 39, wherein said aqueous solution of back extraction contain at least a hydrochloric acid and the vitriolic mineral acid of being selected from.
47, the method for claim 39, the wherein said organic phase that has metal contains nickel and cobalt; And this organic phase that has a metal and described pH contact less than 2.5 aqueous solution of back extraction.
48, the method of claim 39, wherein make described extraction agent carry nickel ion and cobalt ion, and described contact that makes the described organic phase that has a metal and aqueous solution of back extraction comprises the following steps: to make the organic phase that has metal to contact with aqueous solution of back extraction for the first time, to reclaim cobalt ion, with the first time aqueous solution of back extraction separate with the organic phase that has metal, after separation of cobalt, the organic phase that has metal is contacted with aqueous solution of back extraction for the second time, from the organic phase that has metal, to reclaim nickel ion, and obtain not having the organic phase of cobalt/nickel, making for the second time then, aqueous solution of back extraction separates with no cobalt/nickel organic phase.
49, the method for claim 48 is about 0.1 to 2.0N the aqueous solution of back extraction first time described cobalt ion of stripping with having acid concentration wherein, with having the aqueous solution of back extraction second time that acid concentration the is at least about 1.0N described nickel ion of stripping.
50, the method for claim 39, wherein said aqueous solution of raw material contains nickel and cobalt ion, make described extraction agent carry nickel and cobalt ion, be written into the contained cobalt ion of displacement again, form the organic phase and the aqueous solution that is rich in cobalt that are loaded with nickel and do not contain cobalt by the nickel ion that makes aqueous solution of raw material.
51, the method for claim 39, wherein said aqueous solution of raw material contains nickel and cobalt ion, makes described extraction agent carry nickel and cobalt ion, is reclaiming nickel and cobalt ion in described aqueous solution of back extraction contact process.
52, the method for claim 51 is wherein pressed solvent extraction method separating nickel and cobalt ion with amine extractant.
53, the method for claim 39 wherein reclaims described metal in the described aqueous solution of back extraction, the restored acid step f) that is used for capable of circulation from the reextraction aqueous acid of no metal thus by thermolysis with the form of oxide compound.
54, the method for claim 39, wherein aqueous solution of raw material contains mn ion, and most of described mn ion is not written into described extraction agent.
55, the method for claim 39, wherein to be neutralized to pH be about 3 to 5.5 to aqueous solution of raw material.
56, the method for claim 39 is wherein with the lime carbonate described aqueous solution of raw material that partly neutralizes.
57, the method for claim 39, this method be included in after the step c) and before the step d) or among with the Fe(III) ion is reduced to the Fe(II) the other step of ionic.
58, the method for claim 39, wherein step d) is to f) to operate under the atmosphere of ionic oxide formation in described aqueous solution of raw material of restriction or described organic phase, ion is selected from cobalt (II) ion and iron (II) ion.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/216,258 US5378262A (en) | 1994-03-22 | 1994-03-22 | Process for the extraction and separation of nickel and/or cobalt |
| US216,258 | 1994-03-22 | ||
| US337,283 | 1994-11-10 | ||
| US08/337,283 US5447552A (en) | 1994-03-22 | 1994-11-10 | Process for the extraction and separation of nickel and/or cobalt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109913A true CN1109913A (en) | 1995-10-11 |
| CN1046966C CN1046966C (en) | 1999-12-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95102797A Expired - Lifetime CN1046966C (en) | 1994-03-22 | 1995-03-21 | A process for the extraction and separation of nickel and/or cobalt |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP2760956B2 (en) |
| CN (1) | CN1046966C (en) |
| AU (1) | AU687981B2 (en) |
| BR (1) | BR9501135A (en) |
| CA (1) | CA2145054C (en) |
| FR (1) | FR2717826B1 (en) |
| OA (1) | OA10135A (en) |
| PH (1) | PH31603A (en) |
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- 1995-03-20 CA CA002145054A patent/CA2145054C/en not_active Expired - Lifetime
- 1995-03-20 BR BR9501135A patent/BR9501135A/en not_active Application Discontinuation
- 1995-03-20 FR FR9503196A patent/FR2717826B1/en not_active Expired - Lifetime
- 1995-03-21 CN CN95102797A patent/CN1046966C/en not_active Expired - Lifetime
- 1995-03-21 AU AU14966/95A patent/AU687981B2/en not_active Expired
- 1995-03-22 JP JP7063189A patent/JP2760956B2/en not_active Expired - Fee Related
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| CN1101475C (en) * | 1996-01-16 | 2003-02-12 | 中国科学院化工冶金研究所 | Method for recovering cobalt |
| CN1090243C (en) * | 1996-06-04 | 2002-09-04 | 赛特技术有限公司 | Regeneration of dithiophosphorus acid metal extractants |
| CN101343287B (en) * | 2008-08-29 | 2011-05-11 | 清华大学 | Synthesis of sicycle-ring hexyl di-thiophosphinic acid |
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| CN108517406A (en) * | 2018-04-19 | 2018-09-11 | 中国人民解放军国防科技大学 | Solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, and preparation method and application thereof |
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| CN112746168A (en) * | 2019-10-30 | 2021-05-04 | 平顶山德源精细化学品有限公司 | Process method for treating laterite-nickel ore leaching solution by using combined extracting agent |
| CN115427163A (en) * | 2020-06-16 | 2022-12-02 | 雅苒国际集团 | Process for removing heavy metals from phosphoric acid containing compositions |
| CN115427164A (en) * | 2020-06-16 | 2022-12-02 | 雅苒国际集团 | Process for removing heavy metals from phosphorus acid containing compositions using flocculants |
| CN115605430A (en) * | 2020-06-16 | 2023-01-13 | 雅苒国际集团（No） | Method for removing heavy metals from phosphoric acid-containing compositions using ionic polymeric surfactants and use of said surfactants for precipitating heavy metals in phosphoric acid-containing compositions |
| CN112342390A (en) * | 2020-10-26 | 2021-02-09 | 宁波互邦新材料有限公司 | Extraction separation technology of ternary leaching solution and ternary positive electrode material recovery process based on extraction separation technology |
| CN114317961A (en) * | 2021-12-30 | 2022-04-12 | 重庆康普化学工业股份有限公司 | Co-extraction system for nickel-cobalt co-extraction and co-extraction method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PH31603A (en) | 1998-11-03 |
| JP2760956B2 (en) | 1998-06-04 |
| OA10135A (en) | 1996-12-18 |
| CA2145054C (en) | 1999-03-09 |
| FR2717826B1 (en) | 1997-03-14 |
| CA2145054A1 (en) | 1995-09-23 |
| CN1046966C (en) | 1999-12-01 |
| AU687981B2 (en) | 1998-03-05 |
| BR9501135A (en) | 1995-10-24 |
| AU1496695A (en) | 1995-09-28 |
| FR2717826A1 (en) | 1995-09-29 |
| JPH0835023A (en) | 1996-02-06 |
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