EP1841891A1 - Extraction of nickel and cobalt from a resin eluate stream - Google Patents
Extraction of nickel and cobalt from a resin eluate streamInfo
- Publication number
- EP1841891A1 EP1841891A1 EP05819247A EP05819247A EP1841891A1 EP 1841891 A1 EP1841891 A1 EP 1841891A1 EP 05819247 A EP05819247 A EP 05819247A EP 05819247 A EP05819247 A EP 05819247A EP 1841891 A1 EP1841891 A1 EP 1841891A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- cobalt
- resin
- process according
- acid
- 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.)
- Withdrawn
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 252
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- 239000010941 cobalt Substances 0.000 title claims abstract description 109
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 109
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 238000000605 extraction Methods 0.000 title description 14
- 238000000034 method Methods 0.000 claims abstract description 87
- 230000008569 process Effects 0.000 claims abstract description 82
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 19
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 64
- 239000002253 acid Substances 0.000 claims description 53
- 239000002002 slurry Substances 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 229910052742 iron Inorganic materials 0.000 claims description 33
- 229910001710 laterite Inorganic materials 0.000 claims description 28
- 239000011504 laterite Substances 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 25
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 22
- 229910052749 magnesium Inorganic materials 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052598 goethite Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 10
- 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 claims description 9
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical group CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical group [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 3
- KXZQYLBVMZGIKC-UHFFFAOYSA-N 1-pyridin-2-yl-n-(pyridin-2-ylmethyl)methanamine Chemical group C=1C=CC=NC=1CNCC1=CC=CC=N1 KXZQYLBVMZGIKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 22
- 229910000863 Ferronickel Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 238000000638 solvent extraction Methods 0.000 description 10
- 238000005201 scrubbing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 235000019738 Limestone Nutrition 0.000 description 6
- 239000006028 limestone Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 238000005363 electrowinning Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 3
- 229910052935 jarosite Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CNJLMVZFWLNOEP-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[4.1.0]heptan-5-one Chemical compound O=C1C(C)CCC2C(C)(C)C12 CNJLMVZFWLNOEP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- -1 saprolite Chemical compound 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- YTQVNYGLBGECJA-UHFFFAOYSA-L [Fe].[Ni](O)O Chemical compound [Fe].[Ni](O)O YTQVNYGLBGECJA-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- 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
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0484—Separation of nickel from cobalt in acidic type solutions
-
- 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
-
- 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
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
Definitions
- the present invention relates to a method for producing a nickel hydroxide product and a cobalt product from an acidic resin eluate containing nickel and cobalt.
- the cobalt will generally be recovered as a mixed cobalt sulfide product.
- the present invention is particularly suited to the treatment of nickel and cobalt containing eluate that has been stripped from a resin that has been used in a resin-in-pulp process to extract the nickel and cobalt from the product slurry of a laterite acid leach process.
- Laterite nickel and cobalt ore deposits generally contain oxidic type ores, limonites, and silicate type ores, saprolites, as two layers in the same deposits, separated by a transition zone.
- high grade limonite and saprolite are preferred.
- the higher nickel content saprolites tend to be treated by a pyrometallurgical process involving roasting and electrical smelting techniques to produce ferro nickel.
- the power requirements and high iron to nickel ore ratio for the lower nickel content limonite, saprolite, and limonite/saprolite blends in the transition zone make this processing route too expensive.
- the high nickel and cobalt content limonite is normally commercially treated hydrometallurgically by the High Pressure Acid Leach (HPAL) process, or by a combination of pyrometallurgical and hydrometallurgical processes, such as the Caron reduction roast - ammonium carbonate leach process.
- HPAL High Pressure Acid Leach
- the HPAL process is generally less capital and energy intensive than the Caron process.
- a problem with an atmospheric acid leach process is that the leach slurry produced contains, in addition to the dissolved nickel and cobalt values targeted, large quantities of precipitated iron oxides and a variety of other dissolved impurities.
- the purification of similar nickel solutions from commercial laterite acid leach processes involve neutralisation of the acid content, solid/liquid separation followed by production of a nickel/cobalt intermediate, a re-dissolution step, and complex solvent extraction stages to produce saleable nickel and cobalt.
- the purification steps generally aim for complete removal of iron and the other impurities.
- IX Ion Exchange
- Patent WO 00/053820 (BHP Minerals International Inc.) describes the IX extraction of nickel and cobalt from acid sulfate leach solution onto the resin, and the subsequent acid stripping of the metals from the resin, and their separation by solvent extraction for the production of high purity nickel and cobalt by electrowinning.
- US Patent 6350420 (BHP Minerals International Inc.) teaches the use of ion exchange resin in a resin in pulp process to extract nickel and cobalt onto the resin from an acid leach slurry.
- the leach slurry is contacted with the ion exchange resin which selectively loads nickel and cobalt from the pulp.
- the resin is separated from the leach slurry by screening, and stripped of the metal content with an acidic solution.
- the metal depleted slurry can now proceed to waste treatment and disposal and the process eliminates the requirement for the large and capitally intensive solids/liquids separation equipment normally required by the acid leach processes to extract the product solution from the solid residue.
- the above documents all aim to produce relatively pure nickel solution, or nickel and cobalt strip solutions from the IX resins.
- the present invention aims to economically produce a nickel product with low levels of critical impurities such as copper, zinc and manganese, that is suitable for further processing, for example in the production of ferro nickel or in other hydrometallurgical nickel refinery processes.
- the cobalt is generally recovered as cobalt sulfide, and again, is of sufficient grade for further processing.
- the present invention aims to provide a new process which overcomes or at least alleviates one or more of the difficulties associated with the prior art.
- the present invention relates to a method for producing a nickel hydroxide product and a cobalt product from an acidic resin eluate containing nickel and cobalt.
- the cobalt is preferably recovered as a mixed cobalt sulfide product.
- the present invention is particularly suited to the treatment of nickel and cobalt containing eluate that has been stripped from a resin that has been used in a resin-in-pulp process to extract the nickel and cobalt metals from the product slurry of a laterite acid leach process.
- the present invention resides in a process for the recovery of nickel and cobalt from an acidic resin eluate containing nickel and cobalt, including the steps of: a) treating the eluate with an immiscible organic reagent to selectively absorb the majority of the cobalt, and a portion of any copper, zinc and manganese present in the eluate, leaving a raffinate containing the nickel and minor impurities; b) neutralising the raffinate to precipitate the nickel as nickel hydroxide; c) stripping the cobalt from the organic reagent; and d) recovering the cobalt.
- the process forms a part of an overall process for the recovery of nickel and cobalt that utilises a resin-in-pulp circuit to extract the nickel and cobalt.
- the nickel hydroxide product recovered is low in critical impurities and particularly suitable for further processing, for example, in the production of ferronickel, while the cobalt will generally be recovered as an impure cobalt sulfide product.
- the cobalt sulfide is generally recovered by stripping the cobalt from the organic reagent with sulfuric acid to form an acid solution, followed by precipitation of the cobalt sulfide by the addition of a sulfide to the acid solution.
- the sulfide is typically sodium hydrosulfide, hydrogen sulfide or a potassium hydrosulfide.
- the process of the invention is particularly applicable to the recovery of nickel and cobalt from a nickel and cobalt containing acidic resin eluate wherein the eluate is the result of acid stripping an ion-exchange resin in a resin-in-pulp circuit in a nickel and cobalt recovery process.
- the resin is generally stripped by treating the resin with concentrated acid, preferably sulfuric or hydrochloric acid, to produce the acidic eluate.
- the ion exchange resin is a resin having an iminodiactic functional group which loads nickel, cobalt, and any copper, zinc, aluminium, ferrous iron and chromium present almost completely together with quantities of manganese and a small amount of magnesium in a resin-in-pulp process.
- a resin having a bis-picolylamine functionality such as Dowex 4195, may be used.
- the nickel and cobalt recovery process is an atmospheric pressure acid leach of a nickel containing laterite ore, but may also be a high pressure acid leach or a combination of high pressure acid leach and atmospheric pressure acid leach of laterite ores.
- the eluate may be produced by the acid treatment of the resin in a resin-in-pulp treatment of the product slurry from an oxidative leach of a nickel sulfide ore or concentrate, or the product slurry from the acid leach of a combination of laterite and sulfide ores.
- the eluate may be from resin treatment of product liquor solutions containing at least nickel and cobalt, and obtained from acid leaching of lateritic or sulfide ores after separation of the leach residues from the solutions.
- the laterite ore may be processed by first separating the laterite ore into its low magnesium containing limonite fraction, and its high magnesium containing saprolite fraction and sequentially leaching the limonite and saprolite fractions.
- the limonite fraction may be treated with acid in a primary leach step to produce a primary leach slurry.
- the saprolite fraction may then be added to the primary leach slurry which will initiate precipitation of iron as goethite and produce a secondary leach slurry containing at least nickel and cobalt ions. This will also result in higher amounts of acid available for the leach process as acid will be produced upon precipitation of the iron.
- the process preferably includes the additional steps of: (a) separating the laterite ore into its low magnesium limonite fraction and high magnesium saprolite fraction; (b) treating the limonite fraction with acid in a primary leach stage to produce a primary leach slurry; and
- the pH of the secondary leach slurry is partially neutralised to a pH of around 2 to substantially complete precipitation of iron as goethite.
- the secondary leach slurry is then neutralised further to raise and maintain the pH to at least 4, most preferably between 4 and 5, to precipitate or depress ferric ions and other impurities that may be present, prior to or simultaneously with reporting to the resin-in-pulp circuit.
- the resin will absorb at least the nickel, cobalt and some other minor impurities from the seconary leach slurry.
- the resin may be eluted with weak sulfuric acid initially, to remove substantially all or any magnesium, calcium and manganese prior to stripping the resin with the strong sulfuric acid.
- the resin may also be washed with a good quality water prior to stripping the nickel and cobalt from the resin.
- the loaded resin is then treated with a strong acid to strip off the metals from the resin to produce a nickel and cobalt containing acidic eluate.
- the acid is most preferably a strong sulfuric acid, although hydrochloric acid may also be used.
- the acid resin eluate containing the nickel and cobalt preferably is then neutralised with a neutralising agent to a pH of about 4.5 to 5 prior to separation of the nickel and cobalt.
- the neutralising agent is sodium hydroxide, sodium carbonate, magnesium carbonate or calcium carbonate.
- the eluate itself contains from about 10 to 80 g/L nickel following elution from the resin.
- the immiscible organic reagent that is used to selectively absorb the majority of the cobalt and a portion of any copper, zinc and manganese present is preferably Cyanex 272. Cyanex 272 is selective for cobalt over nickel and as such, will separate the nickel and cobalt in the acidic resin eluate. Sulfuric acid is then used to strip the cobalt from the immiscible organic reagent to produce a cobalt containing sulfuric acid solution. A sulfide product is then added to the sulfuric acid solution to precipitate the cobalt as an impure cobalt sulfide.
- the sulfide product is either a sodium hydrosulfide, hydrogen sulfide or a potassium hydrosulfide, but any suitable sulfide product will do, so long as it precipitates the cobalt as a cobalt sulfide product.
- the pH of the raffinate is first raised to a pH of greater than 7.5 by addition of a neutralising agent, preferably a magnesium oxide slurry, to precipitate the nickel as nickel hydroxide.
- a neutralising agent preferably a magnesium oxide slurry
- the nickel hydroxide is then filtered and washed for recovery of the nickel product.
- the nickel hydroxide product produced is low in critical impurities such as copper, zinc and manganese and may be useful for use in further nickel processes.
- the process of the present invention has particular benefits in the recovery of nickel and cobalt from an acidic eluate stream in that the nickel and cobalt is recovered in a form which is readily transportable and has ready uses for further processing.
- the process is particularly beneficial in that impurities may be readily removed, particularly residual ferric ions which are precipitated as goethite during the leach process, leading to recovery of a nickel and cobalt product, that is in a form suitable for use in further refinery processes.
- impurities may be readily removed, particularly residual ferric ions which are precipitated as goethite during the leach process, leading to recovery of a nickel and cobalt product, that is in a form suitable for use in further refinery processes.
- the removal of such impurities in a resin-in-pulp circuit can obviate the need to employ sizable settler tanks used to remove large quantities of iron impurities, saving considerably in capital expenditure.
- Figure 1 illustrates a preferred flow-sheet of a process for the recovery of nickel as a nickel hydroxide, and cobalt as a mixed cobalt sulfide in accordance with a process of the invention.
- the nickel containing laterite ore is preferably separated into a low magnesium containing ore fraction (1 ) and high magnesium ore fraction (2) by selective mining or post mining classification.
- the limonite (low magnesium) fraction of a nickel laterite ore (1 ) is treated with concentrated sulfuric acid (30) in a primary leach stage (3) at atmospheric pressure.
- the saprolite (high magnesium fraction) of the ore (2) is added to the product slurry from the primary leach in a secondary leach step (4) with iron precipitated as goethite.
- the iron which goes into solution is further precipitated as goethite (5), that is FeO(OH), following the addition of a limestone slurry (31 ). This results in a higher amount of acid being available for the second leach step than if the iron was precipitated as, for example, jarosite.
- the primary leaching (3) is carried out at a temperature up to 105°C, most preferably as high as possible to achieve rapid leaching at atmospheric pressure.
- the dose of sulfuric acid is preferably 100 to 140% of the stoichiometric amount to dissolve approximately over 90% of nickel, cobalt, iron, magnesium, aluminium and manganese in the ore.
- a reductant for example, a sulfur dioxide gas or sodium-free metabisulfite or sulfite
- a reductant for example, a sulfur dioxide gas or sodium-free metabisulfite or sulfite
- SHE 100OmV
- SHE 900 mV
- the completion of reduction and leaching is indicated by the formation of 0.5 to 1.0 g/L ferrous ion (Fe 2+ ) and steady acid concentration under these reaction conditions.
- the weight loss of the low magnesium limonite ore is typically over 80% and the extraction of nickel and cobalt is over 90%.
- the secondary leach step (4) which is preferably carried out at atmospheric pressure, includes the simultaneous leaching of saprolite and iron precipitation, preferably as goethite or other relatively low sulfate-containing forms of iron oxide or iron hydroxide. No additional acid is added during the second leach step.
- the secondary leach step (4) is carried out at the temperature, preferably up to 105°C, and most preferably as high as possible to achieve rapid leaching and iron precipitation kinetics, at atmospheric pressure.
- the dose of high-Mg saprolite ore added to the primary leach slurry is determined by the free acid remaining from the first leach step, the acid released during iron precipitation as goethite and the unit stoichiometric acid-consumption of high-Mg saprolite ore at given extractions of nickel, cobalt, iron, magnesium, aluminium and manganese in the ore.
- the saprolite ore With the introduction of the saprolite ore, iron precipitation as goethite will generally occur.
- the saprolite ore generally contains some iron as goethite together with other fine particles that function as seeds, which can initiate goethite precipitation.
- seeds that predominantly contain goethite or jarrosite, may be added to the reactor should this be required, as the addition of seeds may assist in the leaching of saprolite ore and the iron precipitation as goethite, or other relatively low sulfate- containing forms of iron oxide or iron hydroxide, to occur simultaneously.
- the secondary pregnant leach slurry containing the nickel and cobalt is then neutralised with limestone slurry at 80° C to force iron precipitation as goethite substantially to completion (5).
- the end point of goethite precipitation is around pH 2.0.
- the pregnant slurry is further neutralised to at least pH 4 with additional limestone slurry (6), and aerated (32), precipitating the residual ferric ions and other impurities, such as copper, aluminium, chromium, and additional iron, particularly ferric iron.
- the slurry then passes through a trash screen (7) and reports to the resin-in-pulp circuit.
- the oversize material from the trash screen passes to the tailings disposal section (9).
- a neutralizer such as limestone or lime is added during the resin-in-pulp circuit to maintain the pH at around 4.
- the tailings are neutralised with slaked lime, and then thickened (10), undergo tailings impoundment (1 1 ) and then decanted for disposal (12).
- the pregnant slurry (8) is then treated by the resin in pulp process where the nickel and cobalt and some impurities are extracted by the resin.
- the resin-in- pulp process consists of contacting the resin counter-currently with the leach slurry, typically in a series of air agitated or mechanically agitated continuously stirred tank reactors (13). In each of these stages the resin is separated from the slurry by screening and is advanced by pumping to the next stage. The slurry itself is advanced from one tank to the next, typically by gravity.
- an ion exchange resin with an iminodiacetic functional group is used in the resin-in-pulp process, for example iminodiacetic acid Amberlite IRC 718 or 748.
- Concentrated sulfuric acid strip solution (16) is used to strip the metal values from the resin, producing an eluate containing from 10 to 80 gpl nickel as well as cobalt.
- the resin is subjected to a weak acid wash (17) after stripping in order to minimize nickel recycle, and is transported back to the resin-in-pulp reactors.
- the strong nickel and cobalt containing acidic elutate is preferably partially neutralised to around pH 5 with sodium hydroxide to prepare it for the separation of cobalt from nickel.
- the cobalt is separated from the nickel in the eluate by contacting the eluate with an immiscible organic solvent, preferably containing the extractant Cyanex 272, in a solvent extraction step (18).
- Cyanex 272 is selective for cobalt over nickel, and after separation of the extractant, which also removes any remaining zinc, copper and manganese, a nickel containing raffinate remains.
- the raffinate (25) is neutralised with magnesium oxide slurry (27), to a pH of greater than 7.5, precipitating the nickel as nickel hydroxide (19), which can be filtered and washed (20) for direct sale.
- the nickel hydroxide produced contains approximately 40% nickel and low levels of iron (21 ).
- the cobalt is precipitated as a mixed cobalt sulfide (22) by treating the strip solution with sodium hydrogen sulfide solution together with sodium hydroxide (29). The temperature is maintained between 60 and 8O 0 C to ensure that the sulfide product obtained is crystalline. The impure cobalt sulfide solid is then filtered washed (23), and dried for direct sale (24).
- the cobalt may be recovered by known techniques such as solvent extraction or electro winning.
- the new process has the advantage over the current hydrometallurgical routes, in that it has fewer complex and capital intensive process steps to convert ore to a finished metal product, ferro nickel.
- a further advantage of the process over the conventional ferro nickel smelting process is that the valuable metal cobalt is recovered separately for sale, whereas in saprolite smelting the cobalt becomes part of the ferro nickel and its value is lost to the producer.
- a further advantage of the process described is that, as a consequence of the resin elution and solvent extraction process steps, the impurity levels in the ferro nickel produced using this nickel hydroxide product will be significantly lower than those currently achieved by the majority of commercial producers, and even those in the "super pure" ferro nickel grade.
- the process is also particularly attractive where large low grade deposits of saprolite or limonite exist at an established saprolite mining and smelting operation producing ferro nickel from the high grade ore.
- This process would allow treatment of the low grade ores which would normally be rejected to produce a mixed hydroxide feed for the existing smelter, reducing the unit power consumption per ton of nickel produced, producing cobalt for sale, and significantly improving the overall economics of the mining and processing the whole ore body.
- the process also has the flexibility that low iron nickel hydroxide product suitable for feeding to a ferro nickel smelter can be produced by this process in plant located at the laterite ore body, and shipped cost effectively because of its high nickel content to a remote existing ferro nickel smelter if the economics favour this.
- HPAL High Pressure Acid leach
- RIP resin-in-pulp
- the pulp was then screened to 212 microns, and oversize material discharged. Pulp passed through 212-micron screen was collected and used in the RIP circuit. The screened and neutralised pulp was brought to a temperature of 5O 0 C and continuously added into a ten stage RIP pilot plant to contact a Clean TeQ R604 resin.
- R604 is an ion exchange resin containing iminodiacetic acid groups. The nickel cobalt and other metals were adsorbed onto the resin. The resin was then separated from the pulp, and the metals stripped from it by treatment with a 15% sulfuric acid solution.
- Table 1 shows the average metal content of the liquor and solids content of the ore pulp slurry before and after RIP treatment during the 50 hour test run. Extraction rates were greater than 99.7% for both nickel and cobalt from the liquid phase of the pulp, and there was significant recovery of nickel and cobalt from the solid phase also.
- Table 1 Average metal content of pulp liquor and solids before and after Resin in Pulp treatment.
- composition of the eluate from the resin acid strip is indicated in table 2 below. This indicates that nickel concentrations of around 39 gpl in the eluate can be achieved, with low levels of contaminants such as chromium and silica.
- a synthetic solution that would simulate the eluate produced from the atmospheric pressure leaching of a laterite ore was prepared for testing.
- the solution was prepared by dissolving the sulfates of nickel, cobalt, copper, manganese, iron, and magnesium, together with calcium hydroxide and sodium chloride in water, and maintaining the solution under a nitrogen atmosphere to prevent oxidation. It was then subjected to neutralisation by adjusting the pH to 4.5 by the addition of calcium carbonate, allowed to settle and the clear solution decanted to become the feed solution for the tests.
- the solution analysis before and after the neutralisation step are shown in Table 3.
- a solvent extraction pilot plant consisting of 10 water-jacketed mixer-settlers, was used to conduct counter current semi continuous extraction, scrubbing and stripping tests on the Feed solution after neutralisation.
- the organic solution used as the solvent contained 15% Cyanex 272(v/v) and 5%TPB in Shellsol D70.
- the volume of the mixer and settler was 0.16 L and 0.38 L respectively.
- the temperature of the solution was kept constant at 40 °C.
- Impellers (30 mm diameter) with six-vanes were used for solution mixing and diaphragm pumps were used for solution circulation.
- aqueous solution and blank organic solutions were pumped counter-currently through three extraction stage mixer/settlers.
- Sodium hydroxide solution or sulfuric acid were used to maintain a pH of 5.8 in the mixers.
- Aqueous recycling was arranged to obtain an A/O volume ratio of 1 :1 in the mixer when required.
- Nitrogen gas was bubbled in the first stage mixer to prevent the oxidation of Fe(II) to Fe(III).
- Table 4 shows the extent of extraction of the metals in the organic solvent. The test shows that a complete extraction of Co, Cu, Zn, Mn, and Fe was achieved.
- the objective of the semi continuous scrubbing test was to maximise the scrubbing of the loaded organic solution to remove the co-extracted Ni, Mg and Ca
- the loaded organic solution from a series of semi continuous extraction tests similar to Example 1 was combined and used for the semi continuous scrubbing tests.
- the parameters varied were controlled pH (5.4 and 5.6 by the addition of sulfuric acid), number of stages (1 and 2 stages) and scrub solution (solutions 1 and 2) and a temperature of 4O 0 C.
- a synthetic scrub solution was prepared to simulate a diluted solution from the strip liquor.
- a typical result from the semi continuous scrubbing is summarised in Tables 5.
- the Ni scrub efficiency was in the range of 90-93% with 38-53 ppm Ni left in the organic solution.
- the pre-loaded and scrubbed organic solution was stripped using a sulfuric acid solution with the pH in the last stage controlled at 2.0.
- Example 5 The raffinate solutions from the semi continuous extraction tests in Example 1 were combined and subjected to hydroxide precipitation.
- the objective of the batch nickel hydroxide precipitation tests was to determine test conditions for a nickel precipitation efficiency of >99%.
- a total of three tests were conducted with the mole ratio of MgO over Ni to be 1 :1 , 1.2:1 and 1.4:1.
- the purity of MgO used in the precipitation tests was 96%.
- the elemental analysis of the nickel hydroxide precipitate produced indicates very low levels of impurities, cobalt, copper, zinc, manganese and iron, as seen in Table 8 below.
- the solvent extraction strip liquor from the semi continuous organic strip tests in example 3 were combined and subjected to mixed sulfide precipitation using sodium hydrosulfide solution to recover the cobalt content.
- the pH was adjusted to 3.5 with sodium hydroxide solution or sulfuric solution and the temperature controlled at 8O 0 C. After 60 minutes of mixing the slurry was filtered, the cake reslurried with tap water and refiltered three times, before drying at 105 0 C.
- the cobalt precipitation efficiency under these conditions was very high at 99.82%.
- Table 9 indicates the precipitation efficiency of the other metals in the solvent extraction strip liquor.
- Table 9 Metal behaviour in mixed sulfide precipitation (Mole ratio 1.4:1)
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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AU2004907370A AU2004907370A0 (en) | 2004-12-30 | Extraction of nickel and cobalt from a resin eluate stream | |
PCT/AU2005/001950 WO2006069416A1 (en) | 2004-12-30 | 2005-12-23 | Extraction of nickel and cobalt from a resin eluate stream |
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EP1841891A1 true EP1841891A1 (en) | 2007-10-10 |
EP1841891A4 EP1841891A4 (en) | 2008-06-25 |
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EP05819247A Withdrawn EP1841891A4 (en) | 2004-12-30 | 2005-12-23 | Extraction of nickel and cobalt from a resin eluate stream |
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EP (1) | EP1841891A4 (en) |
JP (1) | JP2008527164A (en) |
KR (1) | KR20070094819A (en) |
CN (1) | CN101094926A (en) |
AP (1) | AP2007004030A0 (en) |
BR (1) | BRPI0519687A2 (en) |
CA (1) | CA2593706A1 (en) |
EA (1) | EA010771B1 (en) |
GT (1) | GT200500393A (en) |
WO (1) | WO2006069416A1 (en) |
ZA (1) | ZA200704566B (en) |
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EP2054534A4 (en) * | 2006-08-23 | 2011-07-20 | Murrin Murrin Operations Pty Ltd | Improved hydrometallurgical method for the extraction of nickel from laterite ores |
AU2007100902A4 (en) * | 2006-08-23 | 2007-10-25 | Murrin Murrin Operations Pty Ltd | Improved Hydrometallurgical Method for the Extraction of Nickel from Laterite Ores |
US7935171B2 (en) | 2006-08-23 | 2011-05-03 | Bhp Billiton Ssm Development Pty Ltd. | Production of metallic nickel with low iron content |
BRPI0612374B1 (en) * | 2006-11-10 | 2015-08-11 | Vale Sa | Nickel and cobalt recovery process from lateritic ores using ion exchange resin and product containing nickel or cobalt |
BRPI0605892B1 (en) * | 2006-12-29 | 2015-09-01 | Vale Sa | Nickel and cobalt recovery process from an ion exchange resin eluate |
WO2009018619A1 (en) * | 2007-08-07 | 2009-02-12 | Bhp Billiton Ssm Development Pty Ltd | Atmospheric acid leach process for laterites |
US20090056501A1 (en) * | 2007-08-29 | 2009-03-05 | Vale Inco Limited | Hydrometallurgical process using resin-neutralized-solution of a heap leaching effluent |
US8147782B2 (en) | 2007-09-28 | 2012-04-03 | Vale Inco Limited | Producing nickel hydroxide suitable for pelletization with iron-containing ore and for stainless steel manufacture |
CN101643859B (en) * | 2008-08-07 | 2011-04-20 | 北京有色金属研究总院 | Process method for separating and purifying cobalt solution by extraction chromatography |
TW201034975A (en) * | 2008-12-03 | 2010-10-01 | Rainer Bauder | Systems and methods for wastewater treatment |
JP5157943B2 (en) | 2009-02-04 | 2013-03-06 | 住友金属鉱山株式会社 | Method for recovering nickel from sulfuric acid aqueous solution |
JP5881952B2 (en) * | 2011-01-24 | 2016-03-09 | 住友金属鉱山株式会社 | Method for producing cobalt sulfate |
CN102268537B (en) * | 2011-08-15 | 2013-05-29 | 广西银亿科技矿冶有限公司 | Method for extracting cobalt and nickel from laterite-nickel ore |
CN104745813B (en) * | 2013-12-31 | 2017-02-15 | 北京有色金属研究总院 | Method for comprehensively recovering nickel and magnesium in bio-leaching process of high-magnesium low-nickel sulfide ore |
CN104445424A (en) * | 2014-11-12 | 2015-03-25 | 浙江华友钴业股份有限公司 | Method for preparing high-purity manganese sulfate from manganese-containing waste liquid |
JP6604255B2 (en) * | 2016-04-05 | 2019-11-13 | 住友金属鉱山株式会社 | Method for removing impurities in organic solvents |
KR101950314B1 (en) * | 2017-08-31 | 2019-02-20 | 고려아연 주식회사 | Economical smelting method for nickel from nickel oxide ore, combined hydrometallurgical and pyrometallurgical process |
JP2019173063A (en) * | 2018-03-27 | 2019-10-10 | 住友金属鉱山株式会社 | Recovery method of nickel and cobalt from solution |
CN108660324A (en) * | 2018-05-21 | 2018-10-16 | 金川集团股份有限公司 | A method of extracting nickel, cobalt, copper from monel chloridizing leach solution |
KR102178219B1 (en) * | 2019-02-13 | 2020-11-12 | 고려아연 주식회사 | Economical Smelting Method for Nickel from Nickel Sulfide ore, combined Hydrometallurgical and Pyrometallurgical Process |
CN109867400A (en) * | 2019-02-19 | 2019-06-11 | 北京中科康仑环境科技研究院有限公司 | A kind of method that the depth of nickel (cobalt) raffinate removes nickel, cobalt |
JP7338283B2 (en) * | 2019-07-12 | 2023-09-05 | 住友金属鉱山株式会社 | Scandium recovery method |
CN111115903A (en) * | 2020-01-06 | 2020-05-08 | 湖南中伟新能源科技有限公司 | Method for removing cobalt in cobaltosic wastewater through two-stage ion exchange |
CN117222763A (en) * | 2023-07-31 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for short-process recovery of battery grade nickel and cobalt from laterite nickel ore |
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-
2005
- 2005-12-23 JP JP2007548644A patent/JP2008527164A/en active Pending
- 2005-12-23 EA EA200701407A patent/EA010771B1/en not_active IP Right Cessation
- 2005-12-23 KR KR1020077017513A patent/KR20070094819A/en not_active Application Discontinuation
- 2005-12-23 WO PCT/AU2005/001950 patent/WO2006069416A1/en active Application Filing
- 2005-12-23 CA CA002593706A patent/CA2593706A1/en not_active Abandoned
- 2005-12-23 AP AP2007004030A patent/AP2007004030A0/en unknown
- 2005-12-23 BR BRPI0519687-6A patent/BRPI0519687A2/en not_active IP Right Cessation
- 2005-12-23 EP EP05819247A patent/EP1841891A4/en not_active Withdrawn
- 2005-12-23 CN CNA2005800456511A patent/CN101094926A/en active Pending
- 2005-12-29 GT GT200500393A patent/GT200500393A/en unknown
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2007
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Patent Citations (5)
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US4382016A (en) * | 1981-05-14 | 1983-05-03 | American Cyanamid Company | Extractant for the selective removal of cobalt(II) from aqueous solutions |
WO1996020291A1 (en) * | 1994-12-27 | 1996-07-04 | Bhp Minerals International Inc. | Recovery of nickel and cobalt from laterite ores |
WO2000053820A1 (en) * | 1999-03-09 | 2000-09-14 | Bhp Minerals International, Inc. | Recovery of nickel and cobalt from ore |
WO2001029276A1 (en) * | 1999-10-15 | 2001-04-26 | Bhp Minerals International, Inc. | Resin-in-pulp method for recovery of nickel and cobalt from oxidic ore leach slurry |
US6387239B1 (en) * | 1999-11-17 | 2002-05-14 | Bhp Minerals International, Inc. | Recovery of metals from ore |
Non-Patent Citations (1)
Title |
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See also references of WO2006069416A1 * |
Also Published As
Publication number | Publication date |
---|---|
EA200701407A1 (en) | 2007-10-26 |
AP2007004030A0 (en) | 2007-06-30 |
EP1841891A4 (en) | 2008-06-25 |
CA2593706A1 (en) | 2006-07-06 |
BRPI0519687A2 (en) | 2009-03-03 |
KR20070094819A (en) | 2007-09-21 |
ZA200704566B (en) | 2008-08-27 |
WO2006069416A9 (en) | 2007-10-18 |
WO2006069416A1 (en) | 2006-07-06 |
CN101094926A (en) | 2007-12-26 |
EA010771B1 (en) | 2008-10-30 |
JP2008527164A (en) | 2008-07-24 |
GT200500393A (en) | 2006-09-20 |
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