WO1996020291A1 - Recuperation du nickel et du cobalt contenus dans des minerais laterises - Google Patents
Recuperation du nickel et du cobalt contenus dans des minerais laterises Download PDFInfo
- Publication number
- WO1996020291A1 WO1996020291A1 PCT/US1995/016118 US9516118W WO9620291A1 WO 1996020291 A1 WO1996020291 A1 WO 1996020291A1 US 9516118 W US9516118 W US 9516118W WO 9620291 A1 WO9620291 A1 WO 9620291A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- cobalt
- solution
- resin
- pregnant
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 500
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 238
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 136
- 239000010941 cobalt Substances 0.000 title claims abstract description 136
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000011084 recovery Methods 0.000 title claims abstract description 29
- 229910001710 laterite Inorganic materials 0.000 title description 14
- 239000011504 laterite Substances 0.000 title description 14
- 239000000243 solution Substances 0.000 claims abstract description 179
- 239000011347 resin Substances 0.000 claims abstract description 146
- 229920005989 resin Polymers 0.000 claims abstract description 146
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000000034 method Methods 0.000 claims abstract description 56
- 230000008569 process Effects 0.000 claims abstract description 46
- 238000005342 ion exchange Methods 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 31
- 239000012527 feed solution Substances 0.000 claims abstract description 30
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 4
- 238000002386 leaching Methods 0.000 claims description 37
- 239000003456 ion exchange resin Substances 0.000 claims description 19
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 17
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 12
- 229940044175 cobalt sulfate Drugs 0.000 claims description 12
- KXZQYLBVMZGIKC-UHFFFAOYSA-N 1-pyridin-2-yl-n-(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CNCC1=CC=CC=N1 KXZQYLBVMZGIKC-UHFFFAOYSA-N 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
- 238000009854 hydrometallurgy Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 230000037361 pathway Effects 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000011651 chromium Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 238000005363 electrowinning Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000010828 elution Methods 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 5
- 238000000658 coextraction Methods 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical class NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009291 froth flotation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- SVJCONVIKRDPJV-UHFFFAOYSA-N 1-(pyridin-2-ylmethylamino)propan-2-ol Chemical compound CC(O)CNCC1=CC=CC=N1 SVJCONVIKRDPJV-UHFFFAOYSA-N 0.000 description 1
- -1 42% Fe Chemical compound 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 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 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
-
- 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
- This invention relates to the hydrometallurgical processing of nickeliferous oxide ores and, in particular, to acid leaching of nickeliferous oxide ores selected from the group consisting of limonite and saprolite, which jointly are called laterites.
- nickeliferous oxide ores e.g., limonite and saprolite
- One process for recovering nickel and cobalt is the well known Moa Bay process involving acid leaching at elevated temperatures and pressures at which iron oxide and aluminum oxysulfate are substantially insoluble.
- the leach solution pH which is quite low (e.g., between 0 and 0.5), is then neutralized with coral mud to a pH of about 2.4 in a series of four tanks at a total retention time of about 20 minutes and the thus-treated product liquor (containing about 5.65 gpl Ni, 0.8 gpl Fe and 2.3 gpl A1), after solid-liquid separation, is then subjected to sulfide precipitation.
- the leach liquor is preheated and the sulfide precipitation carried out using H2S as the precipitating reagent in an autoclave at about 120oC (250oF) and a pressure of about 150 psig.
- the solution containing nickel and cobalt was then neutralized with ammonia to a pH (5.35) sufficient to precipitate any residual iron, aluminum, and chromium present using air as an oxidizing agent.
- the precipitate was thereafter separated from the solution and the nickel and cobalt solution then adjusted to a pH of about 1.5. H2S was added to precipitate
- the precipitate was separated from the solution by filtration and the nickel recovered by various methods, one method comprised treating the nickel-containing solution with hydrogen at elevated temperature and pressure to produce nickel powder.
- the hydrometallurgical process employed involves the use of a chelating ion exchange resins in which nickel is preferentially separated from cobalt and impurities typically obtained in the sulfuric acid leaching of laterite ores. While chelating ion exchange resins are known for extracting nickel from solutions, it was not known that, under relatively high acidic conditions, nickel can be separated from cobalt present in laterite leach solutions and provide an eluate with a substantially high Ni to Co ratio, e.g., at least about 50:1 suitable for recovery of substantially pure nickel by electrolysis.
- Another object is to provide a process for
- Fig. 1 is a flowsheet illustrating the process as applied to nickel laterite ores
- Fig. 2 depicts two curves published by Dow Chemical showing the absorption characteristics for each of nickel and cobalt using a Dow ion exchange composition identified by the trade designation XFS-4195 in which an active ingredient thereof is comprised of bis-picolylamine;
- Fig. 3 is a curve depicting the absorption
- Fig. 4 is illustrative of cumulative loading of nickel
- Fig.5 depicts generally an ISEP configuration in the form
- Figs. 5A and 5B are schematics shown as flow sheets illustrating the use of said ISEP carousel configuration in carrying out the ion-exchange extraction of nickel from solution using the resin XFS-4915;
- Fig. 6 is illustrative of cobalt and nickel loading at room temperature as a function of the number of bed volumes (BVS/hr) passed through a column of XFS-4195 resin;
- Fig. 7 depicts curves illustrating the selective stripping of cobalt from the resin employed in extracting the cobalt
- Fig. 8 is a simplified schematic illustrating the counterflow operation of the ISEP configuration through a series of columns
- Fig. 9 illustrates the use of the ISEP configuration for carrying out the Ni + Co IX (i.e. nickel plus cobalt ion exchange).
- Fig. 10 is a flow sheet based on the use of a Recoflo apparatus in recovering the nickel from the pregnant leach liquor, Fig. 10A being a continuation of Fig. 10.
- laterite ores e.g. limonite and saprolite
- Ni, Co, Fe, Al, Mg, Mn, Cr, SiO 2 and a variety of impurity elements along with free and
- An example of a limonite ore is one containing by weight 1.72% Ni, 0.14% Co, 41% Fe, 2.5% Al, 1.58% Mg, 0.8% Mn, 2.05% Cr, 12.1% SiO 2 and 11.3% LOI (Loss on Ignition).
- nickel and cobalt important elements of interest are nickel and cobalt.
- Such ores will generally contain by weight about 0.5% to 3% nickel and about .005 to 0.5% cobalt.
- the oxide ores to which the invention is applied may contain by weight about 0.5% to 3% nickel, about
- the invention is directed to a process for the recovery of nickel from particulate nickel oxide ores, such as saprolites and limonites, by sulfuric acid leaching said ores to form a pregnant solution of metal values, e.g., nickel and cobalt, which are recovered directly by ionexchange.
- the ore may be either
- sulfuric acid leaching is carried out at a relatively high temperature and pressure, e.g., 270° and 810 psi.
- a relatively high temperature and pressure e.g., 270° and 810 psi.
- Another embodiment of the process comprises forming an aqueous slurry in the form of a pulp of particulate oxide ore containing by weight about 1.5% Ni and about
- the leaching may be carried out by either atmospheric or pressure leaching.
- the amount of sulfuric acid solution is at least stoichiometrically sufficient to dissolve
- the pulp is subjected to pressure leaching following injection of sulfuric acid at an elevated temperature of about 150oC to 300oC at a pressure ranging from about 150 psig to 1,000 psig to solubilize at least 80% nickel and at least about 80% of the cobalt present in the ore.
- a typical time of leaching may range from about 15 minutes to 120 minutes.
- a pregnant liquor is obtained containing said nickel and cobalt as sulfates and residual other elements and undissolved residue as tailings.
- the acid in the pregnant solution is adjusted to or provided at a pH of about 0.5 to 4 following which the slurry is subjected to countercurrent decantation to separate the pregnant nickel and cobalt solution from said tailings.
- the acid in the tailings is neutralized with lime or other base to a pH of about 9 and the tailings disposed of.
- cobalt is contacted with an ion exchange resin under pH conditions selective to the absorption of nickel, while providing a raffinate containing cobalt.
- the raffinate is thereafter prepared for the removal of cobalt plus any nickel remaining therein by an ion exchange resin under conditions selective to the absorption of cobalt and nickel.
- the invention provides a process for selectively recovering nickel by ion exchange
- the process comprises contacting the nickelcontaining acid solution at a pH ranging from about 0.3 to 6 with a bed of protonated ion exchange resin in which protons associated with said resin are exchangeable with nickel ions in the solution.
- the protonated resin selectively extracts the nickel in preference to cobalt from the solution at a pH of less than about 2.
- the low pH is generally achieved by proton ions entering the solution as the nickel ions are absorbed by the resin.
- the absorbed nickel is then stripped from the resin with sulfuric acid to form a nickel sulfate solution characterized by a nickel to cobalt ratio of at least about 50:1 suitable for the recover of substantially pure nickel by electrolysis.
- the pregnant nickel solution is passed serially through a plurality of moving columns of the resin which move countercurrently to the flow of the pregnant solution entering the first column and exiting through the last column thereof with the bulk of the nickel removed in the initial columns and the nickel-impoverished solution containing cobalt thereafter passing through the last column.
- the pregnant nickel solution may be passed serially through two stationary columns of resin in a Recoflo ® ion exchange system produced by Eco-Tec Inc. of Pickering, Ontario, Canada.
- the feed solution is stopped and the first column only is stripped of the loaded nickel with sulfuric acid solution.
- the feed solution is again passed through the two columns serially, except the second column now becomes the "lead” column for feeding the pregnant liquor.
- the feed solution is stopped and the second column is stripped. Then feeding commences once again with the first column as the lead column. This is
- the nickel absorbed by the resin is stripped with sulfuric acid to provide a pregnant solution from which substantially pure nickel is recovered, such as by
- the cobalt plus the remaining nickel absorbed in a second ion exchange step is recovered by stripping with a sulfuric acid solution and the mixed cobalt nickel solution then sent to nickel/cobalt
- An important economic advantage of the invention is that sulfide precipitation of nickel and cobalt is
- the invention takes a more simple and economic route in that following the leaching of the nickel oxide ore, e.g., pressure leaching in the
- the limonite ore contained by weight 1.7% Ni, 0.15% Co, 40% Fe, 4% Al, 2% Mg, 2% Mn, 2% Cr, 10% SiO 2 and 15% LOI (Loss On Ignition).
- the technology employed includes an ore preparation step (1) in which the coarse reject 1A thereof may be used for the neutralization of excess acid.
- Sulfuric acid pressure leaching (2) is carried out at about 270° C with a leaching time in the range of about 20-40 minutes and generally ranging up to 30 minutes
- CCD countercurrent
- tailings neutralization (5) with limestone and milk of lime, in which the pH is raised to about 9, the residue is disposed of at a tailings dam.
- the CCD overflow solution 6 is contacted with an ion exchange resin where only nickel (plus copper if present) and only minor quantities of cobalt are loaded (7). Because nickel replaces the proton or hydrogen ion in the active part of the resin, the pH of the solution decreases during ion exchange, whereby the nickel is extracted by the resin in preference to a cobalt at a pH of less than about 2.
- the nickel is stripped from the ion exchange resin (7) with sulfuric acid.
- the nickel-containing solution is neutralized at (8A) with limestone and the neutralized solution subjected to solid/liquid separation with the solids recycled to neutralization (3) and the nickel solution sent to nickel electrowinning (15).
- the raffinate 8 with only minor amounts of nickel plus most of the cobalt and other impurities is further neutralized at (9) with limestone to a pH of about 2 to 4.
- the solids and liquid are separated at (10), the solids sent to tailings disposal (5) and the nickel/cobalt solution (11) sent to cobalt recovery 12 with the
- the nickel/cobalt following ion exchange is substantially pure and free of the contained impurities.
- the purified cobalt solution is treated for recovery of cobalt as a salable commodity, either by soda ash precipitation, sulfide precipitation or electrowinning.
- the nickel loaded on the resin (7) may be stripped with spent electrolyte (16) from the nickel electrowinning circuit (15). Prior to returning the stripped resin to loading, the resin is washed with water which converts the resin from the bisulfate into the sulfate form, releasing sulfuric acid which can be reused for stripping.
- DOW's XFS-4195 as the resin both for nickel loading as well as cobalt/nickel loading.
- Other resins which may be used include Rohm and Haas IR-904, Amberlite XE-318, and DOW XFS-43084. As disclosed hereinafter, the DOW resins have picolylamines as active groups.
- copolymers onto which weakly basic chelating picolylamine derivatives have been attached onto which weakly basic chelating picolylamine derivatives have been attached.
- DOW resin XFS 4195 is a stronger and preferred completing agent for nickel than the other resins
- the functional groups in the XFS 4195 and XFS 4196 resin are more specifically referred to as bis(2-picolyl)amine and N-(2hydroxyethyl-2-picolylamine, respectively.
- the XFS 43084 resin is similar to the resins above, that is, the resin is a macroporous polystyrene copolymer with a weakly basic chelating picolylamine derivative attached, i.e., specifically N-(2-hydroxypropyl)-2-picolylamine.
- the absorption constant is really not a constant but a function of the pH, as shown in the attached Figure 2 published by DOW chemical.
- the importance of keeping the pH low will be apparent from Figure 3. This figure clearly shows that it is advantageous to keep the pH of the pregnant solution low if one wants to
- Ni/Co ratio in the product which is important. For example, if the Ni/Co ratio in the electro-winning of nickel is better than 50:1 and particularly better than 90:1 or 100:1,, a high quality nickel product is
- Co/Ni ratios are similarly important.
- An example of a desirable ratio is a ratio which is at least about 50:1 preferably 80:1 or 100:1.
- these solutions contain between 20 and 100 gpl Co and have a cobalt to nickel ratio of about 100 to 1.
- chromium, aluminum and iron present a problem.
- hexavalent chromium has to be limited to less than 10 ppm to maintain a good quality deposit.
- XFS-4195 has a disadvantage in that it has a very high affinity for hexavalent chromium
- XFS-4195 is also selective for copper.
- Laterite leach solutions have up to about 50 ppm Cu and up to 300 ppm total chromium, of which about 10% or more may be present as hexavalent Cr.
- a pretreatment step for removing both Cu and hexavalent Cr can be included as a preferred embodiment of the
- This pretreatment step can either be a metal cementation step using iron, zinc or even nickel to reduce hexavalent Cr to the trivalent state and to cement copper.
- an ion exchange column may be included that is specifically used to load both hexavalent Cr and Cu from the leach solution. After this treatment, the leach solution can then be treated by the ion exchange approach discussed herein.
- a novel aspect of the invention is the fact that the XFS4195 resin has the ability of being converted from the sulfate to the bisulfate form by taking up sulfuric acid as follows:
- RIP hot resin-in-pulp
- Equation (3) shifts completely to the right under all conditions of the acid leaching process.
- Equation (4) shifts only to the sulfate side at higher pH and lower temperatures.
- the bisulfate to sulfate ratio as a function of the temperature and pH is calculated as
- the ion exchange process can tolerate more free acid in solution as the process temperature is raised.
- the kinetics of nickel loading on the resin are rather slow at room temperature. It is not economically advisable to heat the solution to improve reaction kinetics.
- the leach discharge is generally near its boiling point and an advantage is obtained since the nickel loading will be done hot without the need for additional heating.
- the improved kinetics usually result in a significant increase in resin capacity in that, in carrying out the invention, the resin is capable of being loaded at a rate of at 30 Bed Volumes (BV) per hour while conventionally the maximum is about 5 BV/hr.
- electrowinning cell generally should be at a pH of 2.5 to 3.5 to obtain the best deposition characteristics.
- Test work in the laboratory has shown that raising the pH of the eluate going to the electrolytic cell not to 2.5-3.5, but to 4.5 to 5.5, removes any aluminum and chromium which pass through the ion exchange system, down to less than about 10 ppm levels. Little nickel will precipitate at this pH.
- Example 1 As illustrative of the invention, the following example is given: Example 1
- Particulate lateritic oxide ore is formed into a pulp with water and screened at 28 mesh (U.S. Standard).
- the composition is comprised of 1.5% Ni, 0.14% Co, 4% Al, 0.8% Mg and the balance substantially iron, i.e., 42% Fe, present as oxides or hydroxides.
- the coarse fraction (approximately +20 mesh) is separated from the ore and may be used for atmospheric leaching by
- the fines fraction of the ore which is passed to pressure leaching 2 of the flowsheet, is first pulped with water or an aqueous solution to a pulp density of about 35%.
- Sulfuric acid is added to provide an acid to ore ratio of 0.2:1 to 0.3:1 based on weight of
- the pulp is pressure leached in an autoclave at a temperature of about 270oC under a total pressure of about 810 psia, the sulfuric acid being added to the pulp in the autoclave by injection.
- the ore is leached in about 15 to 60 minutes and the nickel extracted to about 95% based on the amount of nickel in the ore.
- the iron and aluminum in the solution are substantially rejected and appear in the tailings as basic aluminum sulfate (alunite) and hematite (Fe 2 O 3 ).
- the pregnant nickel solution is passed on to acid neutralization at (3).
- the solution is neutralized with limestone to a pH of about 2, after which the neutralized slurry is subjected to solids/liquid separation at (4).
- the neutralized slurry is subjected to solids/liquid separation at (4).
- neutralization step (3) may be omitted.
- the separated solution is passed to an ion-exchange apparatus (7) containing an ion-exchange resin specific to the
- the ratio of nickel in the feed solution to the quantity of resin employed is such as to provide 95% of resin loading capacity while extracting 95% of the nickel. This helps to ensure complete “crowding" off of cobalt, that is, the preferential loading of nickel over that of cobalt.
- a particularly advantageous ion exchange resin is one identified as DOW XFS 4195 in which the active ingredient is bis-picolylamine.
- the raffinate remaining is subjected to acid neutralization at (9) with limestone to a pH of about 2 to 4.5, following which the slurry from acid neutralization is passed to solid-liquid separation at (10) and the solution
- Fig. 8 is a simplified illustration of the general operation of the ISEP configuration.
- Fig. 8 is a schematic of Figs. 5, 5A and 5B,
- a carousel as one embodiment, comprising a series of resin-loaded columns 1, 2, 3 and ranging up to the Nth column, arranged and adapted to provide a serial pathway for the solution 5 from the first column to the Nth column, the interruption in the system at 4 indicating that other resinloaded columns may be present in the system between the 3rd and Nth columns.
- the rotational arrangement of the columns shown in Fig. 5 is such that the flow direction 6 of the resin loaded columns of Fig. 8 (i.e., the direction of travel of the resin columns) is counter to the flow direction of the nickel pregnant solution through the columns as shown, i.e., countercurrent flow) whereby the resins of each succeeding column remove the nickel from solution with the raffinate solution 7 containing cobalt flowing out of the system for the subsequent recovery of said cobalt.
- FIG. 5A and 5B A more detailed schematic is shown in Figs. 5A and 5B to be discussed later.
- the acid pH is preferably maintained at a level selective to the absorption of nickel, the pH being such that the nickel crowds off or substantially inhibits the absorption of cobalt.
- the nickel to cobalt ratio in the resin following substantially complete recovery of nickel is at least about 50:1 or at least 90:1 or higher.
- substantially impoverished in nickel may then be treated after a pH adjustment, if necessary, to recover the cobalt using a resin and conditions selective to the absorption of cobalt, e.g., DOW FXS 4195.
- sulfate/cobalt sulfate solution having a Ni/Co ratio corresponding generally to that produced by leaching a typical limonite ore.
- the solution contained 12.5 gpl Ni and 1 gpl Co and had a pH of 3.
- the solution had a
- Co loading is suppressed because the resin is already loaded with substantial nickel which cannot be easily exchanged for Co, even at the higher pH of the feed solution.
- Florida It consists of a carousel of 30 ion exchange columns connected to a rotary valve arrangement at the top and bottom of the carousel as means for providing serial, flow through the columns of resin.
- Each rotary valve consists of a rotating disc attached to the columns and a stationary disc attached to reservoirs of the various process solutions.
- Each stationary disc has 20 internal ports.
- Each column on the carousel is connected to a port on the rotating disc at the top and the bottom of the carousel. (There are 30 columns and 30 ports in each rotating disc.)
- the carousel and rotating disc portions of.the top and bottom valve rotate continuously and the ports in the rotating disc are connected to the ports of the stationary disc in sequence.
- the solution pumped continuously into a port or ports of the stationary disc flows serially through each column in sequence as the carousel rotates.
- a countercurrent flow of solution and resin can thus be effected in this apparatus by the aforementioned indexing means.
- a second ion exchange system for carrying out the novel aspects of the invention is referred to as the
- Recoflo (trademark) system manufactured by Eco-Tec Inc. of Pickering, Ontario, Canada. In this system, two beds of resin are employed. A cyclic process is used (note Fig. 10) to provide in effect a partial countercurrent flow resin and solution. As will be clearly apparent from Fig. 10, there are eight distinct steps in each cycle,
- step 1 feed solution is passed through beds I and 2 in series.
- Bed 1 has already been partially loaded with nickel in the preceding step while bed 2 contains fresh resin because it was stripped and washed in the preceding steps.
- fresh feed solution is contacted with partially loaded resin and fresh resin is contacted with partially depleted and acidified solution as occurs in the ISEP contactor.
- the stationary ports of the ISEP apparatus are illustrated in the configuration shown in Fig. 5A.
- the carousel containing thirty 1 3/8 inch diameter by lm high columns of Dow XFS 4195 resin, was rotated at 0.2
- compositions of the various solution streams after 15 hours of continuous operation in grams/liter were as follows:
- the Ni and Co extractions from feed solution were 95% and 13%, respectively, producing a Ni/Co ratio in the eluate of >300:1.
- the feed solution composition of 6.6 g/L Mg and the eluate composition of 0.2 g/L Mg Based on the feed solution composition of 6.6 g/L Mg and the eluate composition of 0.2 g/L Mg, only 1.8% of the Mg in the feed was passed to the eluate by solution entrainment, indicating >98% washing efficiency in the load wash stage.
- the other impurities, including Al and Mn behaved similarly to Mg.
- Ni/Co ratio of 310 in the eluate is sufficient for direct electrowinning of good quality Ni cathodes, although not of so-called Class I quality (Ni/Co 1670:1). These cathodes would certainly be usable for stainless steel manufacture as the main source of Ni for the production of stainless steel is ferronickel, which typically has a Ni/Co ratio of only 30-40:1.
- Example 5 The advantage of higher solution temperatures is clearly seen by comparing this result with the result of Example 3.
- Example 5 The advantage of higher solution temperatures is clearly seen by comparing this result with the result of Example 3.
- the configuration of the ISEP for this test was only slightly different from Examples 3 and 4, as shown in Fig. 5B.
- the main difference is that the acidity of the feed solution was 25 g/L H 2 SO 4 , which is about the natural acidity expected for high pressure acid leach solution.
- the strip solution was a "synthetic" spent
- electrolyte as normally produced by electrowinning Ni directly from neutralized eluate, as shown in Fig. 1.
- Ni and Co extractions in this test were approximately 86% and 0.4%, respectively. Surprisingly, very good Ni extraction was achieved despite the high acidity of the feed solution.
- Nickel and sulfuric acid mass balances using the above data show that in the loading section net production of H 2 SO 4 was only 0.5 moles per mole of Ni loaded on the resin. This indicates that some sulfuric acid liberated by Ni loading actually reloads on the resin via reaction (1), thus limiting the free acid content of the raffinate and permitting substantial Ni loading despite the high acidity of the feed solution.
- a test was carried out with a Recoflo apparatus comprised of two 2 inch diameter columns 12 inches high containing DOW XFS 4195 resin. The two columns were connected in series and operated cyclically as illustrated in Fig. 10. The solution flow rates were maintained at about 0.4 L/min and each solution was heated to 70oC.
- the feed solution contained 9.75 g/L Ni, 0.94 g/L Co, 2.1 g/L Al, 5.5 g/L Mg, 2.05 g/L Mn and had a pH of about 2.
- the strip solution contained 100 g/L H 2 SO 4 .
- a steady state condition was achieved after 10 complete cycles of
- the eluate was collected as two separate fractions, the first fraction consisting mainly of displaced wash water.
- the stationary ports were arranged as shown in Fig. 9.
- the carousel was rotating at 0.13 revolutions per hour. All feed, wash and strip solutions were heated to 20oC prior to being fed to the ISEP apparatus.
- the flow rates of each solution were as follows:
- Ni + Co were loaded per liter of resin in the loading step.
- This example illustrates the ability of the ion exchange system to load both nickel and cobalt under conditions of relatively low acidity ( ⁇ 15 g/L H2so4) and a resin loading less than the resin maximum capacity (-0.65 moles Ni+Co per liter resin).
- a pure cobalt plus nickel solution is obtained which can be treated for cobalt recovery via methods apparent to those skilled in the art.
- a sample of limonite of 30% solids was batch leached with concentrated sulfuric acid in an autoclave at 270oC to produce a leach slurry.
- the pH of one liter of leach slurry was adjusted to 3.7 with calcium carbonate and the slurry was then mixed with 200 mL of Dow XFS 4195 resin for 2 hours at room temperature.
- the resin was recovered from the slurry by screening over a 50 mesh screen.
- the leach solution before and after treatment with the resin assayed as follows:
- Ni and Co recoveries were estimated at 96% and 88%, respectively. Iron and zinc were also extracted. It should be noted, however, that iron dissolution during leaching can be prevented by careful control of leaching conditions.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
La présente invention concerne un procédé de récupération sélective de nickel par absorption avec échanges d'ions à partir d'une solution source d'acide sulfurique (6) qui contient du nickel et du cobalt et qui est obtenue au moyen d'un lessivage sous pression d'un minerai de limonite avec de l'acide sulfurique (2) suivi d'une neutralisation (3) puis d'une séparation des phases liquide et solide (4). Cette solution contient, sous forme de sulfates, de 0,5 à 40 g/l environ de nickel et de 0,001 à 2 g/l environ de cobalt. L'élimination des résidus a lieu en (5). Ledit procédé consiste à mettre en contact la solution d'acide, à un pH pouvant aller de 0,3 à 6, avec un lit de résine échangeuse d'ions ayant subi une protonation et dont les protons peuvent être échangés avec des ions nickel dans cette solution au cours de l'échange iionique (7). Le nickel, plutôt que le cobalt, est extrait de manière sélective de la solution ayant un pH inférieur à 2, ce qui provoque la formation d'un raffinat qui contient le cobalt (8). Le raffinat de cobalt est neutralisé (9), et il fait l'objet d'une séparation liquide/solide (10) à partir de laquelle le cobalt est récupéré (11, 12). Le raffinat appauvri en cobalt est envoyé (13) vers l'élimination des résidus (5). Le nickel absorbé est retiré de ladite résine avec de l'acide sulfurique (16) pour former une solution de sulfate de nickel caractérisée par un rapport nickel/cobalt au moins égal à 50 pour 1 environ qui convient à la récupération, par électrolyse (15), de nickel pratiquement pur. La solution de sulfate de nickel fait l'objet d'une neutralisation (8A) et d'une séparation solide/liquide avant de subir l'électrolyse.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU45153/96A AU699127B2 (en) | 1994-12-27 | 1995-12-13 | Recovery of nickel and cobalt from laterite ores |
BR9510115A BR9510115A (pt) | 1994-12-27 | 1995-12-13 | Recuperação de níquel e cobalto a partir de minériosde laterita |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US36489294A | 1994-12-27 | 1994-12-27 | |
US364,892 | 1994-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996020291A1 true WO1996020291A1 (fr) | 1996-07-04 |
Family
ID=23436550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/016118 WO1996020291A1 (fr) | 1994-12-27 | 1995-12-13 | Recuperation du nickel et du cobalt contenus dans des minerais laterises |
Country Status (6)
Country | Link |
---|---|
AU (1) | AU699127B2 (fr) |
BR (1) | BR9510115A (fr) |
CO (1) | CO4560388A1 (fr) |
CU (1) | CU22611A3 (fr) |
OA (1) | OA10492A (fr) |
WO (1) | WO1996020291A1 (fr) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000053820A1 (fr) * | 1999-03-09 | 2000-09-14 | Bhp Minerals International, Inc. | Recuperation de nickel et de cobalt a partir de minerais |
WO2001029276A1 (fr) * | 1999-10-15 | 2001-04-26 | Bhp Minerals International, Inc. | Procede de traitement par resine en pulpe permettant de recuperer du nickel et du cobalt dans une bouillie de lixiviation de minerai oxyde |
WO2001032943A2 (fr) * | 1999-11-03 | 2001-05-10 | Bhp Minerals International, Inc. | Processus de lixiviation a pression atmospherique permettant de recuperer du nickel et du cobalt de limonite et de minerais saprolithiques |
WO2006069416A1 (fr) | 2004-12-30 | 2006-07-06 | Bhp Billiton Ssm Technology Pty Ltd | Extraction de nickel et de cobalt a partir d'un flux d'elution de resine |
WO2008049177A2 (fr) * | 2006-10-27 | 2008-05-02 | Companhia Vale Do Rio Doce | Procédé de production de cobalt métallique à partir de produit raffiné d'extraction par solvant de nickel |
WO2008138039A1 (fr) * | 2007-05-14 | 2008-11-20 | Bhp Billiton Ssm Development Pty Ltd | Récupération de nickel à partir d'un minerai de latérite à haute teneur de matériaux ferreux |
WO2009026693A1 (fr) * | 2007-08-29 | 2009-03-05 | Vale Inco Limited | Processus hydrométallurgique de récupération distincte du nickel et du cobalt à l'aide de résines échangeuses d'ions |
WO2009149522A1 (fr) * | 2008-06-13 | 2009-12-17 | Poseidon Nickel Limited | Procédé rhéologique pour la récupération hydrométallurgique de métaux de base à partir de minerais |
US20120204680A1 (en) * | 2011-02-11 | 2012-08-16 | Emc Metals Corporation | System and Method for Recovery of Nickel Values From Nickel-Containing Ores |
WO2013165735A1 (fr) | 2012-05-01 | 2013-11-07 | Dow Global Technologies Llc | Récupération de nickel de cobalt en utilisant l'échange d'ions continu |
WO2014025568A1 (fr) | 2012-08-06 | 2014-02-13 | Dow Global Technologies Llc | Récupération de nickel à l'aide d'un procédé d'échange d'ions et d'extraction électrolytique continu intégré |
WO2019090389A1 (fr) * | 2017-11-10 | 2019-05-16 | Bhp Billiton Nickel West Pty Ltd | Production de sulfate de nickel de pureté élevée |
CN111270070A (zh) * | 2018-12-04 | 2020-06-12 | 格林美(江苏)钴业股份有限公司 | 一种用于p507钴萃取系统的洗涤方法及装置 |
CN113526576A (zh) * | 2021-05-31 | 2021-10-22 | 金川集团股份有限公司 | 一种高镍低酸低钠硫酸镍溶液的制取方法 |
US11365128B2 (en) | 2017-06-15 | 2022-06-21 | Energysource Minerals Llc | Process for selective adsorption and recovery of lithium from natural and synthetic brines |
WO2022178628A1 (fr) * | 2021-02-24 | 2022-09-01 | Sherritt International Corporation | Co-traitement de concentré de sulfure de cuivre avec du minerai latéritique de nickel |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPO837197A0 (en) * | 1997-08-01 | 1997-08-28 | Centaur Mining & Exploration Limited | Selective precipitation of nickel and cobalt |
CN116325230A (zh) * | 2020-10-14 | 2023-06-23 | 株式会社Lg新能源 | 制造高镍正极活性材料的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3801695A (en) * | 1971-10-19 | 1974-04-02 | Bayer Ag | Process for the separation of nickel and/or cobalt from manganese |
US3991159A (en) * | 1975-01-09 | 1976-11-09 | Amax Inc. | High temperature neutralization of laterite leach slurry |
US3998924A (en) * | 1975-08-04 | 1976-12-21 | The Dow Chemical Company | Recovery of non-ferrous metals from acidic liquors with a chelate exchange resin in presence of iron(III) |
US4320099A (en) * | 1980-07-28 | 1982-03-16 | Inco Limited | Process for nickel removal from concentrated aqueous cobaltous sulfate solutions |
JPS62228436A (ja) * | 1986-03-29 | 1987-10-07 | Miyoshi Oil & Fat Co Ltd | コバルトの分離回収方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CU22568A3 (es) * | 1994-10-05 | 1999-08-03 | Billiton Intelectual Property B V | Recuperación de níquel a partir de mineral laterítico |
-
1995
- 1995-12-13 BR BR9510115A patent/BR9510115A/pt not_active Application Discontinuation
- 1995-12-13 AU AU45153/96A patent/AU699127B2/en not_active Ceased
- 1995-12-13 WO PCT/US1995/016118 patent/WO1996020291A1/fr active Application Filing
- 1995-12-20 CU CU1995138A patent/CU22611A3/es not_active IP Right Cessation
- 1995-12-27 CO CO95061791A patent/CO4560388A1/es unknown
-
1997
- 1997-06-18 OA OA70028A patent/OA10492A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3801695A (en) * | 1971-10-19 | 1974-04-02 | Bayer Ag | Process for the separation of nickel and/or cobalt from manganese |
US3991159A (en) * | 1975-01-09 | 1976-11-09 | Amax Inc. | High temperature neutralization of laterite leach slurry |
US3998924A (en) * | 1975-08-04 | 1976-12-21 | The Dow Chemical Company | Recovery of non-ferrous metals from acidic liquors with a chelate exchange resin in presence of iron(III) |
US4320099A (en) * | 1980-07-28 | 1982-03-16 | Inco Limited | Process for nickel removal from concentrated aqueous cobaltous sulfate solutions |
JPS62228436A (ja) * | 1986-03-29 | 1987-10-07 | Miyoshi Oil & Fat Co Ltd | コバルトの分離回収方法 |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000053820A1 (fr) * | 1999-03-09 | 2000-09-14 | Bhp Minerals International, Inc. | Recuperation de nickel et de cobalt a partir de minerais |
WO2001029276A1 (fr) * | 1999-10-15 | 2001-04-26 | Bhp Minerals International, Inc. | Procede de traitement par resine en pulpe permettant de recuperer du nickel et du cobalt dans une bouillie de lixiviation de minerai oxyde |
US6350420B1 (en) | 1999-10-15 | 2002-02-26 | Bhp Minerals International, Inc. | Resin-in-pulp method for recovery of nickel and cobalt |
WO2001032943A2 (fr) * | 1999-11-03 | 2001-05-10 | Bhp Minerals International, Inc. | Processus de lixiviation a pression atmospherique permettant de recuperer du nickel et du cobalt de limonite et de minerais saprolithiques |
WO2001032943A3 (fr) * | 1999-11-03 | 2001-09-27 | Bhp Minerals Int Inc | Processus de lixiviation a pression atmospherique permettant de recuperer du nickel et du cobalt de limonite et de minerais saprolithiques |
US6680035B2 (en) | 1999-11-03 | 2004-01-20 | Bhp Minerals International Inc. | Atmospheric leach process for the recovery of nickel and cobalt from limonite and saprolite ores |
EP1841891A4 (fr) * | 2004-12-30 | 2008-06-25 | Bhp Billiton Ssm Tech Pty Ltd | Extraction de nickel et de cobalt a partir d'un flux d'elution de resine |
WO2006069416A1 (fr) | 2004-12-30 | 2006-07-06 | Bhp Billiton Ssm Technology Pty Ltd | Extraction de nickel et de cobalt a partir d'un flux d'elution de resine |
EP1841891A1 (fr) * | 2004-12-30 | 2007-10-10 | BHP Billiton Ssm Technology Pty Ltd. | Extraction de nickel et de cobalt a partir d'un flux d'elution de resine |
WO2008049177A2 (fr) * | 2006-10-27 | 2008-05-02 | Companhia Vale Do Rio Doce | Procédé de production de cobalt métallique à partir de produit raffiné d'extraction par solvant de nickel |
WO2008049177A3 (fr) * | 2006-10-27 | 2008-07-03 | Vale Do Rio Doce Co | Procédé de production de cobalt métallique à partir de produit raffiné d'extraction par solvant de nickel |
GB2456701A (en) * | 2006-10-27 | 2009-07-29 | Vale Do Rio Doce Co | Method for production of metallic cobalt from the nickel solvent extraction raffinate |
GB2456701B (en) * | 2006-10-27 | 2012-01-18 | Vale Do Rio Doce Co | Method for production of metallic cobalt from the nickel solvent extraction raffinate |
WO2008138039A1 (fr) * | 2007-05-14 | 2008-11-20 | Bhp Billiton Ssm Development Pty Ltd | Récupération de nickel à partir d'un minerai de latérite à haute teneur de matériaux ferreux |
US8758479B2 (en) | 2007-05-14 | 2014-06-24 | Bhp Billiton Ssm Development Pty Ltd | Nickel recovery from a high ferrous content laterite ore |
AU2008251010B2 (en) * | 2007-05-14 | 2012-07-12 | Cerro Matoso Sa | Nickel recovery from a high ferrous content laterite ore |
WO2009026693A1 (fr) * | 2007-08-29 | 2009-03-05 | Vale Inco Limited | Processus hydrométallurgique de récupération distincte du nickel et du cobalt à l'aide de résines échangeuses d'ions |
WO2009149522A1 (fr) * | 2008-06-13 | 2009-12-17 | Poseidon Nickel Limited | Procédé rhéologique pour la récupération hydrométallurgique de métaux de base à partir de minerais |
US20120204680A1 (en) * | 2011-02-11 | 2012-08-16 | Emc Metals Corporation | System and Method for Recovery of Nickel Values From Nickel-Containing Ores |
WO2013165735A1 (fr) | 2012-05-01 | 2013-11-07 | Dow Global Technologies Llc | Récupération de nickel de cobalt en utilisant l'échange d'ions continu |
US9068247B2 (en) | 2012-05-01 | 2015-06-30 | Dow Global Technologies Llc | Nickel and cobalt recovery using continuous ion exchange |
AU2013256760B2 (en) * | 2012-05-01 | 2017-06-01 | Dow Global Technologies Llc. | Nickel and cobalt recovery using continuous ion exchange |
RU2621504C2 (ru) * | 2012-05-01 | 2017-06-06 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Извлечение никеля и кобальта с использованием непрерывного ионного обмена |
WO2014025568A1 (fr) | 2012-08-06 | 2014-02-13 | Dow Global Technologies Llc | Récupération de nickel à l'aide d'un procédé d'échange d'ions et d'extraction électrolytique continu intégré |
US11365128B2 (en) | 2017-06-15 | 2022-06-21 | Energysource Minerals Llc | Process for selective adsorption and recovery of lithium from natural and synthetic brines |
WO2019090389A1 (fr) * | 2017-11-10 | 2019-05-16 | Bhp Billiton Nickel West Pty Ltd | Production de sulfate de nickel de pureté élevée |
CN111270070A (zh) * | 2018-12-04 | 2020-06-12 | 格林美(江苏)钴业股份有限公司 | 一种用于p507钴萃取系统的洗涤方法及装置 |
WO2022178628A1 (fr) * | 2021-02-24 | 2022-09-01 | Sherritt International Corporation | Co-traitement de concentré de sulfure de cuivre avec du minerai latéritique de nickel |
CN113526576A (zh) * | 2021-05-31 | 2021-10-22 | 金川集团股份有限公司 | 一种高镍低酸低钠硫酸镍溶液的制取方法 |
Also Published As
Publication number | Publication date |
---|---|
CU22611A3 (es) | 2000-02-10 |
BR9510115A (pt) | 1997-12-30 |
AU4515396A (en) | 1996-07-19 |
CO4560388A1 (es) | 1998-02-10 |
AU699127B2 (en) | 1998-11-26 |
OA10492A (en) | 2002-04-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU699127B2 (en) | Recovery of nickel and cobalt from laterite ores | |
US6350420B1 (en) | Resin-in-pulp method for recovery of nickel and cobalt | |
RU2149910C1 (ru) | СПОСОБ ИЗВЛЕЧЕНИЯ НИКЕЛЯ ИЗ Ni-Fe-Mg-ЛАТЕРИТНОЙ РУДЫ С ВЫСОКИМ СОДЕРЖАНИЕМ МАГНИЯ | |
US7901484B2 (en) | Resin-in-leach process to recover nickel and/or cobalt in ore leaching pulps | |
EP1644541B1 (fr) | Procede de recuperation de nickel et de cobalt par lixiviation en tas de matiere contenant du nickel ou du cobalt de basse teneur | |
AU2008251010B2 (en) | Nickel recovery from a high ferrous content laterite ore | |
EP1971697B1 (fr) | Precipitation d'hematite | |
US20040228783A1 (en) | Process for the recovery of value metals from material containing base metal oxides | |
US4008076A (en) | Method for processing manganese nodules and recovering the values contained therein | |
EP1841891A1 (fr) | Extraction de nickel et de cobalt a partir d'un flux d'elution de resine | |
KR20070060120A (ko) | 습식 야금 공정 및 건식 야금 공정의 조합에 의한 페로-니켈 또는 니켈 매트 제조 | |
US20070297960A1 (en) | Extraction of Nickel and Cobalt from a Resin Eluate Stream | |
US3933975A (en) | Nickel-cobalt separation | |
WO2008124904A1 (fr) | Procédé de récupération de nickel et de cobalt à partir d'un éluat par extraction par solvant, et produit contenant du nickel ou du cobalt obtenu par ledit procédé | |
Cole et al. | Solvent extraction developments in Southern Africa | |
EP2553129B1 (fr) | Lixiviation faiblement acide de nickel et de cobalt à partir de minerais de nickel pauvres contenant du fer | |
AU2005321748A1 (en) | Extraction of nickel and cobalt from a resin eluate stream |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AU BR CA MG MX RU SI SK |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: CA |