WO2011006223A1 - Process of recovery of base metals from oxide ores - Google Patents
Process of recovery of base metals from oxide ores Download PDFInfo
- Publication number
- WO2011006223A1 WO2011006223A1 PCT/BR2010/000227 BR2010000227W WO2011006223A1 WO 2011006223 A1 WO2011006223 A1 WO 2011006223A1 BR 2010000227 W BR2010000227 W BR 2010000227W WO 2011006223 A1 WO2011006223 A1 WO 2011006223A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- ore
- ferric
- ferrous chloride
- oxide ore
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000010953 base metal Substances 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims description 36
- 238000011084 recovery Methods 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 31
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 229910052742 iron Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 229910052595 hematite Inorganic materials 0.000 claims description 10
- 239000011019 hematite Substances 0.000 claims description 10
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 4
- 238000004090 dissolution Methods 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010977 unit operation Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 abstract 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 238000000605 extraction Methods 0.000 description 18
- 229910001710 laterite Inorganic materials 0.000 description 11
- 239000011504 laterite Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000007038 hydrochlorination reaction Methods 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- -1 but not limited to Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007928 solubilization Effects 0.000 description 4
- 238000005063 solubilization Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IPRPPFIAVHPVJH-UHFFFAOYSA-N (4-hydroxyphenyl)acetaldehyde Chemical compound OC1=CC=C(CC=O)C=C1 IPRPPFIAVHPVJH-UHFFFAOYSA-N 0.000 description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 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 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910018965 MCl2 Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001238 wet grinding 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
- 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
- C22B3/10—Hydrochloric acid, other halogenated 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0019—Chloridizing roasting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating 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
- C22B23/00—Obtaining nickel or cobalt
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
-
- 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 disclosure relates to recovery of base metal values, such as nickel, cobalt, copper and the like, from oxide type materials.
- High acid consumption is one of the main components of operational costs of laterite leaching.
- Nickel and the other base metals are usually bonded in ferruginous ores, as in limonites, or in saprolite matrixes, both being rich in magnesium. Accordingly, in order to effectively leach those elements, iron and magnesium need to be leached, both iron and magnesium being available in high amounts and thus increasing overall acid consumption. That is the main issue with conventional atmospheric or heap leaching operations, as seen throughout the available literature, for example in patent applications WO/2010/000029,
- Document WO 2010000029 (BHP Billiton SSM) teaches a process for the recovery of nickel and cobalt from a nickeliferous oxidic ore by heap leaching and/or atmospheric agitation leaching, the process generally including mixing a sulfur containing reductant selected from reductants that do not include copper into a nickeliferous oxidic ore, leaching the reductant/ore mixture with an acidic leach reagent to produce a pregnant leach solution including nickel, cobalt, iron
- WO 2009146518 - (VALE S.A.) describes a process of recovering nickel and cobalt and regenerating the main raw materials, the process including granulometric separation, leaching, neutralization, mixed hydroxide precipitate (MHP) production in only one stage and the pressure crystallization of magnesium sulphite.
- the process proposes a way to recover nickel and cobalt from laterite ores through atmospheric and heap leaching with staged addition of ore - by size separation - and H 2 SO 4 , decreasing the nickel losses, simplifying the neutralization circuit and producing a more purified MHP.
- the present process route is employed for nickel extraction, including the one from high magnesium containing lateritic ores.
- WO 2009 018619 (BHP Billiton SSM) describes an atmospheric leach process in the recovery of nickel and cobalt from lateritic ores, the process including providing limonitic and saprolitic ore fractions of a laterite ore, separately slurrying the limonitic and saprolitic ore fractions to produce a limonitic ore slurry and a saprolitic ore slurry, separating any limonitic type minerals from the saprolitic ore slurry to produce a saprolitic feed slurry, milling or wet grinding the saprolitic feed slurry, leaching the limonitic ore slurry with concentrated sulfuric acid in a primary leach step, introducing the saprolitic feed slurry to the leach process in a secondary leach step by combining the saprolitic feed slurry with the leached limonite slurry following substantial completion of the primary leach step, and releasing sulfuric acid to assist
- EP 1790739 (Companhia Vale do Rio Doce) teaches a process for extraction of nickel, cobalt, and other metals from laterite ores by heap leaching, and of the product obtained as well, characterized by the fact that it is comprised of crushing, agglomeration, stacking and heap leaching stages, with this last stage being a continuous, countercurrent, heap leaching system with two or more stages, comprised of two phases, one of which is composed of the ore, or solute, and the other is composed of the leaching solution, or solvent, which are supplied at opposite ends of the series of stages and flow in opposite directions.
- a neutralizing agent such as, but not limited to, lime, limestone or magnesia, is needed to increase solution pH and hydrolyze some impurities from solution. This operation produces hydroxides, as ferric hydroxides, that make solid-liquid separation very onerous. Rheology is often a problem too. To avoid that problem, high dilution of the solution is needed, and higher volumes of poorer solution are needed to be purified.
- Effluent treatment could also be an issue, as magnesium levels can be prohibitive. There are several methods for removing magnesium from solution, but all come with a high cost. Solid residue is also not very stable and needs large tailings ponds.
- Ferric or ferrous chloride is agglomerated with the ore and later submitted to selective hydrolysis of the iron chloride.
- the agglomeration and hydrolysis depend on the iron oxidation stage and generates in-situ HCI that attacks base metals oxides, forming metal chlorides.
- These chlorides are later solubilized in water, generating an iron and aluminum-free leach effluent. This effluent can then be submitted to any known and more simplified purification technology because there is no longer a need for an iron removal stage.
- aspects of this invention reduce the impact of using direct HCI to leach oxide ores by indirect hydrochlorination using ferric or ferrous chloride. As a result, the use of HCI is limited to a smaller unit operation, reducing overall costs and maintenance.
- the ore includes a first metal selected from the group consisting of at least one of iron, magnesium and aluminum and a second metal selected from nickel, cobalt and copper.
- the method may include the steps of reducing ore particle size to suit the latter unit operations, favoring contact of the metal elements, contacting the ore with at least one of ferric or ferrous chloride, hydrated or anhydrous, to produce a mix of ore and iron(ll or III) chloride, subjecting the mixture of the ore and ferric or ferrous chloride to enough energy to decompose the chlorides into
- hydrochloric acid and a iron oxide, preferably hematite contacting the readily-formed hydrochloric acid with the base metal oxides from the second group described above, forming their respective chlorides, and selectively dissolve the produced base metal chlorides, leaving the metals from the first group as oxides and in the solid state.
- the method may also include methods of recovering the dissolved base metal from aqueous solution.
- FIG. 1 is an illustration of a method for extracting base metals from laterite ore, according to various aspects of the present invention
- Fig. 2 is a graph illustrating Gibbs free energy behavior with temperature for indirect hydrochlorination utilizing ferric chloride, according to various aspects of the present invention.
- Fig. 3 is a graph illustrating Gibbs free energy behavior with temperature for indirect hydrochlorination utilizing ferrous chloride, according to various aspects of the present invention. DETAILED DESCRIPTON OF THE INVENTION
- aspects of the present invention relate to a process for recovering base metal values from oxide materials, specifically metals found, e.g., in laterite ores, such as nickel, cobalt and copper.
- oxide materials such as, for example, laterite ores
- ferric or ferrous chloride to produce an iron, aluminum and magnesium-free solution that carries base metals chlorides, such as nickel, cobalt and copper, through indirect hydrochlorination, as described by equations (1 ) to (3) below.
- Fig. 1 is an illustration of a method 100 for extracting base metals from laterite ore, according to various aspects of the present invention.
- the oxide material may be initially crushed or granulated to liberate the oxide base metals prior to mixing with ferric or ferrous chloride, as indicated in step S101.
- the particle reduced oxide material may be mixed with ferric or ferrous chloride and agglomerated with a mineral acid if necessary, as indicated in step S102.
- the mix of particle-reduced ore and ferric or ferrous chloride is contacted with enough wet air at high temperature to convert base metals into chlorides and iron, and aluminum and magnesium to their respective oxides, as indicated in step S103.
- Figs. 2 and 3 Gibbs free energy behavior for hydrochlorination with using both ferric chloride and ferrous chloride is illustrated in Figs. 2 and 3.
- water may be added to the converted ore at a pH of between about 8 and 2.
- the pH can be controlled using a mineral acid such as, for example, hydrochloric acid, in order to avoid the newly formed oxides from leaching.
- the solution becomes therefore iron-, aluminum- and magnesium-free.
- the solubilized base metals can then be purified into sellable products by various methods known by those skilled in the art.
- the solid portion of the solid liquid separation after proper washing of residual solution, may be submitted to a high intensity magnetic separation to separate hematite from other oxides. Neutralization may optionally be needed. Hematite may then be contacted with hydrochloric acid to produce ferric chloride and water.
- a reducing agent such as, but no limited to, iron may be added to the system.
- ore is extracted from the mine to provide beneficiation plant a run-of-mine.
- the run of mine may then be prepared to be fed into the extraction plant.
- the size of the ore is reduced to an appropriate size to liberate base metals oxides for proper indirect hydrochlorination and efficient solubilization.
- ore size may be kept between 2mm and 0.050mm, and optionally less than 0.5mm. These sizes can be obtained by different conventional unit operations well known and described in the literature, such as, but not limited to, crushing and grinding.
- Ore may be separated in two fractions: a first one that is rich in nickel and having about the sizes described above, and another one that is poor in nickel. The fraction of ore that is poor in nickel may be discarded. It should be noted that the above-discussed fractions and sizes are exemplary, and those skilled in the art may provide more or less fractions of varying sizes.
- ferric or ferrous chloride sufficient for total hydrochlorination of payable base metals.
- Ferric or ferrous chloride can be added in the ratio between, for example, 0.05 and 1.5 times the ore mass, and optionally between 0.1 and 0.5 times the ore mass.
- Water or a mineral acid may optionally also be added to improve agglomeration.
- an oxidizing agent may also be added to the ore, such as, but not limited to, oxygen, potassium permanganate, ozone or hydrogen peroxide.
- the oxidizing agent may be added in a similar mass ratio range as ferrous chloride. It should be noted that ferric or ferrous chloride may be obtained by any available source.
- the oxidizing agent reacts with ferrous chloride, forming hematite and HCI, as shown by the reaction below.
- the temperature range needed for this reaction ranges may be between 60 0 C and 600 0 C, optionally between about 100 0 C and about 300 0 C for kinetics reasons.
- Residence time may range between 0.5 hour and 12 hours, optionally between 1 hour and 2 hours.
- ferric chloride When using ferric chloride, an oxidizing agent may not be necessary.
- the properly agglomerated ore is taken to a hydrolysis stage, usually but not limited to a kiln, where the ore is submitted to conditions under which ferric and/or ferrous chloride is decomposed, producing stable hematite or other hydrated iron oxide, and HCI. During this step, the agglomerated ore is then submitted to elevated
- the temperature range needed for this second reaction mechanism may ranges between 60 0 C and 600 0 C, and optionally around 150 0 C to 350 0 C. Residence time requirements may be the same as the residence time requirements for ferrous chloride.
- the newly formed chlorides are soluble in water, but the metal M such as iron, aluminum and
- equation (3) would yield an iron, magnesium and aluminum-free effluent, easily purified by various methods available in the literature and known by those skilled in the art.
- hydrochlorination as described before is terminated, the ore could be stacked in a heap and leached with acidified water, with a pH of at least 7.
- Any mineral acid may. be used such as, for example, sulfuric acid, nitric acid or hydrochloric acid.
- the acid content may be increased up 100g/L, but the pH may be kept between about 1 and about 3.
- Leaching solution could be recycled, with acid make-up, to increase payable metals concentration.
- Another possible way of solubilizing the payable metals is through agitated tanks, keeping pH at the same ranges. Residence times may be determined to be between about 5 minutes and about 24 hours, and optionally between 30 minutes and 120 minutes.
- the solution may be heated to increase solubilization kinetics, and the percentage of solids may be kept between about 5% and about 50%, depending on how
- the percentage of solids may be in the range 15% and 35%. It should be noted that any other form of solubilization known by those skilled in the art may also be employed.
- any method of downstream purification may be used. According to various aspects, there is no need of an iron removal stage and an aluminum removal stage, or of effluent treatment for magnesium or manganese removal, because these elements were already stabilized as oxides in the furnace.
- tailings produced from the solid-liquid separation may be contacted with a high intensity magnetic field, after first been washed to remove residual base metals solution. Neutralization may also be needed, but may not be necessary.
- the magnetic field separates hematite from other oxides. It should be noted that other separation methods, known from those skilled in the art, can be used instead of a magnetic separator.
- hematite in order to produce ferric or ferrous chloride, hematite may be contacted with hydrochloric acid, producing the chosen iron chloride, as described by equations below:
- ferrous chloride such as, for example, metal iron (Fe).
- Ferric chloride may also be produced by contacting metal iron with hydrochloric acid in oxidizing conditions.
- Hydrochloric acid may be produced by reacting a chloride salt, such as sodium chloride, potassium chloride, with an acid, such as sulfuric acid.
- a chloride salt such as sodium chloride, potassium chloride
- an acid such as sulfuric acid.
- potassium chloride may be used as a chloride salt. Reacting potassium chloride with sulfuric acid produces dry hydrochloric acid (e.g., free of water) and potassium sulfate, a useful byproduct.
- HCI is used in a controlled form, reducing the need for expensive equipments.
- Cheaper construction materials and simpler equipments are needed.
- Gas-solid interaction is not a big concern because HCI is generated within the agglomerated ore, diffusing throughout the material. That way, a simple kiln such as, but not limited to, a rotary kiln, can be employed at the hydrolysis stage, thus reducing capital costs.
- Downstream equipments are also simpler because no high chloride solution will be produced.
- a laterite charge is subjected to a 90 minute indirect hydrochlorination at 300 0 C with wet air injection.
- the sample contains 2.01 % Ni, 0.073% Co, 49.1 %Fe, 3.07%Mg and 06% SiO 2 . Extraction results are show in Table 2 below.
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Abstract
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Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
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EP10799302.4A EP2454389B1 (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
KR1020127003905A KR101751084B1 (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
CA2768021A CA2768021C (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
JP2012519852A JP5567670B2 (en) | 2009-07-14 | 2010-07-14 | Method for recovering base metals from oxide ores |
AP2012006101A AP3427A (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
DK10799302T DK2454389T3 (en) | 2009-07-14 | 2010-07-14 | A process for the recovery of base metals from oxidårer |
US13/384,207 US8802042B2 (en) | 2002-07-19 | 2010-07-14 | Process of recovery of base metals from oxide ores |
EA201270162A EA019801B1 (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
CN201080036095.2A CN102712965B (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
AU2010273197A AU2010273197B2 (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
NZ597637A NZ597637A (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores |
IN702DEN2012 IN2012DN00702A (en) | 2009-07-14 | 2010-07-14 | |
BR112012000999-0A BR112012000999B1 (en) | 2009-07-14 | 2010-07-14 | BASE METAL RECOVERY PROCESS FROM OXIDE ORE |
MX2012000634A MX2012000634A (en) | 2009-07-14 | 2010-07-14 | Process of recovery of base metals from oxide ores. |
CU20120009A CU24015B1 (en) | 2009-07-14 | 2012-01-16 | BASIC METALS RECOVERY PROCESS FROM OXIDIZED MINERALS |
ZA2012/00549A ZA201200549B (en) | 2009-07-14 | 2012-01-23 | Process of recovery of base metals from oxide ores |
MA34632A MA33557B1 (en) | 2009-07-14 | 2012-02-14 | PROCESS FOR RECOVERING BASE METALS PRESENT IN OXIDIZED ORES |
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US22526409P | 2009-07-14 | 2009-07-14 | |
US61/225,664 | 2009-07-14 | ||
US12/835,445 US8469112B1 (en) | 2002-07-19 | 2010-07-13 | Dry sprinkler |
US12/835,445 | 2010-07-13 |
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PCT/BR2010/000227 WO2011006223A1 (en) | 2002-07-19 | 2010-07-14 | Process of recovery of base metals from oxide ores |
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US (1) | US8173086B2 (en) |
EP (1) | EP2454389B1 (en) |
JP (1) | JP5567670B2 (en) |
KR (1) | KR101751084B1 (en) |
CN (1) | CN102712965B (en) |
AP (1) | AP3427A (en) |
AU (1) | AU2010273197B2 (en) |
BR (1) | BR112012000999B1 (en) |
CA (1) | CA2768021C (en) |
CL (1) | CL2012000120A1 (en) |
CU (1) | CU24015B1 (en) |
DK (1) | DK2454389T3 (en) |
DO (1) | DOP2012000009A (en) |
EA (1) | EA019801B1 (en) |
EC (1) | ECSP12011639A (en) |
GT (1) | GT201200054A (en) |
IN (1) | IN2012DN00702A (en) |
MA (1) | MA33557B1 (en) |
MX (1) | MX2012000634A (en) |
MY (1) | MY157851A (en) |
NZ (1) | NZ597637A (en) |
PE (1) | PE20130461A1 (en) |
WO (1) | WO2011006223A1 (en) |
ZA (1) | ZA201200549B (en) |
Cited By (3)
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US20140020510A1 (en) * | 2012-07-23 | 2014-01-23 | Vale S/A | Recovery of base metals from sulphide ores and concentrates |
CN106916944A (en) * | 2017-03-09 | 2017-07-04 | 昆明理工大学 | A kind of method that Solid Inclusion cupric oxide ore selecting smelting combination is recycled |
US9914648B2 (en) | 2013-07-03 | 2018-03-13 | Sumitomo Metal Mining Co., Ltd. | Process for producing hematite for ironmaking |
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US8802042B2 (en) * | 2002-07-19 | 2014-08-12 | Vale S.A. | Process of recovery of base metals from oxide ores |
FI125216B (en) * | 2013-05-23 | 2015-07-15 | Outotec Finland Oy | Method for recovering metals |
JP5743305B2 (en) * | 2015-01-06 | 2015-07-01 | 住友金属鉱山株式会社 | Method for producing hematite for iron making |
EP3882365A1 (en) * | 2018-11-14 | 2021-09-22 | Nova Mineralis S.A. | Solid-liquid-solid method for the solubilisation of copper minerals and concentrates, independent of the redox potential and with low consumption of water and acid |
CN109777953B (en) * | 2019-03-11 | 2021-06-08 | 刘冠诚 | Low-grade oxidation and copper sulfide ore environment-friendly recovery process |
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- 2010-07-14 PE PE2012000060A patent/PE20130461A1/en not_active Application Discontinuation
- 2010-07-14 BR BR112012000999-0A patent/BR112012000999B1/en active IP Right Grant
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