ZA200402802B - Method for obtaining cobalt and nickel from ores and ore concentrates. - Google Patents
Method for obtaining cobalt and nickel from ores and ore concentrates. Download PDFInfo
- Publication number
- ZA200402802B ZA200402802B ZA200402802A ZA200402802A ZA200402802B ZA 200402802 B ZA200402802 B ZA 200402802B ZA 200402802 A ZA200402802 A ZA 200402802A ZA 200402802 A ZA200402802 A ZA 200402802A ZA 200402802 B ZA200402802 B ZA 200402802B
- Authority
- ZA
- South Africa
- Prior art keywords
- process according
- conversion
- sulfur
- metals
- cobalt
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 35
- 239000010941 cobalt Substances 0.000 title claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052759 nickel Inorganic materials 0.000 title claims description 19
- 229910017052 cobalt Inorganic materials 0.000 title claims description 18
- 239000012141 concentrate Substances 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- -1 platinum metals Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001495 arsenic compounds Chemical class 0.000 claims description 2
- 229940093920 gynecological arsenic compound Drugs 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 229910052953 millerite Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052954 pentlandite Inorganic materials 0.000 description 4
- 229910052964 arsenopyrite Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052957 realgar Inorganic materials 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004520 agglutination Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052965 gersdorffite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical compound [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
SMB
The invention relates to a process for the extraction of cobalt and nickel from arsenosulfidic or sulfidic ores or ore concentrates.
By far the biggest part of the world's nickel and cobalt production is extracted from arsenosulfidic or sulfidic minerals. Cobalt and nickel frequently appear together or accompanied by other metal ores.
Among the cobalt-containing arsenosulfides, there may be mentioned, above all, safflorite (CoAs,), skutterudite (CoAss), arsenopyrite ((Fe,Co,Ni)AsS) and cobaltine (CoAsS). Among the sulfides, there may be mentioned, above all, linnaeite (Co3S,).
Among the arsenosulfides, there may be mentioned, above all, rammelsbergite (NiAs,), arsenopyrite (FeAsS), Gersdorffite (NiAsS) and nickeline (NiAs). Among the sulfides, there may be mentioned, above all, pentlandite ((Fe,Ni)sSg), millerite (NiS) and bravoite ((Ni,Fe)S,).
Among the cobalt minerals, cobaltine is the most widespread mineral, and among the nickel minerals, it is pentlandite; therefore, these are of the greatest scientific and economic importance in the development of new extraction methods.
In addition, both minerals are characterized by regularly containing deposited or dissolved gold, platinum metals and other rare metals as well as rare earth metals.
The arsenosulfidic and/or sulfidic cobalt minerals are extracted from ores, which are usually milled and concentrated by a flotation process to yield an ore concen-
trate, whereby a substantial part of the silicates contained in the ground stock, in particular, is separated off. : The processing of the ores or ore concentrates is conventionally effected by calcining the ores, whereby the sulfide is oxidized into SO; at high temperatures, and metal oxides remain. The ores thus obtained can then be reduced by adding carbon, and the individual metals are optionally further purified by special meth- ods.
Today, in addition to the known pyrometallurgical and hydrometallurgical proc- : esses, there are various approaches to leaching cobalt, nickel and other metals from the arsenosuldific and/or sulfidic cobalt minerals.
The term "leaching" comprises both chemical leaching by Fe™ and biological leaching (bioleaching) by microorganisms which are able to utilize sulfur as an energy source. Especially when iron-containing copper and nickel ores are used, only incomplete leaching has been possible to date. : :
It is the object of the invention to provide an improved process for extracting cobalt and nickel and other metals from arsenosulfidic and/or sulfidic ores or ore concentrates. oo
This object is achieved by a process in which e the arsenosulfidic and/or sulfidic cobalt and/or nickel ore or ore concentrate is converted to a reaction product by sulfur or sulfur-containing arsenic com- pounds; and : e soluble metals and rare earth metals are leached from the reaction product. -
This conversion is represented by the following equations: 4C0ASS + 4S — 4C0S + AssSa (1) (Fe,Ni)sSs + 55 — 4NiS + 5FeS, 2) 4CoAs + 4As,;5; — 4C0S + 3As,S, (3)
~ 3 -
It has been found that cobaltine can be converted to CoS and realgar almost completely when the process is conducted appropriately. In contrast, when the process is conducted in this way, pentlandite can be converted almost completely to NiS and pyrite. In this conversion, a cobaltine grain from the ground stock yields a grain predominantly having a core of realgar and a shell of CoS. In contrast to : cobaltine, from cobalt sulfide, cobalt and the remaining metals enriched therein can be leached out with no problems using conventional oxidation methods. In the case of nickel, a pentlandite grain from the ground stock also yields a grain having a core of pyrite and a shell of NiS. It can be leached out with no problems using conventional leaching methods. It is particularly appropriate for the sulfur to be in a liquid state of aggregation. Depending on temperature, the sulfur is low-viscous oe - and yellow to high-viscous and dark red/brown. In the liquid phase, conversions between A-, m- and p-sulfur occur. The different forms cause a depression of the solidification point. Therefore, sulfur is generally liquid within a range of from 111 to 444 °C, the boiling point being dependent on pressure. Therefore, this tempera- ture range is preferably employed, the range around 187 °C being less advanta- geous because the sulfur has a particularly high viscosity there, which again decreases at higher temperatures. Preferred are, on the one hand, temperature : ranges of from 111 to 159 °C, and alternatively from 350 to 444 °C. Low tempera- tures are of course more favorable in terms of the necessary energy supply, while higher temperatures accelerate the reaction.
These reactions are exothermic so that a comparatively low expenditure of energy is necessary for the conversion.
A possible process for extracting cobalt or nickel from CoS or NiS, respectively, is described by the following equations: -
CoS + Fey(S04);3 — CoSO4 + 2FeS0, + S 4)
NiS + Fey(S04)3 — NiSO, + 2FeS0O, + S (5) :
The cobalt or nickel sulfate produced, like the iron sulfate, is soluble in acid. Thus, cobalt, nickel and iron are solubilized successively and can be separated from one another and from the solution when the process is conducted appropriately.
What remains is a mixture of precious and other metals and rare earth metals contained in the ground stock, especially of gold, silver, platinum, platinum metals and zinc, which will deposit as a residue on the bottom of the tank in which the leaching process is performed.
With novel bioleaching processes, the cobalt and nickel can be leached out in a particularly environment-friendly manner and with a relatively low production of sulfuric acid. In this process, the cobalt sulfide is oxidized in accordance with
CoS + 0; —» CoS0, (6) or
NiS + O; — NiSO, : (7) in the presence of special bacteria and separated in an aqueous solution and - electrolyzed. : The conversion of the ores or ore concentrates should preferably proceed in an inert atmosphere, for example, under nitrogen or argon. ]
A range of between 50°C and 550°C has been established as a preferred tem- perature range for the conversion. Especially between 350°C and 450°C, the : conversion can proceed at a relatively high rate. The duration of the conversion depends on the size of the ground grains and the temperature and can be opti- mized by the skilled person by simple experimentation.
The conversion process of the ores or ore concentrates can be promoted by microwave irradiation. Since the microwaves heat up the individual grains of the ground stock in both inner and outer portions thereof, the diffusion processes proceeding in the conversion can be accelerated thereby. By this improvement of reaction kinetics, the: process can be accelerated. : : Depending on the reaction temperature and, if employed, the degree of the microwave irradiation, the conversion can proceed for a period of from 0.5 h to h, especially from 2 hto 5 h.
The sulfur should be added to the cobaltine in stoichiometric amounts. This means that an analysis should be usually performed prior to the conversion in order to establish what amounts of sulfur are required for achieving a conversion according to equation (1), (2), (3) or comparable conversions, depending on the ore em- ployed. An excess of sulfur should be avoided since it mostly yields a tacky mass ‘ when cooling down. Thus, in this case, "stoichiometric amounts" means that virtually no free sulfur should remain after completion of the reaction, based on the metal content of the ores or ore concentrates.
The sulfur can be added to the ground stock in a solid form, in which case the - conversion of the ore or ore concentrate should be effected under ambient pressure, but may also be performed under a pressure above atmospheric of up to bar. To avoid that too much sulfur evaporates at the temperatures for conver- sion, it may be advantageous for the conversion to proceed in an atmosphere saturated with sulfur vapor. .
On the other hand, the conversion may also be effected without the addition of solid sulfur in an atmosphere containing gaseous sulfur under reduced pressure.
Conversion with the addition of a sulfur plasma is also possible. : It is also possible to react liquid sulfur with appropriately preheated ore or ore concentrate, since this highly accelerates the reaction and reduces the formation of by-products.
The process can be realized, for example, in a three-chamber tunnel furnace. The three-chamber tunnel furnace has first and third chambers which serve as sluices for the second chamber. The second chamber of the furnace is provided with electric heating coils and has an inlet for nitrogen or argon, which is used as a flushing gas. In addition, the second chamber may be provided with fused silica windows for introducing microwaves.
Experiments have shown that the conversion is optimized, in particular, when the mixture of ground stock and sulfur is irradiated with microwaves having a specific
‘energy density of from 8 to 35 kWh/t, based on the quantity of the ground stock.
Both microwaves of 815 MHz and those of 2.45 GHz can be used.
The conversion may also be effected in a fluidized bed reactor. surprisingly, the process according to the invention yields free-flowing products, : i.e., the sulfur added does not cause agglutination of the reaction products, but is required for the conversion. Any agglutinations occurring can be easily broken up.
Due to the pores formed, which are also due to the exothermic reaction, the © . product exhibits an at least 50fold increase of surface area, based on the starting material. This permits a significantly improved attack by biological and/or chemical leaching agents.
A unit which is used in this specification and which is not in accordance with the metric system may be converted to the metric system with the aid of the following table: 1 bar = 1 x 10%Pa
Amended Sheet - 21-04-2005
Claims (1)
- CLAIMS: (amended December 1, 2003)1. A process for extracting metals from an arsenosulfidic and/or sulfidic cobalt and/or nickel ore or ore concentrate in which ) the arsenosulfidic and/or sulfidic cobalt and/or nickel ore or ore concentrate is converted to a reaction product containing CoS and/or NiS by sulfur or sulfur-containing arsenic compounds; and. soluble metals and rare earth metals are leached from the reaction product.2. The process according to claim 1, characterized in that arsenic is leached from the reaction product and that the metals and rare earth metals depos- ited on the reaction product are separated off.3. The process according to claim 2, characterized in that the metals and rare earth metals are selected from gold, silver, platinum, platinum metals, nickel, cobalt and zinc.4. The process according to any of the preceding claims, characterized in that the metals are leached out from the reaction product using a bioleaching process.5. The process according to any of the preceding claims, characterized in that said conversion is performed in an inert atmosphere.6. The process according to any of the preceding claims, characterized in that said conversion is performed at a temperature of between 50°C and 550°C.7. The process according to claim 6, characterized in that said conversion is performed at a temperature of between 350°C and 450°C. AMENDED SHEET Amended Sheet — 21-04-20058. The process according to any of the preceding claims, characterized in that ol “sl said conversion is promoted by microwave irradiation. eH , E-¥ The process according to any of the preceding claims, characterized in that said conversion is effected for a period of from 0.5 h to 10 h. E10. The process according to claim 9, characterized in that said conversion is effected for a period of from 2 h to 5 h.11. The process according to any of the preceding claims, characterized in that sulfur is added.. +12. The process according to any of the preceding claims, characterized ‘in that sulfur is added in a solid state and the conversion is effected under a pres- sure of from 1 to 10 bar (1 x 10° Pa to 10 x 10° Pa). E : 13.- The process according to claim 11, characterized in that said conversion proceeds in an atmosphere saturated with sulfur vapor.14. The process according to any of claims 1 to 10, characterized in that sulfur is added in a gaseous state and the conversion is effected under reduced pressure. © +15. The process according to any of claims 1 to 10, characterized in:that the conversion is effected with a sulfur plasma. Amended Sheet —- 21-04-2005
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10145419 | 2001-09-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200402802B true ZA200402802B (en) | 2005-04-13 |
Family
ID=34812965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200402802A ZA200402802B (en) | 2001-09-14 | 2004-04-13 | Method for obtaining cobalt and nickel from ores and ore concentrates. |
Country Status (1)
| Country | Link |
|---|---|
| ZA (1) | ZA200402802B (en) |
-
2004
- 2004-04-13 ZA ZA200402802A patent/ZA200402802B/en unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU772950B2 (en) | Sulphidisation of sulphide ores for hydrometallurgical extraction of copper and other metals | |
| EP1825010A1 (en) | Consecutive or simultaneous leaching of nickel and cobalt containing ores | |
| AU2008200206A1 (en) | Integrated hydrometallurgical and pyrometallurgical processing of base-metal sulphides | |
| US7416712B2 (en) | Method for obtaining cobalt and nickel from ores and ore concentrates | |
| Peng et al. | Leaching of a sphalerite concentrate with H2SO4–HNO3 solutions in the presence of C2Cl4 | |
| CN105177307A (en) | Method for recycling copper-nickel-cobalt from low grade nickel matte through abrasive flotation separation | |
| Zhao et al. | Comprehensive review on metallurgical upgradation processes of nickel sulfide ores | |
| EP1587964A1 (en) | Process for nickel and cobalt extraction from laterite ores | |
| Habashi | Nitric acid in the hydrometallurgy of sulfides | |
| CN113699368B (en) | Method for extracting low-temperature polymetallic from oxidized minerals by using citric acid | |
| CN103773952B (en) | The method of Leaching of Gold from auriferous pyrite concentrate | |
| ZA200402802B (en) | Method for obtaining cobalt and nickel from ores and ore concentrates. | |
| Stopić et al. | Recovery of cobalt from primary and secondary materials-an overiew | |
| WO1996007762A1 (en) | Mineral processing | |
| Mackiw et al. | Recent Developments in Pressnre Hydrometallurgy | |
| CN103131864A (en) | Method for pre-treating complex indium-containing smoke dust by microwave roasting | |
| CA1054778A (en) | Hydrometallurgical processing of metal sulfides | |
| CN105063353B (en) | A kind of method of the leaching valuable metal from cobalt-copper white alloy | |
| AU709751B2 (en) | Mineral processing | |
| FINISHING et al. | SCRAP OR CEMENT COPPER | |
| Moats et al. | Nickel and Cobalt | |
| AU2005306572B2 (en) | Consecutive or simultaneous leaching of nickel and cobalt containing ores | |
| EP1327693A1 (en) | Process for extracting cobalt and nickel from ores and ore concentrates |