AU2003269743B2 - Method for recovery of nonferrous, rare and precious metals from robust minerals - Google Patents
Method for recovery of nonferrous, rare and precious metals from robust minerals Download PDFInfo
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- AU2003269743B2 AU2003269743B2 AU2003269743A AU2003269743A AU2003269743B2 AU 2003269743 B2 AU2003269743 B2 AU 2003269743B2 AU 2003269743 A AU2003269743 A AU 2003269743A AU 2003269743 A AU2003269743 A AU 2003269743A AU 2003269743 B2 AU2003269743 B2 AU 2003269743B2
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- ore
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- nonferrous
- rare
- metal
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- 238000000034 method Methods 0.000 title claims description 57
- 239000010970 precious metal Substances 0.000 title claims description 45
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 32
- 239000011707 mineral Substances 0.000 title claims description 32
- 238000011084 recovery Methods 0.000 title claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 51
- 239000003638 chemical reducing agent Substances 0.000 claims description 46
- 230000001590 oxidative effect Effects 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- -1 Sperchlorate Chemical compound 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 7
- 239000003795 chemical substances by application Substances 0.000 claims 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 235000010755 mineral Nutrition 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 14
- 238000000605 extraction Methods 0.000 description 14
- 238000002386 leaching Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000013459 approach Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 101100460584 Chaetomium thermophilum (strain DSM 1495 / CBS 144.50 / IMI 039719) NOC1 gene Proteins 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 101100022229 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MAK21 gene Proteins 0.000 description 2
- 101100313929 Schizosaccharomyces pombe (strain 972 / ATCC 24843) tip1 gene Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical class OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 2
- 229910021646 siderite Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-YPZZEJLDSA-N cobalt-57 Chemical compound [57Co] GUTLYIVDDKVIGB-YPZZEJLDSA-N 0.000 description 1
- 229910052955 covellite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 101150058217 mec-10 gene Proteins 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-RNFDNDRNSA-N nickel-63 Chemical compound [63Ni] PXHVJJICTQNCMI-RNFDNDRNSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 102220298895 rs1025502215 Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
Description
WO 2004/087970 PCT/RU2003/000131 1 METHOD FOR RECOVERY OF NONFERROUS, RARE AND PRECIOUS METALS FROM ROBUST MINERALS The method is referred to hydrometallurgy process and it serves for recovery of nonferrous, rare and precious metals from robust (hard to process) minerals, which may contain natural carbon or other robust compounds.
Very frequently the well-known techniques for recovery of nonferrous, rare and precious metals from robust minerals containing carbonaceous component or other robust compounds, do not provide satisfactory performance.
First of all it stems from high resistance to oxidation and high sorption activity of carbonaceous component of the minerals involving great loss of nonferrous, rare and precious metals with solid residue of processing.
In the framework of the present method ores and concentrates containing organometallic, cluster, colloid and other chemical and composite compounds, hindering the process of useful components recovery, should be classified among technologically robust minerals.
Hence, during cyanidation of robust carbonaceous ores and concentrates, for instance, no traces of precious metals are detected in solution in some cases, i.e. precious metal complexes formed as a result of interaction with cyanide are completely adsorbed by carbonaceous component in the mineral. Cyanidation in the presence of ion-exchange resins and carbons, as well as using sorption passivators like kerosene or apolar liquids, somewhat improves the recovery of precious metals but not infrequently its processing characteristics are as low.
WO 2004/087970 PCT/RU2003/000131 2 Methods for carbonaceous ore leaching are described in the book "Precious Metals Metallurgy" by Maslenitsky et al, published in Moscow in 1987, pages 288-291 as follows: in some ores carbonaceous substances feature different settling capability, which complicates largely the cyanidation process. During cyanidation of carbonaceous ores kinetics of precious metal transfer to solution is determined by the ratio of two opposite processes, i.e. dissolution and sorption.
Certain rate of leaching promotes maximum extraction in the course of carbonaceous ores cyanidation. The rate of sorption depends also on carbonaceous substance surface area. Optimal degree of material grinding should be maintained.
Thus, one of the methods of carbonaceous ore direct cyanidation consists in arrangement of usual cyanide process, observing the optimal degree of grinding and period of contact between the ore and cyanic solution. Another method...
consists in arrangement of leaching in several successive stages with solution renewal at each stage. Adsorption capacity of carbonaceous substances may be somewhat decreased by preliminary treatment of ore using flotation oils, kerosene, bituminous coal sublimation products and some other reagents....
However, the efficiency of the method is not very high. Cyanidation of carbonaceous ores using water-soluble organic nitriles, their actual applications not being ultimately ascertained, is of interest. Sorption leaching proved the most efficient method for cyanidation of carbonaceous ores and concentrates".
Attempts to reduce sorption activity of carbon-containing raw materials by thermal treatment in vacuum (for removing unsaturated oxides from carbon) failed to be widely used due to problems in hardware implementation, high costs of the process and low process performance.
In monograph "Solvents for Gold and Silver in Hydrometallurgy" by Mineev G.G. and Panchenko A.F. published by "Metallurgiya" (Metallurgy) Publishing House in 1994 in Moscow some problems arising from application of the known methods of leaching are mentioned in pages 192-205: "Bacterial leaching involves problems of intracellular metal accumulation, low performance of subsequent sorption leaching, build-up of biomass on the equipment". Leaching WO 2004/087970 PCT/RU2003/000131 3 by heterotrophic microorganism metabolism products and amino acid solutions yielded rather low results in reference to recovery into solution. Filtration leaching of gold-containing source materials necessitates recycling of productive solutions.
That is why the latter shall be processed in situ, while methods of gold recovery from solutions shall feature high efficiency, simplicity of hardware implementation and no pollution of gold-free filters by other components. Hence, sorption biochemical leaching was chosen as the basic method for gold recovery from ores.
Passivation of carbon sorption activity using bacteria active life products (bacterial leaching) necessitates special fermenters for growing bacteria, fine grinding of the material, strict observance of temperature and chemical conditions, long duration of the process. In some cases, when there are great amounts of As and Sb, for instance, bacterial leaching proved impossible due to bacteria poisoning with heavy metals. Bearing in mind the above-mentioned, bacterial leaching has not been used extensively for processing robust carbonaceous minerals.
Chlorination method of precious metal recovery from ores, consisting in ore treatment by aqueous solution of hypochlorite, iron ions and acid at elevated temperature, is its immediate analog (prior art), solving the problem of precious metal recovery from robust minerals, which is described in US Patent No.
4439235 of 14.06.1982, Int.Cl,.: C22D 3\00, U.S. Cl.: 75\101 R After filtration the solid residue is treated repeatedly by hypochlorite and iron-ion aqueous solutions at pH=7. Compounds of precious metals are extracted from liquid phase.
The prior art mentioned and the stated technical approach have the following in common: treatment of robust carbon-containing mineral with oxygen-containing oxidant and subsequent extraction of precious metal compounds from liquid phase.
Great consumption of hypochlorite for mineral oxidation, explained by the fact that hypochlorite decomposition, especially at elevated temperature, proceeds according to chlorates and chlorides formation mechanism, can be mentioned WO 2004/087970 PCT/RU2003/000131 4 among drawbacks of the method described. Meanwhile, hypochlorite and its disproportionation products do not take part in oxidation of precious metals and their transfer to solution: 2NaC10 NaCIO NaCIO 3 2 NaCl High oxidizing activity of hypochlorites combined with their thermodynamic instability results in a very rapid decrease in effective oxidant concentration in the slurry, giving rise to high cost of processing and insufficient degree of precious metal recovery from minerals.
This invention is aimed at increasing the recovery of nonferrous, rare and precious metals from robust minerals with simultaneous reduction of processing costs.
The objective is attained, as the method for recovery of nonferrous, rare and precious metals from robust minerals envisages the processing of robust carbon-containing minerals by oxygen-containing oxidant with subsequent exyraction of precious metal compounds from liquid phase, moreover, the treatment of robust carbon-containing minerals by oxygen-containing oxidant is performed in the presence of reducing agents featuring donor-acceptor properties, which are manifested in the fact that at the first stage of chemical reactions the reducing agents give their electrons to oxygen-containing oxidant and, as a result, form a stronger oxidant than the initial one, in the from of short-lived radicals and intermediate oxidation products of donor-acceptor reducing agents, which are oxidants, as well.
According to the method proposed, the treatment of robust carboncontaining minerals by oxygen-containing oxidant is realized in the presence of reducing agents featuring donor-acceptor properties. Donor-acceptor properties of the reducing agents used are pronounced in the fact that at the first stage of chemical reactions the reducing agents give their electrons to oxygen-containing oxidant and as a result form a stronger than initial oxidant, in the form of short- WO 2004/087970 PCT/RU2003/000131 lived radicals and intermediate oxidation products of donor-acceptor reducing agents, which are mild and selective oxidants.
Technically, the essence of the invention proceeds from specific features of using oxygen-containing compounds as oxidants for robust minerals.
Introduction of the donor-acceptor reducing agents into hydrometallurgical process permits: first, directing the decomposition of oxygen-containing oxidants in line with the most favorable mechanism for oxidation of nonferrous, rare and precious metals; second, prolonging the action of oxidants by mediating their oxidizing potential via the reducing agents oxidation products, which are milder and more selective oxidizing agents; third, making use of complexing capability of the reducing agents for overcoming kinetic and electrochemical difficulties in dissolving nonferrous, rare and precious metals and stabilizing the dissolved precious metals in liquid phase; fourth, transforming the intermediate compounds formed as a result of oxygencontaining oxidant disproportionation into short-lived "fast radicals", permitting oxidation of organometallic, cluster, colloid and other chemical and composite compounds, which increases essentially the utilization factor of robust minerals.
Existence of the above-mentioned mechanisms of chemical interactions is confirmed by the following theoretical and experimental data: 1) In solutions of oxygen-containing oxidants without donor-acceptor reducing agents the decomposition of oxidants proceeds by the following reactions: Cl 2
H
2 0 HC1 HCIO 2HC1O 2 HCI 02 MeCIO 2 HC10 MeC10 3 2 HCI
H
2
S
2 0s H 2 0 H 2 S0 5 H2S04 H2SO 5 H20 I-I2SO 4 H202 H2SO 5 H202 H 2 S0 4 02 H 2 0 WO 2004/087970 PCT/RU2003/000131 6 It follows from the reactions presented that as a result of decomposition of oxygen-containing oxidants, not involving donor-acceptor reducing agents, the decomposition and disproportionation products are accumulated in solution along with evolution of gaseous oxygen, which are not effective oxidants under normal conditions. Accordingly, it gives rise to high consumption of oxidants and low performance of recovery process.
2) In the presence of donor-acceptor reducing agents the oxidation potential of oxygen-containing compounds is actually entirely used for the formation of shortlived radicals and reducing agent oxidation products. The following reactions take place as a result: 2NaNO2 Cl NaNO 3 NOC1 NaCl NaNO 2 C12 NO 2 CI NaCI C12 H20 HCI HCI NaNO2 NaCl+ HN0 2 4NaNO 2 4HC10 4NaCl 2120 20 4N0 2 2SO 2 C12= 2S02C1 H2SO4 HC10 HCI H 2
SO
5 CI2 Using NaNO 2 and SOz by way of example, it follows from the reactions presented that interaction between the Cl 2 HC10 oxidant and donor-acceptor reducing agents gives rise to formation of many products, i.e. NaNO3, NOC1, N02C1, HN02, S02C1, 02, H2S05C12, etc., each of them can serve an independent oxidant for nonferrous, rare and precious metals.
Meanwhile, the oxidation potentials developed by the compounds during reduction to lower valency states, fall within a wide range relative to normal hydrogen electrode. Actually all the substances feature complexing properties and form compounds with nonferrous, rare and precious metals, required for the process. The presence of various compounds featuring diverse electrochemical and complexing properties during oxidation of nonferrous, rare and precious WO 2004/087970 PCT/RU2003/000131 7 metals permits increasing thermodynamic probability of the metals oxidation and their transfer to solution.
Compounds of higher oxidation state, e.g. chlorates, perchlorates, persulfates, perbromates, other oxygen-containing oxidants and their derivatives have great bound chemical energy, but chemical energy cannot be used for oxidation of nonferrous, rare and precious metals owing to stability of chlorates and perchlorates as compounds and their low chemical activity.
In the invention proposed oxidants featuring the highest valency of acid residue atom, for instance, chlorates, perchlorates, persulfates, perbromates, other oxygen-containing oxidants and their derivatives are used as oxidants in the presence of donor-acceptor reducing agents. As a result, the donor-acceptor reducing agents give rise to the formation of radical, i.e. oxygen superoxide, atomic oxygen and other highly reactive compounds, including the reducing agents oxidation products, which permits effective oxidation and dissolution of nonferrous, rare and precious metals contained in the minerals, i.e.: 2NaC10 4
SO
2 Na 2
SO
4 2 C10 2 NaNO 2 HC1 HN0 2 NaCl 2 H20 NO 2
NO
4 NO NaNO 3 C102 2HC103 NaNO 2 NaNO 3 2C10 2
H
2 0 Na 2 S20s 2NO 2NO 2 Na 2
SO
4 S02 2 3N0 2
N
2 0 5 CINO3 It becomes obvious from the reasoning above that the proposed method for recovery of precious metals differs from the known ones, as robust minerals are treated with oxygen-containing oxidants in the presence of reducing agents featuring donor-acceptor properties. Thus, the proposed method complies with the "novelty" criterion.
WO 2004/087970 PCT/RU2003/000131 8 Comparison of the approach proposed with the prior art and other approaches in this field of engineering permitted revealing the signs, making the proposed approach different from the prior art, moreover, the differences considered are implicit, which suggests conclusion about compliance of the approach proposed with the "invention level" criterion. The approach proposed has industrial applications.
Examples of specific applications for the process proposed: Example No. 1.
Hydrometallurgical oxidation was realized using ore featuring the following mineral composition: a) non-metallic minerals siderite 18.2%, calcite quartz- kaolin- 4.5 chlorite albite- hydromica apatite 0.3%; b) ore mineral goethite, limonite 61.5%, pyrite chalcopyrite 0.85%, bomite covellite 0.1%.
The ore contained gold 7.4 g/ton ore, platinum 56 g/ton ore, palladium 12 g/ton ore, and silver 150 g/ton ore, as well as copper 0.7% and cobalt 0.2%.
The ore, its amount 1 kg, was subjected to hydrometallurgical oxidation in hydrochloric acid solution, its concentration 100 g per liter, in liquid-to-solid ratio 3:1, at a temperature of 80 0 C with intense agitation.
Ammonium persulfate (NH 4 2
S
2 0g was used as oxidant in the amount providing concentration of 10 g per liter, which was introduced into the slurry immediately after heating to assigned temperature. Check sample was agitated in parallel with the basic one without addition of donor-acceptor reducing agents.
Solution containing 10 g/l of sodium nitrite NaNO 2 and 10 g/1 of sodium sulfite Na 2 SOs was introduced gradually into the basic sample. The feed rate depended WO 2004/087970 PCT/RU2003/000131 9 on gas evolution intensity. Altogether 100 ml of solution containing donoracceptor reducing agents was consumed in 30 minutes. Hence, 1 gram of NaNO2 and 1 gram Na 2
SO
3 was consumed per total amount of the oxidant equal to grams.
The solutions prepared and solid residue were analyzed by atomicabsorption and assay analyses for ascertaining the extraction of nonferrous and precious metals into solution.
In the check sample (without addition of donor-acceptor reducing agents) the extraction into solution made up: Copper 73%, cobalt 68%, silver 57%, gold 64%, platinum 31%, palladium 47% of their content in the sample.
In the sample with donor-acceptor reducing agents metal extraction into solution amounted to: Copper 98.5%, cobalt 97%, silver 94%, gold 98.3%, platinum 94%, palladium 97%.
The results suggest that the use of donor-acceptor reducing agents increases essentially the extraction of nonferrous and precious metals from robust minerals.
Example No. 2.
Hydrometallurgical oxidation was realized using ore featuring the following mineral composition: a) non-metallic minerals siderite 12.2%, calcite quartz 37.8%, kaolin 3.7 chlorite albite hydromica 12.0%, apatite 0.7%, carbonaceous matter b) ore minerals goethite, limonite 11.5%, pyrite pyrrhotine arsenopyrite 0.1%.
WO 2004/087970 PCT/RU2003/000131 The ore contained gold 3.4 g/ton ore, platinum 2.6 g/ton ore, palladium 3.2 g/ton ore, and silver 5 g/ton ore.
The ore, its amoint 1 kg, was subjected to hydrometallurgical oxidation in hydrochloric acid solution, its concentration 10 g per liter, at L:S 3:1, at a temperature of 40 0 C with intense agitation.
Sodium hypochlorite NaC10 was used as oxidant in the amount providing the concentration of 5 g/l, which was introduced into the slurry immediately after heating up to the assigned temperature. The check sample was agitated in parallel with the basic one without addition of donor-acceptor reducing agents.
Solution containing 10 g/1 of sodium nitrite NaNO 2 was introduced gradually into the basic sample. The feed rate depended on gas evolution intensity. Altogether 200 ml of solution containing donor-acceptor reducing agent was consumed in minutes. Hence, 2 grams of NaNO 2 was consumed per total amount of the oxidant equal to 15 grams.
The solutions prepared and solid residue were analyzed by atomicabsorption and assay analyses for ascertaining the extraction of nonferrous and precious metals into solution.
In the check sample (without addition of donor-acceptor reducing agent) the extraction into solution made up: silver 37%, gold 52%, platinum 21%, palladium 37% of their content in the sample.
In the sample with donor-acceptor reducing agents metal extraction into solution amounted to: silver 87%, gold 92.3%, platinum 74%, palladium 87%.
The results suggest that the use of donor-acceptor reducing agents increases essentially the extraction of nonferrous and precious metals from robust minerals.
WO 2004/087970 PCT/RU2003/000131 11 Example No. 3.
Hydrometallurgical oxidation was performed using gravity concentrate featuring the following chemical composition: SiOz 23%, A1 2 0 3 Fe (total) 28%, S (total) 36%, crystallization water 1.34%, CaO 1.12 MgO 0.8%.
The concentrate contained gold 378 g/ton ore, platinum 47 g/ton ore, palladium 126 g/ton ore, and silver 2480 g/ton ore, as well as 3.8% of nickel and 2.4% of cobalt.
The concentrate in the amount of 1 kg was subjected tb hydrometallurgical oxidation in hydrochloric acid solution, its concentration 70 g per liter, at L:S 2:1, at a temperature of 70 0 C under intensive agitation.
Ammonium perchlorate (NH) 2 Cl20 7 was used as oxidant in the amount providing concentration of 10 g per liter, and sodium iodate NaJO 3 in the amount providing concentration of 5 g per liter, were introduced into the slurry immediately after heating to assigned temperature. The check sample was agitated in parallel with the basic one without addition of donor-acceptor reducing agents.
Solution containing 10 g/1 of sodium sulfite Na 2
SO
3 and 5 g/1 sodium thiosulfate NazS20 3 was gradually introduced in the basic sample. The feed rate depended on gas evolution intensity. In total 300 ml of solution containing donoracceptor reducing agents was consumed in 45 minutes. So, 3 grams of Na 2
SO
3 and 1.5 grams of Na 2
S
2 03 were consumed per total amount of oxidants equal to grams.
The solutions prepared and solid residue were analyzed by atomicabsorption and assay analyses for ascertaining the extraction of nonferrous and precious metals into solution.
In the check sample (without addition of donor-acceptor reducing agents) the extraction into solution made up: nickel 63%, cobalt 57%, silver 48%, gold 63%, platinum 42%, palladium 54% of their content in the sample.
WO 2004/087970 PCT/RU2003/000131 12 In the sample with donor-acceptor reducing agents metal extraction into solution amounted to: nickel- 98.5%, cobalt 95%, silver 89%, gold 94%, platinum 89%, palladium 92%.
The results suggest that the use of donor-acceptor reducing agents increases essentially the extraction of nonferrous and precious metals from robust minerals.
Claims (21)
1. A method for extracting a nonferrous, rare or precious metal from an t'q Sore, comprising treating the ore with an oxygen-containing oxidant in the t'q presence of a solvent and a reducing agent that has donor-acceptor properties, whereby the oxygen-containing oxidant and the reducing c agent react to generate reaction products that oxidize or form 0complexes with said metal, thereby extracting said metal from the ore, c 10 wherein the method is performed in an environment where agents forming complexes with the metal are selected from the group consisting of the ore, the oxygen-containing oxidant, the solvent, the reducing agent, and products of their reactions.
2. The method of claim 1, wherein the ore includes robust minerals.
3. The method of claim 1, wherein the ore includes a carbonaceous component.
4. The method of claim 1, wherein the ore includes more than one nonferrous, rare or precious metals.
The method of claim 1, wherein the metal is selected from the group consisting of gold, silver, platinum, palladium, copper, cobalt and nickel.
6. The method of claim 1, wherein the solvent is acidic.
7. The method of claim 6, wherein the solvent is a hydrochloric acid solution. 00 AMENDED C
8. The method of claim 1, wherein the oxygen-containing oxidant is aselected from the group consisting of: persulfate, hypochlorite, Sperchlorate, iodate, bromate and any combination thereof.
9. The method of claim 1, wherein the reducing agent is selected from the groups consisting of: nitrite, sulfite, thiosulfite and any combination thereof.
The method of claim 1, wherein the reaction products include S 10 radicals.
11. The method of claim 1, wherein the reactions products are capable of oxidizing more than one metal, said more than one metal being selected from the group consisting of nonferrous, rare and precious metal.
12. A method for recovering nonferrous, rare or precious metals, comprising: combining in a solution an oxygen-containing oxidant and a donor-acceptor reducing agent to form additional oxidizing agents, the oxygen-containing oxidant and said additional oxidizing agents reacting with a nonferrous, rare or precious metal in an ore, to transfer said metal to the solution, wherein the method is performed in an environment where agents forming complexes with the metal are selected from the group consisting of the ore, the oxygen-containing oxidant, the solvent, the reducing agent, and products of their reactions.
13. A method for a liquid phase recovery of a nonferrous, rare or precious metal from an ore, the method comprising treating an ore that 0 AMENDED Nincludes nonferrous, rare or precious metals with an oxygen- containing oxidant, and with oxidizing agents formed by reactions between the oxygen-containing oxidant and a donor-acceptor reducing agent, to form metal compounds that dissolve in the liquid phase, thereby extracting the nonferrous, rare or precious metal from the ore, 1 wherein the method is performed in an environment where Nagents forming complexes with the metal are selected from the group Oconsisting of the ore, the oxygen-containing oxidant, the solvent, the reducing agent, and products of their reactions.
14. A method for recovering nonferrous, rare or precious metals from an ore, the method comprising: a. combining the ore with an oxygen-containing oxidant in the presence of a solvent; b. reacting at least a portion of the oxygen-containing oxidant with a donor-acceptor reducing agent to forms radicals and reducing agent oxidation products; and c. reacting said radicals and reducing agent oxidation products with nonferrous, rare or precious metals in the ore, to form soluble metal compounds, thereby recovering the nonferrous, rare or precious metals from the ore, wherein the method is performed in an environment where agents forming complexes with the metal are selected from the group consisting of the ore, the oxygen-containing oxidant, the solvent, the reducing agent, and products of their reactions.
The method of claim 14, wherein the ore includes robust minerals. 0 0 AMENDED O
16. The method of claim 14, wherein the ore includes a carbonaceous component.
17. A method of claim 14, wherein the nonferrous, rare or precious metals are selected from the group consisting of gold, silver, platinum, palladium, copper, cobalt and nickel.
CI S18. The method of claim 14, wherein the solvent is acidic. 0 cM
19. The method of claim 18, wherein the solvent is a hydrochloric acid solution.
The method of claim 14, wherein the oxygen-containing oxidant is selected from the group consisting of: persulfate, hypochlorite, perchlorate, iodate, bromate and any combination thereof.
21. The method of claim 14, wherein the reducing agent is selected from the group consisting of: nitrite, sulfite, thiosulfite and any combination thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/RU2003/000131 WO2004087970A1 (en) | 2003-04-02 | 2003-04-02 | Method for recovery of nonferrous, rare and precious metals from robust minerals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2003269743A1 AU2003269743A1 (en) | 2004-10-25 |
| AU2003269743B2 true AU2003269743B2 (en) | 2009-01-15 |
Family
ID=33129389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2003269743A Ceased AU2003269743B2 (en) | 2003-04-02 | 2003-04-02 | Method for recovery of nonferrous, rare and precious metals from robust minerals |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060144191A1 (en) |
| AU (1) | AU2003269743B2 (en) |
| CA (1) | CA2521110C (en) |
| GB (1) | GB2414740B (en) |
| WO (1) | WO2004087970A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009017434A1 (en) * | 2007-07-30 | 2009-02-05 | Shapovalov Viatcheslav Dmitrie | Method for recovering non-ferrous, rare, radioactive and precious metals from refractory mineral raw materials |
| AU2011217757A1 (en) | 2010-02-18 | 2012-08-23 | Neomet Technologies Inc. | Process for the recovery of gold from an ore in chloride medium with a nitrogen species |
| WO2011100820A1 (en) | 2010-02-18 | 2011-08-25 | Neomet Technologies Inc. | Process for the recovery of metals and hydrochloric acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4561947A (en) * | 1983-02-22 | 1985-12-31 | Skw Trostberg Aktiengesellschaft | Process for the recovery of noble metals from ores; which process uses thiourea |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793429A (en) * | 1972-02-18 | 1974-02-19 | Kennecott Copper Corp | Nitric acid process for recovering metal values from sulfide ore materials containing iron sulfides |
| US4439235A (en) * | 1982-02-04 | 1984-03-27 | James J. Shepard, Jr. | Chlorination process for removing precious metals from ore |
| US4505537A (en) * | 1982-06-24 | 1985-03-19 | Ricoh Company, Ltd. | Light scanning apparatus |
| US4626417A (en) * | 1983-09-29 | 1986-12-02 | Union Oil Company Of California | Methods for chemically reducing nitrogen oxides |
| US4605537A (en) * | 1984-09-17 | 1986-08-12 | Freeport Minerals Company | Sulfide as a hypochlorite kill agent |
| US4979986A (en) * | 1988-02-22 | 1990-12-25 | Newmont Gold Company And Outomec U.S.A., Inc. | Rapid oxidation process of carbonaceous and pyritic gold-bearing ores by chlorination |
| US5158582A (en) * | 1988-05-30 | 1992-10-27 | Hitachi Zosen Corporation | Method of removing NOx by adsorption, NOx adsorbent and apparatus for purifying NOx-containing gas |
| US5425800A (en) * | 1993-10-26 | 1995-06-20 | Fmc Corporation | Recovery of precious metal values from refractory ores |
| US6264909B1 (en) * | 1996-02-29 | 2001-07-24 | Drinkard Metalox, Inc. | Nitric acid production and recycle |
| WO2002042503A1 (en) * | 2000-11-21 | 2002-05-30 | Orthotech Industrial Corporation | Recovery of precious metals from carbonaceous refractory ores |
-
2003
- 2003-04-02 US US10/540,362 patent/US20060144191A1/en not_active Abandoned
- 2003-04-02 WO PCT/RU2003/000131 patent/WO2004087970A1/en not_active Application Discontinuation
- 2003-04-02 AU AU2003269743A patent/AU2003269743B2/en not_active Ceased
- 2003-04-02 GB GB0519960A patent/GB2414740B/en not_active Expired - Fee Related
- 2003-04-02 CA CA002521110A patent/CA2521110C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4561947A (en) * | 1983-02-22 | 1985-12-31 | Skw Trostberg Aktiengesellschaft | Process for the recovery of noble metals from ores; which process uses thiourea |
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| Publication number | Publication date |
|---|---|
| US20060144191A1 (en) | 2006-07-06 |
| CA2521110A1 (en) | 2004-10-14 |
| WO2004087970A1 (en) | 2004-10-14 |
| GB2414740A (en) | 2005-12-07 |
| CA2521110C (en) | 2008-02-19 |
| AU2003269743A1 (en) | 2004-10-25 |
| GB0519960D0 (en) | 2005-11-09 |
| GB2414740B (en) | 2006-07-19 |
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