CA2706414A1 - Method for processing pyritic concentrate containing gold, copper and arsenic - Google Patents
Method for processing pyritic concentrate containing gold, copper and arsenic Download PDFInfo
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- CA2706414A1 CA2706414A1 CA 2706414 CA2706414A CA2706414A1 CA 2706414 A1 CA2706414 A1 CA 2706414A1 CA 2706414 CA2706414 CA 2706414 CA 2706414 A CA2706414 A CA 2706414A CA 2706414 A1 CA2706414 A1 CA 2706414A1
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- Prior art keywords
- copper
- arsenic
- gold
- leaching
- iron
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 52
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 49
- 239000010931 gold Substances 0.000 title claims abstract description 49
- 239000012141 concentrate Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 35
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 8
- 238000000638 solvent extraction Methods 0.000 claims abstract description 8
- 238000005363 electrowinning Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 43
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000005864 Sulphur Substances 0.000 claims description 20
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052683 pyrite Inorganic materials 0.000 claims description 16
- 239000011028 pyrite Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229960003280 cupric chloride Drugs 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 229910052598 goethite Inorganic materials 0.000 claims description 5
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000005188 flotation Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- -1 platinum group metals Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052964 arsenopyrite Inorganic materials 0.000 description 4
- 229910052971 enargite Inorganic materials 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000008346 aqueous phase 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
-
- 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
- C22B11/00—Obtaining noble metals
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
-
- 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
- C22B11/042—Recovery of noble metals from waste materials
-
- 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
- C22B11/08—Obtaining noble metals by cyaniding
-
- 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
-
- 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
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0095—Process control or regulation methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- 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
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- 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
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- Manufacturing & Machinery (AREA)
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- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a method for processing pyritic copper sulphide concentrate, in which, in addition to copper, there is arsenic and gold bound to the sulphide minerals, or invisible gold.
In the method concentrate is leached into a chloride-containing solution. Raw material leaching is performed in conditions where the copper, iron and arsenic of the raw material dissolve, but the gold-containing material remains undissolved. The chloride solution obtained is routed to neutralisation, where the iron and arsenic in it are precipitated. The purified copper solution is routed to liquid- liquid extraction, in the stripping stage of which copper is transferred to a sulphate solution, which is routed to copper electrowinning. Gold is recovered from the leaching residue by some known method.
In the method concentrate is leached into a chloride-containing solution. Raw material leaching is performed in conditions where the copper, iron and arsenic of the raw material dissolve, but the gold-containing material remains undissolved. The chloride solution obtained is routed to neutralisation, where the iron and arsenic in it are precipitated. The purified copper solution is routed to liquid- liquid extraction, in the stripping stage of which copper is transferred to a sulphate solution, which is routed to copper electrowinning. Gold is recovered from the leaching residue by some known method.
Description
METHOD FOR PROCESSING PYRITIC CONCENTRATE CONTAINING
GOLD, COPPER AND ARSENIC
FIELD OF THE INVENTION
The invention relates to a method for processing pyritic copper sulphide concentrate, in which, in addition to copper, there is arsenic and fine gold or invisible gold bound to the sulphide minerals. In the method, concentrate is leached into a chloride-based solution. Raw material leaching is performed in conditions where the copper, iron and arsenic of the raw material dissolve, io but the gold-containing material remains undissolved. The chloride solution obtained is routed to neutralisation, in which the iron and arsenic in it are precipitated. The purified copper solution is routed to liquid-liquid extraction.
In the stripping stage of extraction, copper is transferred to a sulphate solution, which is routed to copper electrowinning. Gold is recovered from the leaching residue by some known method.
BACKGROUND OF THE INVENTION
The problem with many gold-copper concentrates is that a considerable amount of the gold is bound to pyrite as invisible gold. This is the case for instance in arsenic-bearing gold-copper ores, in which up to 50 % of the gold is in pyrite. The rest of the gold is either metallic, or bound to enargite (Cu2AsS4), arsenopyrite (FeAsS) and other minerals. These kinds of ores also contain copper, which is most often in the form of enargite or chalcopyrite (CuFeS2). The beneficiation of the ores in question requires the fabrication of the kind of bulk concentrate that include copper, free gold and the maximum amount of pyrite. Arsenic treatment and the large amount of pyritic sulphur set the major limitations on the creation of a profitable overall process for this type of concentrate.
3o A method is described in WO patent application 2004/035840, which relates to the recovery of metals, in particular copper, from a copper-bearing raw material, where the material is leached into a chloride-containing solution.
GOLD, COPPER AND ARSENIC
FIELD OF THE INVENTION
The invention relates to a method for processing pyritic copper sulphide concentrate, in which, in addition to copper, there is arsenic and fine gold or invisible gold bound to the sulphide minerals. In the method, concentrate is leached into a chloride-based solution. Raw material leaching is performed in conditions where the copper, iron and arsenic of the raw material dissolve, io but the gold-containing material remains undissolved. The chloride solution obtained is routed to neutralisation, in which the iron and arsenic in it are precipitated. The purified copper solution is routed to liquid-liquid extraction.
In the stripping stage of extraction, copper is transferred to a sulphate solution, which is routed to copper electrowinning. Gold is recovered from the leaching residue by some known method.
BACKGROUND OF THE INVENTION
The problem with many gold-copper concentrates is that a considerable amount of the gold is bound to pyrite as invisible gold. This is the case for instance in arsenic-bearing gold-copper ores, in which up to 50 % of the gold is in pyrite. The rest of the gold is either metallic, or bound to enargite (Cu2AsS4), arsenopyrite (FeAsS) and other minerals. These kinds of ores also contain copper, which is most often in the form of enargite or chalcopyrite (CuFeS2). The beneficiation of the ores in question requires the fabrication of the kind of bulk concentrate that include copper, free gold and the maximum amount of pyrite. Arsenic treatment and the large amount of pyritic sulphur set the major limitations on the creation of a profitable overall process for this type of concentrate.
3o A method is described in WO patent application 2004/035840, which relates to the recovery of metals, in particular copper, from a copper-bearing raw material, where the material is leached into a chloride-containing solution.
Raw material leaching is performed acidically at a pH value of at least 1.5 and a redox potential of 480 - 500 mV vs. Ag/AgCI, so that the copper in the copper chloride solution exiting leaching is mostly divalent. At the same time the sulphur contained in the concentrate is precipitated in elemental form, and also the iron precipitates. The precious metals included in the concentrate do not dissolve but go into the leaching residue. The leaching residue is subjected to sulphur flotation, whereby a sulphur concentrate is obtained, which also contains precious metals (gold + PGM). The majority of the sulphur is separated from the sulphur concentrate by known methods io and thus a PGM concentrate is formed containing precious metals. The chloride solution formed in raw material leaching, which contains copper and other possible valuable metals, is routed to liquid-liquid extraction. In extraction copper is transferred first to the organic phase by means of extraction, and in stripping to a sulphate solution, which is routed to copper electrowinning. There is no mention in the method of how any arsenic that may be contained in the raw material behaves or how gold-containing pyrite is recovered.
US patent 4,023,964 describes a method for fabricating copper. In the method copper sulphide concentrate is leached into a solution of copper (II) chloride and sodium chloride. The NaCl concentration is 100-300 g/I and the pH value at most 1, so that the iron dissolves. The solution obtained, in which the majority of copper is monovalent, is divided into two parts, one of which is subjected to iron precipitation as goethite by injecting air into the solution. The cupric chloride solution formed during goethite precipitation is routed back to concentrate leaching. The other part of the solution is contacted with the extraction solution. During extraction, air is introduced into the solution in order to oxidise the monovalent copper to divalent. In extraction the copper is bound to the organic phase and the cupric chloride solution that is depleted with regard to copper is routed back to concentrate leaching. In stripping, the organic phase and the copper bound to it are contacted with an aqueous solution of sulphuric acid. The copper sulphate solution that is formed is routed to fabrication of elemental copper and the organic phase back to the extraction stage.
The method described in US patent 4,023,964 is practical in so far as the copper sulphide concentrate is leached as chloride, which is routed to liquid-liquid extraction and copper is recovered from extraction as copper sulphate solution. The further processing of the copper sulphate solution for example in electrowinning is a well-known technique and produces pure copper. The method is made complicated by the fact that the solution is divided into two io branches, in one of which the dissolved iron is precipitated and only the other is routed to extraction. The copper in the copper chloride solution exiting leaching is mainly monovalent, so it has to be oxidised separately during extraction. When oxidation occurs during extraction, there is a danger that the extractant will be oxidised at the same time, making it no longer fit for use. It is recommended in the method that extraction be performed at a temperature of 60 C, which in practice is far too high and causes the destruction of the extractant. The processing of arsenic-bearing material is not mentioned in the method, nor the behaviour of the gold contained in pyrite or the behaviour of gold in general.
PURPOSE OF THE INVENTION
Now a method has been developed for processing pyritic copper sulphide concentrate that contains gold, copper and arsenic. Bulk concentrate containing copper pyrite, pyrite, enargite and possibly other arsenic-bearing minerals, such as arsenopyrite, is leached into a chloride-based aqueous solution in conditions where copper, iron and arsenic dissolve, but pyrite and gold remain in the leaching residue.
SUMMARY OF THE INVENTION
3o The invention relates to a method for processing pyritic copper sulphide concentrate containing gold and/or platinum group metals (PGM) and arsenic, whereby the concentrate is leached into an aqueous solution of copper chloride and alkali chloride containing hydrochloric acid. It is typical of the method that the redox potential of the concentrate leaching is regulated to be in the range of 400 - 600 mV vs. Ag/AgCI electrode by means of the feed of an oxidising agent and the pH is adjusted to the range of 0.2 - 1, whereupon the copper, iron and arsenic in the copper and arsenic minerals of the concentrate dissolve and the gold and/or PGM bound to these minerals is released. Pyrite and the gold and/or PGM it contains as well as free gold and/or PGM and sulphur remain in the leaching residue. The cupric chloride solution containing iron and arsenic that is formed is neutralised to 1o precipitate the iron and arsenic, after which the neutralised iron- and arsenic-free cupric chloride solution is routed to the liquid-liquid extraction stage, where the copper is recovered into an aqueous solution of sulphuric acid, and is routed to electrolysis for recovery of elemental copper. The raffinate formed in liquid-liquid extraction is fed back to concentrate leaching.
According to one embodiment of the invention the leaching residue is subjected to sulphur flotation. Sulphur concentrate or leaching residue containing gold and/or PGM is preferably routed to pyrometallurgical processing to recover the gold and/or PGM, in which case they are routed to a smelter or roasted. The leaching residue may also be subjected to hydro metallurgical processing in the form of pressure leaching.
The iron- and arsenic-containing cupric chloride solution generated in copper sulphide concentrate leaching in accordance with the invention is neutralised to a pH value of 2 - 2.5 in order to precipitate the iron and arsenic out of the solution. Neutralisation is preferably carried out by means of limestone, lime or lye. Iron and arsenic are precipitated out of the solution as ferric arsenate and goethite or as ferric hydroxide.
3o The small amount of gold that may have dissolved in the leaching stage is precipitated back into the leaching residue by means of a reducing agent or adsorbent. A typical adsorbent is activated carbon.
US patent 4,023,964 describes a method for fabricating copper. In the method copper sulphide concentrate is leached into a solution of copper (II) chloride and sodium chloride. The NaCl concentration is 100-300 g/I and the pH value at most 1, so that the iron dissolves. The solution obtained, in which the majority of copper is monovalent, is divided into two parts, one of which is subjected to iron precipitation as goethite by injecting air into the solution. The cupric chloride solution formed during goethite precipitation is routed back to concentrate leaching. The other part of the solution is contacted with the extraction solution. During extraction, air is introduced into the solution in order to oxidise the monovalent copper to divalent. In extraction the copper is bound to the organic phase and the cupric chloride solution that is depleted with regard to copper is routed back to concentrate leaching. In stripping, the organic phase and the copper bound to it are contacted with an aqueous solution of sulphuric acid. The copper sulphate solution that is formed is routed to fabrication of elemental copper and the organic phase back to the extraction stage.
The method described in US patent 4,023,964 is practical in so far as the copper sulphide concentrate is leached as chloride, which is routed to liquid-liquid extraction and copper is recovered from extraction as copper sulphate solution. The further processing of the copper sulphate solution for example in electrowinning is a well-known technique and produces pure copper. The method is made complicated by the fact that the solution is divided into two io branches, in one of which the dissolved iron is precipitated and only the other is routed to extraction. The copper in the copper chloride solution exiting leaching is mainly monovalent, so it has to be oxidised separately during extraction. When oxidation occurs during extraction, there is a danger that the extractant will be oxidised at the same time, making it no longer fit for use. It is recommended in the method that extraction be performed at a temperature of 60 C, which in practice is far too high and causes the destruction of the extractant. The processing of arsenic-bearing material is not mentioned in the method, nor the behaviour of the gold contained in pyrite or the behaviour of gold in general.
PURPOSE OF THE INVENTION
Now a method has been developed for processing pyritic copper sulphide concentrate that contains gold, copper and arsenic. Bulk concentrate containing copper pyrite, pyrite, enargite and possibly other arsenic-bearing minerals, such as arsenopyrite, is leached into a chloride-based aqueous solution in conditions where copper, iron and arsenic dissolve, but pyrite and gold remain in the leaching residue.
SUMMARY OF THE INVENTION
3o The invention relates to a method for processing pyritic copper sulphide concentrate containing gold and/or platinum group metals (PGM) and arsenic, whereby the concentrate is leached into an aqueous solution of copper chloride and alkali chloride containing hydrochloric acid. It is typical of the method that the redox potential of the concentrate leaching is regulated to be in the range of 400 - 600 mV vs. Ag/AgCI electrode by means of the feed of an oxidising agent and the pH is adjusted to the range of 0.2 - 1, whereupon the copper, iron and arsenic in the copper and arsenic minerals of the concentrate dissolve and the gold and/or PGM bound to these minerals is released. Pyrite and the gold and/or PGM it contains as well as free gold and/or PGM and sulphur remain in the leaching residue. The cupric chloride solution containing iron and arsenic that is formed is neutralised to 1o precipitate the iron and arsenic, after which the neutralised iron- and arsenic-free cupric chloride solution is routed to the liquid-liquid extraction stage, where the copper is recovered into an aqueous solution of sulphuric acid, and is routed to electrolysis for recovery of elemental copper. The raffinate formed in liquid-liquid extraction is fed back to concentrate leaching.
According to one embodiment of the invention the leaching residue is subjected to sulphur flotation. Sulphur concentrate or leaching residue containing gold and/or PGM is preferably routed to pyrometallurgical processing to recover the gold and/or PGM, in which case they are routed to a smelter or roasted. The leaching residue may also be subjected to hydro metallurgical processing in the form of pressure leaching.
The iron- and arsenic-containing cupric chloride solution generated in copper sulphide concentrate leaching in accordance with the invention is neutralised to a pH value of 2 - 2.5 in order to precipitate the iron and arsenic out of the solution. Neutralisation is preferably carried out by means of limestone, lime or lye. Iron and arsenic are precipitated out of the solution as ferric arsenate and goethite or as ferric hydroxide.
3o The small amount of gold that may have dissolved in the leaching stage is precipitated back into the leaching residue by means of a reducing agent or adsorbent. A typical adsorbent is activated carbon.
LIST OF DRAWINGS
The method according with the invention is described in the appended Figure 1, which shows a flow chart of one of the preferred embodiments of 5 the invention.
DETAILED DESCRIPTION OF THE INVENTION
Pyritic bulk concentrate containing gold, copper and arsenic, is fed to a leaching stage, in which leaching is performed using a solution of io hydrochloric acid containing copper chloride and alkali chloride. Leaching takes place generally in several stages, but for the sake of simplicity it is shown in the flow chart as a single stage. Leaching is carried out as countercurrent or concurrent leaching. The redox potential of the leaching is regulated to be in the region of 400-600 mV vs. Ag/AgCI by means of oxygen or some other oxidant. The acid concentration of the leaching stage is adjusted to be in the range of 20 - 100 g/l, so that the pH value is below 1, but preferably at least 0.2. In these conditions, iron and arsenic dissolve, but sulphur precipitates. In the description of the invention the general term gold refers to gold and/or platinum group metals (PGM).
The amount of alkali chloride in the solution used in leaching is around 100 g/l. The alkali is preferably sodium. The amount of alkali chloride is relatively low, because the copper in solution is divalent, so the required alkali chloride concentration is also low. Leaching conditions are regulated to be such that the iron in the sulphide minerals contained in the concentrate, apart from the pyrite, dissolves, as does the arsenic contained in the concentrate. The gold does not dissolve, but is released as the enargite and other arsenic minerals decompose, and the gold enters the leaching residue.
3o The reactions occurring in the leaching method accordant with the invention are described by means of the following reaction equations:
The method according with the invention is described in the appended Figure 1, which shows a flow chart of one of the preferred embodiments of 5 the invention.
DETAILED DESCRIPTION OF THE INVENTION
Pyritic bulk concentrate containing gold, copper and arsenic, is fed to a leaching stage, in which leaching is performed using a solution of io hydrochloric acid containing copper chloride and alkali chloride. Leaching takes place generally in several stages, but for the sake of simplicity it is shown in the flow chart as a single stage. Leaching is carried out as countercurrent or concurrent leaching. The redox potential of the leaching is regulated to be in the region of 400-600 mV vs. Ag/AgCI by means of oxygen or some other oxidant. The acid concentration of the leaching stage is adjusted to be in the range of 20 - 100 g/l, so that the pH value is below 1, but preferably at least 0.2. In these conditions, iron and arsenic dissolve, but sulphur precipitates. In the description of the invention the general term gold refers to gold and/or platinum group metals (PGM).
The amount of alkali chloride in the solution used in leaching is around 100 g/l. The alkali is preferably sodium. The amount of alkali chloride is relatively low, because the copper in solution is divalent, so the required alkali chloride concentration is also low. Leaching conditions are regulated to be such that the iron in the sulphide minerals contained in the concentrate, apart from the pyrite, dissolves, as does the arsenic contained in the concentrate. The gold does not dissolve, but is released as the enargite and other arsenic minerals decompose, and the gold enters the leaching residue.
3o The reactions occurring in the leaching method accordant with the invention are described by means of the following reaction equations:
2Cu3AsS4+12H+ + 51/2 0 2= 6Cu2+ + 2H3AsO4 + 8S + 3H20 (1) CuFeS2 + 4H+ + 02 = Cu2+ + Fe 2+ + 2S + 2H20 (2) FeAsS + 202 + 3H+ = S + Fe 2+ + H3AsO4 (3) If a small amount of gold has dissolved in the concentrate leaching step, it is precipitated back into the leaching residue by means of a suitable reducing agent or adsorbent, for example activated carbon. After this, liquid/solids io separation is performed, whereby the sulphur, pyrite and gold contained in the solids are separated from the solution. The arsenic-free leaching residue thus obtained is treated in an appropriate way to recover the gold. In addition to sulphur, the leaching residue comprises gold, pyrite and the gold contained in it that is released as a result of the decomposition of the minerals, but not iron and arsenic. Therefore the quantity of leaching residue is relatively small and there are many possible ways to process it further.
Sulphur flotation can be performed on the leaching residue (not shown in the drawing), whereby concentrate is obtained that is formed of pyrite and sulphur, containing nearly all the gold of the concentrate used as feedstock.
Depending on the composition of the leaching residue or the type of further processing, the leaching residue may be treated without a sulphur concentration stage. The gold content of the generated sulphur concentrate and/or of the leaching residue is so large, that it can be routed to pyrometallurgical processing. This may take place for instance in a smelter, in which case the recovery yield of precious metals is high. The other possible further processing method is roasting, in which pyrite is oxidised and sulphur is burnt and gold is leached from the calcine with cyanide.
Leaching waste can likewise be processed hydrometallurgically by pressure leaching in an autoclave, whereupon the pyrite decomposes and the gold can be leached into cyanide with a good yield.
Sulphur flotation can be performed on the leaching residue (not shown in the drawing), whereby concentrate is obtained that is formed of pyrite and sulphur, containing nearly all the gold of the concentrate used as feedstock.
Depending on the composition of the leaching residue or the type of further processing, the leaching residue may be treated without a sulphur concentration stage. The gold content of the generated sulphur concentrate and/or of the leaching residue is so large, that it can be routed to pyrometallurgical processing. This may take place for instance in a smelter, in which case the recovery yield of precious metals is high. The other possible further processing method is roasting, in which pyrite is oxidised and sulphur is burnt and gold is leached from the calcine with cyanide.
Leaching waste can likewise be processed hydrometallurgically by pressure leaching in an autoclave, whereupon the pyrite decomposes and the gold can be leached into cyanide with a good yield.
When leaching is performed at the high acid concentration described above, the solution obtained in solids separation has to be neutralised before routing it to the extraction stage. In the method accordant with the invention, iron and arsenic removal from the solution are also carried out during neutralisation by precipitating them as ferric arsenate (FeAsO4-2H20). Since the amount of iron is generally greater than that of arsenic, the excess iron is precipitated in the same stage as goethite (FeOOH) or ferric hydroxide (Fe(OH)3). Precipitation is performed by neutralising the solution to a pH
value of about 2 - 2.5. Neutralisation is carried out by means of a suitable io neutralising agent such as limestone, lime or lye (NaOH).
The divalent copper chloride solution, cleaned of impurities and solids, is routed to extraction. Copper recovery from the organic solution is performed into an aqueous solution of sulphuric acid, which is fed to electrowinning to recover elemental copper. Since the known copper extractants are mostly selective with regard to divalent copper, the copper chloride solution can be fed directly to extraction without an oxidation stage.
The extraction stage is depicted in the drawing as a single step, but it consists of the extraction and stripping stages normally included in extraction. In the extraction stage, an aqueous solution of cupric chloride is contacted with an organic extractant and the copper is made to transfer to the organic phase. The extraction stage includes the normal mixing and settling section, although they are not shown in detail in the drawing. Any known copper extractant is suitable as the extractant, such as oximes, which are diluted with an appropriate solvent, for example kerosene.
The chloride-containing aqueous solution of the extraction stage, the raffinate, which is depleted with regard to copper and has a raised acid concentration, is routed back to concentrate leaching. The organic solution exiting the extraction stages is conveyed via scrubbing to stripping. In stripping, the organic solution containing divalent copper ions is contacted with an aqueous solution of sulphuric acid and the copper transfers to the aqueous phase as sulphate, from where it is recovered by electrowinning.
When copper recovery takes place in copper electrolysis, the electrolysis return acid can be used as the aqueous solution of sulphuric acid in stripping.
value of about 2 - 2.5. Neutralisation is carried out by means of a suitable io neutralising agent such as limestone, lime or lye (NaOH).
The divalent copper chloride solution, cleaned of impurities and solids, is routed to extraction. Copper recovery from the organic solution is performed into an aqueous solution of sulphuric acid, which is fed to electrowinning to recover elemental copper. Since the known copper extractants are mostly selective with regard to divalent copper, the copper chloride solution can be fed directly to extraction without an oxidation stage.
The extraction stage is depicted in the drawing as a single step, but it consists of the extraction and stripping stages normally included in extraction. In the extraction stage, an aqueous solution of cupric chloride is contacted with an organic extractant and the copper is made to transfer to the organic phase. The extraction stage includes the normal mixing and settling section, although they are not shown in detail in the drawing. Any known copper extractant is suitable as the extractant, such as oximes, which are diluted with an appropriate solvent, for example kerosene.
The chloride-containing aqueous solution of the extraction stage, the raffinate, which is depleted with regard to copper and has a raised acid concentration, is routed back to concentrate leaching. The organic solution exiting the extraction stages is conveyed via scrubbing to stripping. In stripping, the organic solution containing divalent copper ions is contacted with an aqueous solution of sulphuric acid and the copper transfers to the aqueous phase as sulphate, from where it is recovered by electrowinning.
When copper recovery takes place in copper electrolysis, the electrolysis return acid can be used as the aqueous solution of sulphuric acid in stripping.
Claims (12)
1. A method for processing pyritic copper sulphide concentrate containing gold and/or platinum group metals (PGM) and arsenic, whereby the concentrate is leached into an aqueous solution of copper chloride and alkali chloride containing hydrochloric acid and the sulphur remains in the residue formed in leaching, characterised in that the redox potential of concentrate leaching is regulated by the feed of an oxidising agent to the range of 400 - 600 mV vs. Ag/AgCl-electrode and the pH is adjusted to the region of 0.2 - 1, whereupon the copper of the concentrate and the copper, iron and arsenic in the arsenic minerals dissolve, and the gold and/or PGM bound to these minerals is released, the pyrite and the gold and/or PGM it contains plus the released gold and/or PGM and sulphur remain in the leaching residue; the iron- and arsenic-containing cupric chloride solution is neutralised to precipitate the iron and arsenic, after which the neutralised iron- and arsenic-free cupric chloride solution is routed to a liquid-liquid extraction stage, where the copper is recovered into an aqueous solution of sulphuric acid and is routed to electrowinning to recover elemental copper and the liquid-liquid extraction raffinate is routed back to concentrate leaching.
2. A method according to claim 1, characterised in that the leaching residue is subjected to sulphur flotation.
3. A method according to claim 1 or 2, characterised in that the leaching residue is subjected to pyrometallurgical treatment in order to recover gold and/or PGM.
4. A method according to claim 3, characterised in that the leaching residue is routed to a smelter.
5. A method according to claim 3, characterised in that the leaching residue is roasted.
6. A method according to claim 1 or 2, characterised in that the leaching residue is subjected to hydrometallurgical processing as a pressure leach in order to recover gold and/or PGM.
7. A method according to claim 1, characterised in that an iron- and arsenic-containing cupric chloride solution is neutralised to a pH value of 2 - 2.5 in order to precipitate iron and arsenic from the solution.
8. A method according to claim 7, characterised in that neutralisation is performed with limestone, lime or lye.
9. A method according to claim 7, characterised in that iron and arsenic are precipitated from solution as ferric arsenate and goethite or as ferric hydroxide.
10.A method according to claim 1, characterised in that the small amount of gold dissolved in the leaching stage is precipitated into the leaching residue by means of a reducing agent or adsorbent.
11.A method according to claim 10, characterised in that the adsorbent is activated carbon.
12.A method according to claim 1, characterised in that the oxidising agent is oxygen or an oxygen-containing gas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20070912A FI120315B (en) | 2007-11-27 | 2007-11-27 | A process for treating a pyrite concentrate containing gold, copper and arsenic |
| FI20070912 | 2007-11-27 | ||
| PCT/FI2008/050672 WO2009068735A1 (en) | 2007-11-27 | 2008-11-20 | Method for processing pyritic concentrate containing gold, copper and arsenic |
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| CA2706414A1 true CA2706414A1 (en) | 2009-06-04 |
| CA2706414C CA2706414C (en) | 2014-02-11 |
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| CA 2706414 Expired - Fee Related CA2706414C (en) | 2007-11-27 | 2008-11-20 | Method for processing pyritic concentrate containing gold, copper and arsenic |
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| AU (1) | AU2008328638B2 (en) |
| BR (1) | BRPI0819618A2 (en) |
| CA (1) | CA2706414C (en) |
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| FI (1) | FI120315B (en) |
| MX (1) | MX2010005599A (en) |
| PE (1) | PE20091287A1 (en) |
| WO (1) | WO2009068735A1 (en) |
| ZA (1) | ZA201003204B (en) |
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| US8052774B2 (en) * | 2009-03-31 | 2011-11-08 | Sumitomo Metal Mining Co., Ltd. | Method for concentration of gold in copper sulfide minerals |
| CN101817553B (en) * | 2010-04-02 | 2012-03-07 | 云南锡业集团（控股）有限责任公司 | Method for treating arsenic-containing smoke dust |
| FI124954B (en) * | 2013-04-30 | 2015-04-15 | Outotec Oyj | A process for preparing a solution containing gold and a process arrangement for recovering gold and silver |
| CN105734300B (en) * | 2014-12-08 | 2018-03-27 | 云南云铜锌业股份有限公司 | A kind of method that recovery copper, arsenic are cured as scorodite from copper fumes |
| WO2016134420A1 (en) * | 2015-02-24 | 2016-09-01 | Intec International Projects Pty Ltd | Processing of sulfidic ores |
| WO2016168930A1 (en) | 2015-04-21 | 2016-10-27 | University Of Saskatchewan | Methods for simultaneous leaching and extraction of precious metals |
| RU2651017C1 (en) * | 2017-09-20 | 2018-04-18 | Общество с ограниченной ответственностью "Золотодобывающая Корпорация" | Method of leaching pyrite containing raw materials |
| CN108220618A (en) * | 2018-01-19 | 2018-06-29 | 中国地质科学院矿产综合利用研究所 | Arsenic-fixing and copper-extracting method for high-arsenic copper sulfide ore |
| JP6998259B2 (en) | 2018-03-30 | 2022-01-18 | Ｊｘ金属株式会社 | How to treat copper ore |
| CN111225988B (en) * | 2018-09-29 | 2022-04-29 | 长沙有色冶金设计研究院有限公司 | Oxygen pressure leaching method of copper sulfide concentrate and copper smelting method |
| CN110216018A (en) * | 2019-05-28 | 2019-09-10 | 西北矿冶研究院 | Beneficiation method for high-mud fine-grain copper oxide ore |
| CN110256079B (en) * | 2019-06-26 | 2021-01-26 | 中国科学院地球化学研究所 | Preparation method of high-purity compact arsenopyrite electrode |
| CN112063833B (en) * | 2020-08-21 | 2022-03-29 | 向双清 | Method for removing arsenic and inhibiting sulfur loss of copper concentrate |
| CN113088702B (en) * | 2021-04-01 | 2022-04-05 | 云南黄金矿业集团股份有限公司 | Method for recovering valuable elements from acid leaching solution of roasting slag of gold-containing sulfur concentrate |
| CN114934170B (en) * | 2022-05-23 | 2024-04-19 | 江西理工大学 | Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper |
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| US5820966A (en) * | 1997-12-09 | 1998-10-13 | Inco Limited | Removal of arsenic from iron arsenic and sulfur dioxide containing solutions |
| AUPP543798A0 (en) * | 1998-08-24 | 1998-09-17 | Technological Resources Pty Limited | Hydrometallurgical extraction of copper and other valuable metals |
| FI115534B (en) * | 2002-10-15 | 2005-05-31 | Outokumpu Oy | Process for extraction of metals by means of chloride solution and extraction |
| FI117708B (en) * | 2004-04-30 | 2007-01-31 | Outokumpu Technology Oyj | Procedure for the extraction of gold in connection with the manufacture of copper |
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- 2008-11-20 WO PCT/FI2008/050672 patent/WO2009068735A1/en active Application Filing
- 2008-11-20 MX MX2010005599A patent/MX2010005599A/en active IP Right Grant
- 2008-11-20 AU AU2008328638A patent/AU2008328638B2/en not_active Ceased
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| CL2008003513A1 (en) | 2009-06-05 |
| AU2008328638A1 (en) | 2009-06-04 |
| FI20070912A (en) | 2009-05-28 |
| AU2008328638B2 (en) | 2013-01-24 |
| FI120315B (en) | 2009-09-15 |
| MX2010005599A (en) | 2010-06-09 |
| PE20091287A1 (en) | 2009-09-03 |
| FI20070912A0 (en) | 2007-11-27 |
| CA2706414C (en) | 2014-02-11 |
| ZA201003204B (en) | 2011-06-29 |
| WO2009068735A1 (en) | 2009-06-04 |
| BRPI0819618A2 (en) | 2015-05-05 |
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