CN105339511B - 回收铜和贵金属的方法 - Google Patents
回收铜和贵金属的方法 Download PDFInfo
- Publication number
- CN105339511B CN105339511B CN201480036875.5A CN201480036875A CN105339511B CN 105339511 B CN105339511 B CN 105339511B CN 201480036875 A CN201480036875 A CN 201480036875A CN 105339511 B CN105339511 B CN 105339511B
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- Prior art keywords
- copper
- solution
- aqueous
- silver
- cupric
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- 239000010949 copper Substances 0.000 title claims abstract description 170
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910000510 noble metal Inorganic materials 0.000 title abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 84
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 42
- 238000000638 solvent extraction Methods 0.000 claims abstract description 25
- 239000012141 concentrate Substances 0.000 claims abstract description 21
- 150000004820 halides Chemical class 0.000 claims abstract description 20
- 239000003978 infusion fluid Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 40
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 239000004332 silver Substances 0.000 claims description 40
- 238000000605 extraction Methods 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- -1 hydroxyl oxime Chemical class 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- VQSXKKXMSXGLBZ-UHFFFAOYSA-L copper;chloride;hydroxide Chemical compound [OH-].[Cl-].[Cu+2] VQSXKKXMSXGLBZ-UHFFFAOYSA-L 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- MXRLZCWBOJMFJG-UHFFFAOYSA-N tris(2-methylpropyl)-sulfanylidene-$l^{5}-phosphane Chemical group CC(C)CP(=S)(CC(C)C)CC(C)C MXRLZCWBOJMFJG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical group 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical group S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 claims description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 claims description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 230000033116 oxidation-reduction process Effects 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000000658 coextraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UHSURKDCQCGNGM-UHFFFAOYSA-N 5-(2-hydroxyimino-2-phenylethyl)nonan-2-ol Chemical class CCCCC(CCC(C)O)CC(=NO)C1=CC=CC=C1 UHSURKDCQCGNGM-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 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
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- PDMKBIZYOLJQFE-UHFFFAOYSA-N S.OS(O)(=O)=S Chemical compound S.OS(O)(=O)=S PDMKBIZYOLJQFE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005059 solid analysis Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DAGQYUCAQQEEJD-UHFFFAOYSA-N tris(2-methylpropyl)phosphane Chemical compound CC(C)CP(CC(C)C)CC(C)C DAGQYUCAQQEEJD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/06—Oxychlorides
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical 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
- C22B15/0063—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
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods 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
- 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
- C22B3/08—Sulfuric acid, other sulfurated 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
- 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
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- 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
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
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Abstract
本发明涉及从含铜硫化物矿石或精矿回收铜和一种或多种贵金属的方法,包括:在大气条件或略微加压的条件下在低于浸出溶液的沸点的温度下,在硫酸溶液中在一种或多种碱金属或碱土金属卤化物的存在下浸出含铜矿石和/或精矿,由此总卤化物浓度为从30至115g/L,以溶解铜和获得包含处于溶液中的铜、硫物质和卤化物的浸出液。随后使该浸出液经受固‑液分离,此后获得第一含水富集浸出溶液和贫铜的浸出残余物。通过溶剂萃取从该第一含水富集浸出溶液提纯铜,以获得第一含铜负载有机溶液和第一含水萃余液。对该含铜负载有机溶液进行反萃取,并且从包含痕量的氯化物的反萃取溶液回收铜。
Description
发明领域
本发明涉及从矿石和/或精矿回收金属的方法,并且特别涉及从含铜硫化物原料回收铜和任选回收一种或多种贵金属。
发明背景
从含氧化性铜的原料回收铜可通过如下方法实现:用pH为1至2.5的硫酸浸出原料,接着在溶剂萃取后通过电解沉积进行铜回收。然而,特别对于主硫化物矿物,仅可以在高的温度和压力下用硫酸浸出铜,由于单质硫的高氧化水平,导致了含有高硫酸浓度的富集浸出溶液。这使得铜的溶剂萃取昂贵,因为必须在溶剂萃取阶段之前中和溶液中过量的酸。
存在关于从含铜硫化物矿石回收金属特别是铜的几篇公开文献,其中利用盐酸或高氯化物浓度。虽然可以在与硫酸工艺相比降低的压力和温度下进行浸出,但是富集浸出溶液中的高氯化物浓度降低了溶剂萃取中的铜萃取产率并且使该工艺更加没有吸引力。
WO2004035840例如涉及用于从含铜原料回收金属特别是铜的方法,由此将材料浸出到含氯化物的溶液中。氧化性地进行原料的浸出,并且该浸出在来自浸出的氯化铜溶液中的铜主要是二价的足够高的氧化还原电势下进行。所获得的氯化物溶液,含有铜和潜在的其他有价值的金属,被供给到液-液萃取。在萃取中首先用萃取将铜转移到有机相,然后在反萃取中转移到硫酸盐溶液,将该硫酸盐溶液供给到铜电解沉积。
另一方面US2010/0031779A1公开了通过用阳离子交换萃取剂溶剂萃取来从含有氯化铜和碱金属和/或碱土金属氯化物的酸性水溶液回收铜的方法,其包括在硫酸根离子的存在下处理溶剂萃取的步骤。
发明简述
本发明的一个目的是提供一种用于从含铜硫化物矿石和/或精矿回收铜和任选回收一种或多种贵金属的方法。通过特征在于在独立权利要求中所述的方法来实现本发明的目的。在从属权利要求中公开了本发明的优选实施方案。
本发明提供了一种用于湿法冶金回收铜和其他金属的方法,其中以这样的方式优化了含铜硫化物矿石和/或精矿的浸出条件:使得可以在大气压或稍微提高的压力(最高至300kPa)下和在温和条件下实现铜和其他贵金属的回收。另外,可以实现通过溶剂萃取来回收铜而没有额外的中和步骤的必要性。由于相对低的氯化物浓度,可以以高产率回收金属。这将允许直接回收铜并且同时浸出铜和银贵金属。
本发明涉及从含铜硫化物矿石或精矿回收铜和一种或多种贵金属的方法,包括:在大气条件或略微加压的条件下在低于浸出溶液的沸点的温度下,在硫酸溶液中在一种或多种碱金属或碱土金属卤化物的存在下浸出含铜矿石和/或精矿,由此总卤化物浓度为从30至115g/L,以溶解铜和获得包含处于溶液中的铜、硫酸盐和卤化物的浸出液。随后使该浸出液经受固-液分离,此后获得第一含水富集浸出溶液和贫铜的浸出残余物。通过溶剂萃取从该第一含水富集浸出溶液提纯铜,以获得第一含铜负载有机溶液和第一含水萃余液。对该含铜负载有机溶液进行反萃取,并且从包含痕量的氯化物的反萃取溶液回收铜。
附图简要说明
在下面将通过优选实施方案参考附图更详细地描述本发明,其中
图1示出说明本发明的第一实施例的铜和银浸出和回收工艺。
发明详述
本发明涉及从矿石和/或精矿回收金属的湿法冶金方法,并且特别地涉及从含铜硫化物原料回收铜和任选回收一种或多种其它贵金属。
本发明提供了从含铜硫化物矿石和/或精矿回收铜的方法,包括以下步骤:(a)在大气条件或略微加压的条件下在低于浸出溶液的沸点的温度下,在硫酸溶液中在一种或多种碱金属和/或碱土金属卤化物的存在下浸出含铜矿石和/或精矿,由此总卤化物浓度为从30至115g/L,以溶解铜和获得包含处于溶液中的铜、硫物质和卤化物的浸出液;(b)将该浸出液固-液分离以获得第一含水富集浸出溶液和贫铜的浸出残余物;(c)通过溶剂萃取从该第一含水富集浸出溶液萃取铜,以获得第一含铜负载有机溶液和第一含水萃余液;(d)用电解质溶液从该第一含铜负载有机溶液反萃取铜,以获得贫铜有机溶液和含铜电解质溶液;和(e)从该含铜电解质溶液回收铜。
本发明还提供了从含铜硫化物矿石或精矿回收铜和一种或多种贵金属的方法,该方法还包括以下步骤:(f)通过溶剂萃取从第一含水萃余液萃取银,以获得含银负载有机溶液和第二含水萃余液;(g)对该含银负载有机溶液进行反萃取以获得含银水溶液;(h)从该含银水溶液回收银。
本发明特别适用于从铜精矿和/或矿石(其中主要矿物是黄铜矿(CuFeS2))回收铜和任选回收一种或多种贵金属。除了铜和贵金属例如银和金以外,矿石和/或精矿还可包含其它贵金属或稀有金属例如镍、铂和/或钯。矿石和/或精矿还可包含例如铁、砷、锑和/或钙。
图1示出了铜和银浸出和回收工艺的工艺流程的实例。将含铜原料(1)供给到铜和银浸出阶段(10),其中在大气条件或略微加压的条件下浸出原料(1)。可以在特别是从70到300kPa的总压力下,有利地在大气压下进行浸出。浸出阶段的温度低于酸溶液的沸点,有利地从80至105℃,优选从90至99℃。由于流体静压力,浸出阶段的温度可局部地上升高于浸出溶液的沸点。在卤化物(2)的存在下用硫酸溶液(3)进行浸出。硫主要作为硫酸根或硫酸氢根离子存在于溶液中。它们的总量取决于铁的沉淀,这可使硫物质例如作为黄钾铁矾共沉淀。优选地,不同硫物质(特别是硫酸根和硫酸氢根离子)的总浓度,作为硫给出是从2至25g/L。总卤化物浓度为从30至115g/L,优选为从35至110g/L,更优选为从40至95g/L。卤化物防止黄铜矿在浸出过程中钝化并且使银的溶解成为可能。所需的卤化物浓度可以根据进料的银含量而变化,并因此根据该银含量适当地进行调节。过量的卤化物将不会增强铜浸出,并且还可以通过溶剂萃取而损害铜和银的回收。优选以一种或多种碱金属和/或碱土金属卤化物的形式将卤化物提供到浸出阶段。碱金属优选是钠。所述卤化物优选是氯化物,以便防止金的溶解。有利地,使用NaCl作为卤化物源。优选地,浸出溶液包含从30至115g/L氯化物。
使用氧化剂进料(4),将浸出的氧化还原电势调节到400至600、特别是500到600mVAg/AgCl(相对于Pt)的范围内。该氧化剂可以是氧、富氧空气或空气,优选为氧。浸出阶段的pH优选保持为从1.7至3,更优选从1.7至2.6,最优选从2.0至2.4,以便沉淀铁而防止铜作为羟基氯化铜、特别是氯铜矿(Cu2Cl(OH)3))沉淀。可使铁沉淀为赤铁矿、黄钾铁矾、针铁矿和/或其他铁沉淀物中的一种或多种。杂质例如砷或锑不会被浸出或它们立即与铁共沉淀。可以浸出少量的金(约0.1%至10%)。如果少量的金溶解在浸出步骤中,可以通过合适的还原剂将它沉淀回到浸出残余物中或通过已知的方法例如在WO2011154603中公开的方法进行回收。
在铜和银浸出阶段中发生的反应可以由下列反应方程式描述:
CuFeS2(s)+3CuCl2(aq)→4CuCl(aq)+FeCl2(aq)+S0(s) (i)
4Cu+(aq)+O2(g)+4H+(aq)→4Cu2+(aq)+2H2O(aq) (ii)
4Fe2+(aq)+O2(g)+6H2O(aq)→4FeOOH(s)+8H+(aq) (iii)
2S0(s)+3O2(g)+2H2O(aq)→4H+(aq)+2SO4 2-(aq) (iv)
在铜和银浸出阶段之后,进行液体/固体分离(未在图1中示出),由此将包含在固体中的金从溶液分离。分离可以通过任何已知的液体/固体分离技术来实现,包括过滤和浓缩。然后可以以合适的方式处理贫铜的浸出残余物(5)以回收金。
参考图1,使从固/液分离阶段获得的富集浸出溶液(PLS,6)经受铜溶剂萃取(CuSX)阶段(20)。通常,PLS包含溶解的金属,包括从1至100g/L、特别是从1至70g/L的铜和从1至100mg/L、特别是从1至80mg/L的银。在萃取之前将PLS冷却到低于60℃,优选低于45℃,更优选至40℃。然后用包含稀释在烃溶剂中的基于羟肟(hydroxyoxime)的商业铜萃取剂的有机溶液从水溶液萃取铜。铜萃取剂优选选自醛肟、酮肟以及它们的任何混合物。第一含水富集浸出溶液和有机溶液的体积比在1:6和6:1之间。
萃取剂可以进一步包含改性剂。有利的是铜萃取剂是5-壬基水杨醛肟或5-十二烷基水杨醛肟和2-羟基-5-壬基苯乙酮肟的混合物,特别是5-壬基水杨醛肟和2-羟基-5-壬基苯乙酮肟的混合物,体积比为1:1(LIX984N)。由于浸出条件,在萃取之前和/或萃取期间不需要中和。优选在萃取之前和/或萃取期间在没有任何的水相中和的情况下完成铜的萃取,因为它会对该工艺的操作成本具有负面影响。然而,中和会增加萃取中的铜产率,但它不补偿成本,因为萃余液中的铜不会损失而是再循环回到浸出或通过其它方式得到回收。
可以在一个或几个阶段中萃取铜。萃取阶段的数目取决于水相的铜和氯化物浓度。通过洗涤将离开萃取阶段的有机溶液带至反萃取。可通过用稀释的酸溶液、特别是含有硫酸铜的硫酸溶液洗涤含铜负载有机溶液来除去杂质和共萃取的金属。当在铜电解(即电解沉积)中回收铜时,可以利用来自铜电解沉积的稀释的铜电解质溶液作为稀释的含有硫酸铜的硫酸溶液。在一个或几个阶段中洗涤含铜负载有机溶液,以确保没有或仅有痕量卤化物进入铜电解沉积阶段。可使洗涤溶液经受残留铜的回收或返回到铜溶剂萃取中的萃取阶段。
Cu SX阶段中发生的反应可以由下列反应方程式描述:
其中R是铜萃取剂。
然后在一个或几个阶段中用电解质溶液从含铜负载有机溶液反萃取铜。该电解质溶液包含高量的硫酸并且铜被转移到水相。然后可以将有机相再循环回到铜萃取阶段。该电解质溶液优选为硫酸盐水溶液,特别是酸性硫酸铜溶液。该电解质溶液优选包含150至190g/L硫酸和30至55g/L、优选35至45g/L的Cu。随后可以通过电解沉积(EW,21)从该电解质溶液将铜回收为铜阴极(91)。可替代地,例如可以通过化学置换或结晶来回收铜。在回收铜之前,可以使含铜电解质溶液经受通过经由双介质过滤器来过滤电解质溶液的提纯,用于在电解之前除去任何残留的有机残余物。
在铜电解沉积(Cu EW)中发生的反应可以由下列反应方程式描述:
Cu2+(aq)+H2O(aq)→Cu(s)+2H+(aq)+0.5O2(g) (vi)
可以在铜电解沉积中使大于50%的在铜和银浸出阶段中所需要的酸(3)再生并经由铜萃取萃余液转移到浸出阶段。剩余部分可由盐酸或硫酸补充物获得,然而硫酸是优选的。
然后使贫铜含水萃余液(7)即从铜萃取得到的第一含水萃余液经受银溶剂萃取(Ag SX,30)。用与水不混溶的叔膦硫化物例如三异丁基硫化膦(TIBPS,Cyanex 471x)的有机溶液从第一含水萃余液(7)萃取银。银萃取剂溶液还可以包含有机磷酸、有机膦酸、有机次膦酸和/或羧酸改性剂。有利地,使用有机磷酸例如二-(2-乙基己基)磷酸(D2EHPA),或叔羧酸例如新癸酸(Verastic 10)作为改性剂,以增加银-硫化物络合物在有机相中的溶解度。优选地,银萃取剂包含TIBPS和5体积%的D2EHPA或从1至15体积%的Versatic 10。由于萃取工艺条件,在萃取过程中不需要pH调节或中和。因此,铜溶剂萃取萃余液中的酸不会损失,并且可以在浸出中得到再利用。
在Ag SX阶段(30)中发生的反应可以由下列反应方程式描述:
AgCl(aq)+L(org)→L·AgCl(org) (vii),
其中L是银萃取剂。
可在一个或几个步骤中萃取银。经由洗涤将离开萃取阶段的有机溶液带至反萃取。可通过用含有从0到4M氯化物和从1至4M硫酸或盐酸的酸溶液洗涤含银负载有机相来去除杂质和共萃取的金属。
然后可以用硫代硫酸盐溶液反萃取银。该硫代硫酸盐溶液优选包含亚硫酸钠,以防止硫代硫酸盐的氧化。在一个或几个步骤中反萃取银,并且随后可以将有机相再循环回到银溶剂萃取阶段。例如可以通过如下方式从反萃取溶液回收银:沉淀或化学置换(31),例如与Cu粉(14)置换和通过过滤来分离以获得置换的银(13)。可替代地,可通过电解沉积来回收银。
将来自铜和银溶剂萃取阶段(20,30)的贫铜和贫银和含酸的萃余液(8)的主要部分再循环回到铜浸出阶段(10)。使来自萃余液的1至50%之间的排出流经受铜去除阶段(40),其中通过向溶液添加碱、特别是CaCO3和/或Ca(OH)2(15)优选使铜作为羟基氯化铜沉淀。氯铜矿Cu2Cl(OH)3是优选的羟基氯化铜沉淀物。可以在2.6至7、优选2.6至5.5、更优选3至5.5的pH下进行羟基氯化铜从第一含水萃余液和/或第二含水萃余液的沉淀。在液体/固体分离之后,则在20至60℃的温度和20至150g/L的硫酸浓度下用硫酸水溶液(18)浸出(41)所获得的沉淀物,并且将浆料再循环回到浸出(10),其中使用过量的酸。可替代地,可以使浆料经受液体/固体分离,并且将所获得的液体再循环回到浸出(10)。来自铜去除阶段的溶液进入杂质沉淀,其中通过用Ca(OH)2沉淀来除去杂质金属。
实施例
实施例1
铜和银浸出:在95℃下将黄铜矿精矿供给到大气铜浸出阶段。用硫酸和来自溶剂萃取的酸性萃余液在氯化钠的存在下浸出精矿。硫酸盐浓度为约50g/L并且氯化物浓度(concentrate)为80g/L。使用氧气作为氧化剂。通过添加硫酸将pH保持在2.2。采用12小时停留时间的铜和银浸出产率分别为约94%和95%。
铜和银回收:富集浸出溶液具有2至2.4的pH,并且它包含40g/L的铜。将其冷却至40℃。在三个阶段中用处于高闪点烃稀释剂(LIX984N)中的40体积%的5-壬基水杨醛肟和2-羟基-5-壬基苯乙酮肟的1:1体积混合物萃取铜。萃余液含有10g/L铜和约55g/L H2SO4,并且使其经受银萃取。在一个洗涤阶段中用来自铜电解沉积的稀释的电解质溶液洗涤来自含铜有机相的杂质。在两个阶段中用电解质反萃取铜。将有机相再循环回到铜萃取。
用具有5体积%的二-(2-乙基己基)磷酸(D2EHPA)改性剂的26g/L三异丁基硫化膦溶液(Cyanex 471x)萃取银。温度是40℃。在两个阶段中萃取的银产率是98%。将大部分含有酸的萃余液再循环回到铜浸出阶段。用2M HCl洗涤共萃取的金属。用含有15g/L亚硫酸钠的108g/L的硫代硫酸钠溶液反萃取银。在两个阶段中反萃取银,并且将有机相再循环回到银萃取。银反萃取溶液含有0.5至2g/L的银。用铜粉置换银。用过滤器分离所置换的银。将硫代硫酸盐溶液再循环回到反萃取。
来自铜和银溶剂萃取的大部分萃余液进入铜和银浸出阶段。将来自萃余液的排出流泵送到铜沉淀阶段,其中通过添加氢氧化钙在pH3.8下沉淀氯铜矿Cu2(OH)3Cl。在固液分离之后用硫酸浸出沉淀物,然后将浆料返回到铜和银浸出。来自铜沉淀的溶液进入杂质沉淀,其中在pH 10下沉淀杂质。
实施例2
在大气压下在5L钛衬里的反应器中浸出含有29.2wt%的铜(主要作为黄铜矿)和235g/t银的铜精矿。该反应器装有4块隔板。用含有10g/L铜和80g/L氯化物的溶液填充该反应器。向该反应器添加620g精矿,并且将浆料加热至95℃。氧进料为400mL/分钟且其在实验开始1小时后开始。将氧供给至混合器下方。通过添加浓硫酸将pH保持在2至2.3之间。通过泵送来添加酸并通过测量的pH来自动控制该泵。在15小时后,浸出残余物含有1.6%的铜和10g/t的银。
实施例3
用处于C11-C14链烷烃和环烷烃(naphtene)溶液(Shellsol D70煤油)中的40体积%的2-羟基-5-壬基水杨醛肟(Acorga M5640)测量铜的溶剂萃取,在测试之前该溶液含有4.3g/L的铜。水相含有41.1g/L的铜、78.8g/L的氯化物和19g/L的锌。在室温下在没有pH控制的情况下在分液漏斗中进行摇动测试。摇动时间和沉降时间均为15分钟。测试中的有机相体积为60mL并且水相体积为30mL。萃取后水相含有19g/L的铜。
实施例4
以实验室规模连续地操作铜精矿浸出和溶剂萃取,并且收集小部分的溶剂萃取含水萃余液用于铜去除阶段测试。铜去除由两个2L的反应器构成,其中停留时间为2.6小时。将反应器中的温度保持在40℃。进料浓度为Cu 11.3-12.3g/L,Zn 10-10.4g/L,Fe 0.136-0.228g/L,S 11.1-13.7g/L,钙0.761-0.834g/L,Cl 85-90g/L。将固体浓度为250g/L的氢氧化钙浆料供给到第一反应器以控制pH。在表1和表2中分别示出了来自溶液和固相的pH测量和样品分析。结果表明:采用介于1.82-1.94之间的铜:氯化物摩尔比,铜如何沉淀为氯化物沉淀物。在大多数锌沉淀之前铜也沉淀。沉淀物还含有石膏,因为使过量的硫酸盐沉淀。
表1.铜去除测试的溶液分析
表2.铜去除测试的固体分析
对于本领域技术人员将显而易见的是,随着技术进步,可以以各种方式来实施本发明构思。本发明及其实施方案不限于上述的实施例,而是可以在权利要求的范围内变化。
Claims (25)
1.从含铜硫化物矿石和/或精矿回收铜的方法,包括以下步骤:
(a)在大气或最高至300kPa的提高压力下,在80-105℃的低于浸出溶液的沸点的温度下在硫酸溶液中在一种或多种碱金属或碱土金属卤化物的存在下浸出含铜矿石和/或精矿,由此总卤化物浓度为从30至115g/L,以溶解铜和获得包含处于溶液中的铜、硫物质和卤化物的浸出液;
(b)将该浸出液固-液分离以获得第一含水富集浸出溶液和贫铜的浸出残余物;
(c)通过溶剂萃取从该第一含水富集浸出溶液萃取铜,以获得第一含铜负载有机溶液和第一含水萃余液;使该第一含水萃余液的排出流经受羟基氯化铜沉淀步骤;并且在固-液分离后使杂质从贫铜溶液沉淀;
(d)用电解质溶液从该第一含铜负载有机溶液反萃取铜,以获得贫铜有机溶液和含铜电解质溶液;和
(e)从该含铜电解质溶液回收铜。
2.如权利要求1所述的方法,其特征在于:通过电解沉积从该含铜电解质溶液回收铜,以获得金属铜和贫铜电解质溶液。
3.如权利要求1或2所述的方法,其特征在于:该方法包括使大部分的第一含水萃余液再循环至铜浸出步骤(a)。
4.如权利要求1或2任一项所述的方法,其特征在于:该方法还包括以下步骤:
(f)通过溶剂萃取从第一含水萃余液萃取银,以获得含银负载有机溶液和第二含水萃余液;
(g)对该含银负载有机溶液进行反萃取以获得含银水溶液;和
(h)从该含银水溶液回收银。
5.如权利要求4所述的方法,其特征在于:通过沉淀、置换或电解沉积从含银水溶液回收银。
6.如权利要求4所述的方法,其特征在于:该方法包括使大部分的第二含水萃余液再循环至铜浸出步骤(a)。
7.如权利要求1或2所述的方法,其特征在于:通过溶剂萃取利用包含稀释在烃溶剂中的基于羟肟的铜萃取剂的有机溶液作为铜萃取剂从第一含水富集浸出溶液萃取铜。
8.如权利要求7所述的方法,其特征在于:基于羟肟的铜萃取剂选自醛肟、酮肟以及它们的任何混合物。
9.如权利要求7所述的方法,其特征在于:该第一含水富集浸出溶液和该有机溶液的体积比在1:6和6:1之间。
10.如权利要求1或2所述的方法,其特征在于:在反萃取步骤(d)之前,用稀释的酸溶液洗涤该第一含铜负载有机溶液以移除杂质。
11.如权利要求10所述的方法,其特征在于:在反萃取步骤(d)之前,用来自铜电解沉积的稀释的铜电解质洗涤该第一含铜负载有机溶液以移除杂质。
12.如权利要求4所述的方法,其特征在于:用稀释在烃稀释剂中的叔膦硫化物的有机溶液从该第一含水萃余液萃取银,该烃稀释剂任选地包含有机磷酸、有机膦酸、有机次膦酸和/或羧酸改性剂。
13.如权利要求12所述的方法,其特征在于:该叔膦硫化物是三异丁基硫化膦。
14.如权利要求12所述的方法,其特征在于:该改性剂是二-(2-乙基己基)磷酸(D2EHPA)或叔羧酸。
15.如权利要求14所述的方法,其特征在于:该叔羧酸为新癸酸(Versatic 10)。
16.如权利要求4所述的方法,其特征在于:在反萃取步骤(g)之前,用稀释的酸溶液洗涤含银负载有机溶液以移除杂质。
17.如权利要求16所述的方法,其特征在于:在反萃取步骤(g)之前,用包含0至4M的氯化物和1至3M的硫酸或盐酸的溶液洗涤含银负载有机溶液以移除杂质。
18.如权利要求4所述的方法,其特征在于:该方法包括使该第二含水萃余液的排出流经受羟基氯化铜沉淀;并且在固-液分离后使杂质从贫铜溶液沉淀。
19.如权利要求18所述的方法,其特征在于:在从第一含水萃余液和/或第二含水萃余液沉淀羟基氯化铜中,pH为2.6至7。
20.如权利要求19所述的方法,其特征在于:在从第一含水萃余液和/或第二含水萃余液沉淀羟基氯化铜中,pH为2.6至5.5。
21.如权利要求19所述的方法,其特征在于:在从第一含水萃余液和/或第二含水萃余液沉淀羟基氯化铜中,pH为3至5.5。
22.如权利要求1或2所述的方法,其中在400至600mV Ag/AgCl对Pt的氧化-还原电势和从1.7至3的pH下进行步骤(a)中的金属浸出。
23.如权利要求22所述的方法,其中在400至600mV Ag/AgCl对Pt的氧化-还原电势和从1.7至2.6的pH下进行步骤(a)中的金属浸出。
24.如权利要求1或2所述的方法,其特征在于:在步骤(a)中的金属浸出中使用氧、富氧空气或空气;并且其在从87至300kPa的总压力下进行。
25.如权利要求1或2所述的方法,其特征在于:该第一含水富集浸出溶液含有从1至100g/L的铜。
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