WO2018188537A1 - 一种铜镍硫化矿综合回收利用的方法及其系统 - Google Patents
一种铜镍硫化矿综合回收利用的方法及其系统 Download PDFInfo
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- WO2018188537A1 WO2018188537A1 PCT/CN2018/082209 CN2018082209W WO2018188537A1 WO 2018188537 A1 WO2018188537 A1 WO 2018188537A1 CN 2018082209 W CN2018082209 W CN 2018082209W WO 2018188537 A1 WO2018188537 A1 WO 2018188537A1
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- WIPO (PCT)
- Prior art keywords
- leaching
- nickel
- copper
- iron
- cobalt
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- 238000000034 method Methods 0.000 title claims abstract description 91
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 417
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 372
- 238000002386 leaching Methods 0.000 claims abstract description 334
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 204
- 229910052742 iron Inorganic materials 0.000 claims abstract description 199
- 229910052802 copper Inorganic materials 0.000 claims abstract description 162
- 239000010949 copper Substances 0.000 claims abstract description 162
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 149
- 239000010970 precious metal Substances 0.000 claims abstract description 125
- 238000003723 Smelting Methods 0.000 claims abstract description 111
- 239000010941 cobalt Substances 0.000 claims abstract description 108
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 106
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 225
- 239000002893 slag Substances 0.000 claims description 123
- 238000006243 chemical reaction Methods 0.000 claims description 121
- 239000007788 liquid Substances 0.000 claims description 86
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 66
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 46
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000000605 extraction Methods 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 20
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 15
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 14
- 239000003350 kerosene Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000010409 ironing Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000863 Ferronickel Inorganic materials 0.000 claims 1
- 239000012141 concentrate Substances 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 170
- 238000011084 recovery Methods 0.000 description 40
- 235000010269 sulphur dioxide Nutrition 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 22
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 17
- 229940044175 cobalt sulfate Drugs 0.000 description 16
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 13
- -1 platinum group metals Chemical class 0.000 description 13
- 238000007664 blowing Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 10
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 10
- 239000011790 ferrous sulphate Substances 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- 239000001117 sulphuric acid Substances 0.000 description 9
- 235000011149 sulphuric acid Nutrition 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 229910052598 goethite Inorganic materials 0.000 description 8
- 229910052595 hematite Inorganic materials 0.000 description 8
- 239000011019 hematite Substances 0.000 description 8
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 8
- 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 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004291 sulphur dioxide Substances 0.000 description 6
- 229910000570 Cupronickel Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RGZVRADFLSQOLD-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl) hydrogen phosphate Chemical compound CC(C)(C)CC(C)COP(O)(=O)OCC(C)CC(C)(C)C RGZVRADFLSQOLD-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- FIZHYLRXUDIWQW-UHFFFAOYSA-H cobalt(2+) iron(2+) nickel(2+) trisulfate Chemical compound S(=O)(=O)([O-])[O-].[Ni+2].[Co+2].[Fe+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] FIZHYLRXUDIWQW-UHFFFAOYSA-H 0.000 description 1
- RFYUQSQGLHNNOY-UHFFFAOYSA-N cobalt;sulfuric acid Chemical compound [Co].OS(O)(=O)=O RFYUQSQGLHNNOY-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
-
- 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
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0484—Separation of nickel from cobalt in acidic type 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
- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- 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
Abstract
Description
Claims (15)
- 一种铜镍硫化矿综合回收利用的方法,其特征在于,包括以下步骤:1)选择性浸出:通过方案A或方案B获取富集有镍铁钴的浸出液和富集有铜的浸出渣:方案A:即为从铜镍硫化矿中回收主伴生元素的方法,其选择性浸出步骤为:向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍以及浸出反应液,进行选择性浸出,分别收集硫化氢气体、第一浸出液和第一次浸出渣,其中,所述反应底液为质量分数20%-60%的硫酸溶液,所述浸出反应液为质量分数60%-95%的硫酸溶液;向所述第一次浸出渣中加入水,溶解,分别收集第二浸出液和第二浸出渣;方案B:即为对铜镍硫化矿综合利用的方法,其选择性浸出步骤为:对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出,分别收集硫化氢气体、浸出液和浸出渣,其中,常压选择性浸出的温度为25-80℃;方案A的第二浸出液、方案B的浸出液即为富集有镍铁钴的浸出液;方案A的第二浸出渣、方案B的浸出渣为富集有铜的浸出渣;2)对步骤1)富集有镍铁钴的浸出液进行除铁,分别收集除铁后液和除铁渣,除铁后液用于镍和钴的提取,除铁渣用于炼铁;和/或,对步骤1)的富集有铜的浸出渣送铜冶炼系统冶炼,分别得到铜和贵金属。
- 根据权利要求1所述的方法,其特征在于,在步骤1)方案A中,所述选择性浸出为常压非氧化性浸出;和/或,所述浸出反应液为质量分数为85%-90%的硫酸溶液。
- 根据权利要求1所述的方法,其特征在于,在步骤1)方案A中,所述低冰镍和浸出反应液同时连续加入,且两者的加入量与消耗量相同;所述第一浸出液返回作为下一批物料的反应底液,循环使用。
- 根据权利要求1所述的方法,其特征在于,在步骤1)方案A中,加料完成后继续浸出0.5-2h。
- 根据权利要求1所述的方法,其特征在于,在步骤1)方案B中,所述硫酸浓度为1mol/L-6mol/L,常压选择性浸出的液固比为2:1-20:1,常压选择性浸出时间为0.5-5h。
- 根据权利要求5所述的方法,其特征在于,在步骤1)方案B中,所述步骤1)中硫酸浓度为3mol/L-4mol/L,常压选择性浸出时间为0.5-2h,浸出温度为50-70℃,液固比为5:1-10:1。
- 根据权利要求1-6中任一项所述的方法,其特征在于,所述造锍熔炼中产生的二氧化硫与步骤1)中的硫化氢气体反应制备硫磺,以及将剩余二氧化硫转换成步骤1)中进行常压选择性浸出所使用的硫酸溶液。
- 根据权利要求1-6中任一项所述的方法,其特征在于,所述步骤2)中,对浸出液进行除铁具体为:向富集有镍铁钴的浸出液或调整pH为3~7的富集有镍铁钴的浸出液中通入富含氧气的气体,得到除铁后液和除铁渣;或,对富集有镍铁钴的浸出液加入到高压反应釜中与氧化性气体进行反应,反应完成后进行固液分离,将滤渣洗涤干燥后即为除铁渣,所得滤液为除铁后液。
- 根据权利要求1~6任一项所述的方法,其特征在于,所述除铁后液用于镍和钴的提取,具体为:将除铁后液pH调至4.0-5.5后,向除铁后液中加入萃取剂,萃取分离得到含钴溶液和含镍溶液,再将含镍溶液的pH调至5.5-7.0使用所述萃取剂进行镍的萃取;其中,所述萃取剂为P507的煤油溶液或Cyanex272的煤油溶液,体积分数为10-50%。
- 根据权利要求1所述的方法,其特征在于,所述铜和贵金属的回收方法具体为:将处理低冰镍所得富集有铜的浸出渣送转炉吹炼制得粗铜,再经电解分别得到精铜和富集贵金属的阳极泥,阳极泥用于提取贵金属;或,将处理低冰镍所得富集有铜的浸出渣经氧化焙烧后采用酸浸出,分别收集富集铜的浸出液和富集贵金属的浸出渣,浸出渣用于提取贵金属;或,将处理低冰镍所得富集有铜的浸出渣进行氧压浸出,分别收集富集铜的浸出液和富集贵金属的浸出渣,浸出渣用于提取贵金属。
- 一种实施权利要求1~10任一项所述方法的系统,包括:获取富集有镍铁钴的浸出液和富集有铜的浸出渣装置,为选择性浸出装置和水溶解装置;或者为常压选择性浸出装置:选择性浸出装置:具有低冰镍和浸出反应液各自的连续加料口,所述选择性浸出装置中含有反应底液,且使得向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液时发生选择性浸出反应;所述选择性浸出装置还包括硫化氢气体的收集装置、第一浸出液的收集装置和第一次浸出渣的收集装置,其中,所述反应底液为质量分数20%-60%的硫酸溶液,所述浸出反应液为质量分数60%-95%的硫酸溶液;水溶解装置,用于使用水溶解第一次浸出渣,分别收集第二浸出液和第二次浸出渣;常压选择性浸出装置,用于对低冰镍直接使用硫酸进行常压选择性浸出,分别收集硫化氢气体、浸出液和浸出渣;除铁装置,用于将水溶解装置中得到的第二次浸出液进行除铁,或用于将常压选择性浸出装置中得到的浸出液进行除铁;镍和钴的提取装置,用于收集除铁装置中除铁后液,用于镍和钴的提取;炼铁装置,用于处理除铁装置中的除铁渣,用于炼铁;和/或,铜冶炼装置,用于将所述第二浸出渣或常压选择性浸出装置中得到的浸出渣进行铜冶炼,分别得到铜和贵金属。
- 根据权利要求11所述的系统,其特征在于,还包括:硫磺制备装置,用于将造锍熔炼中产生的二氧化硫与所述常压选择性浸出装置中产生硫化氢气体反应制得硫磺;硫酸制备装置,用于将造锍熔炼中产生的部分二氧化硫转换成硫酸,并将其提供给所述常压选择性浸出装置;造锍熔炼装置,用于处理铜镍硫化矿,并向所述常压选择性浸出装置中提供低冰镍,所述低冰镍为铜镍硫化矿经造锍熔炼制得。
- 根据权利要求12所述的系统,其特征在于,所述常压选择性浸出装置中还包括温度调控装置,用于将所述常压选择性浸出的温度控制在25-80℃。
- 一种对铜镍硫化矿综合利用的方法,其特征在于,包括:1)对铜镍硫化矿经造锍熔炼得到的低冰镍直接使用硫酸进行常压选择性浸出,分别收集硫化氢气体、浸出液和浸出渣,其中,所述常压选择性浸出的温度为25-80℃;2)对步骤1)的浸出液进行除铁,分别收集除铁后液和除铁渣,所述除铁后液用于镍和钴的提取,所述除铁渣用于炼铁;和/或,对步骤1)的浸出渣送铜冶炼系统冶炼,分别得到铜和贵金属。
- 一种从铜镍硫化矿中回收主伴生元素的方法,其特征在于,包括:1)向反应底液中持续加入铜镍硫化矿经造锍熔炼得到的低冰镍和浸出反应液,选择性浸出,分别收集硫化氢气体、第一浸出液和第一次浸出渣,其中,所述反应底液为质量分数20%-60%的硫酸溶液,所述浸出反应液为质量分数60%-95%的硫酸溶液;2)向所述第一次浸出渣中加入水,溶解,分别收集第二浸出液和第二浸出渣;3)对所述第二浸出液进行除铁,分别收集除铁后液和除铁渣,所述除铁后液用于镍和钴的提取,所述除铁渣用于炼铁;和/或,将所述第二浸出渣送铜冶炼装置冶炼,分别得到铜和贵金属。
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