CN102859012A - Method of processing nickel bearing raw material - Google Patents
Method of processing nickel bearing raw material Download PDFInfo
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- CN102859012A CN102859012A CN2011800200873A CN201180020087A CN102859012A CN 102859012 A CN102859012 A CN 102859012A CN 2011800200873 A CN2011800200873 A CN 2011800200873A CN 201180020087 A CN201180020087 A CN 201180020087A CN 102859012 A CN102859012 A CN 102859012A
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- Prior art keywords
- nickel
- solution
- leaching
- chloride
- stage
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 238000000034 method Methods 0.000 title claims abstract description 126
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 123
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 238000012545 processing Methods 0.000 title claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 100
- 238000000638 solvent extraction Methods 0.000 claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000005363 electrowinning Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- 239000012141 concentrate Substances 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 30
- 238000000605 extraction Methods 0.000 claims description 27
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 22
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 22
- 229910052749 magnesium Inorganic materials 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 20
- 239000003978 infusion fluid Substances 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005272 metallurgy Methods 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229960003280 cupric chloride Drugs 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910021654 trace metal Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 239000005864 Sulphur Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000003570 air Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000009853 pyrometallurgy Methods 0.000 description 6
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic 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
- 125000004429 atom Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052953 millerite Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910052954 pentlandite Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- WXMBHSUHAJYVEA-UHFFFAOYSA-N [Na][Cl][Ni] Chemical compound [Na][Cl][Ni] WXMBHSUHAJYVEA-UHFFFAOYSA-N 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052898 antigorite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
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
- C22B3/20—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
- 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
- C22B23/0423—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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching 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
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A hydrometallurgical method of processing nickel containing raw material such is provided. The raw material is leached in chloride-based leaching media in a process integrated with chlorine-alkali electrolysis, solvent extraction and electrowinning process stages for producing metallic nickel. The solvent extraction stage comprises a nickel solvent extraction stage, where nickel is extracted from an aqueous solution containing high concentration of chloride. The electrolyte in the electrowinning stage is a sulphate containing aqueous liquid.
Description
Invention field
The present invention relates to process nickel-bearing raw material for example nickel sulfide concentrate or nickel sulfide ores be used for obtaining the Wet-process metallurgy method of metallic nickel, use based on muriatic leaching medium in the technique of wherein with solvent extraction and electrolytic metallurgy the treatment stage, integrating described raw material leached.The solvent extraction stage comprises the nickel solvent extraction stage, wherein from containing the extraction with aqueous solution nickel of high concentration chloride.
Background technology of the present invention
Nickel resources in the world is divided into main two classes, sulfide ore and oxidized ore (laterite).It then is the hydrometallurgical processes step that the exploitation of conventional nickel sulfide ores consists essentially of the fire metallurgy process step, and wherein ore at first carries out fine grainding, then by pneumatic flotation with nickelous sulfide mineral simmer down to nickel ore concentrate.Further process described concentrate to produce the nickeliferous impure metal of also containing copper, cobalt and iron by melting and reduction.Then by known Wet-process metallurgy method refining is carried out in the impure metal, method can comprise Oxidation Leaching or pressure leaching, then is to remove impurity and hydrogen reduction or electrolytic metallurgy.
The shortcoming of melting method is to produce sulfurous gas, and it has to process to generate sulfuric acid in the acid plant, and sulfurous gas is not easy to remove from the smelting furnace position usually.The loss of nickel and cobalt is significant in the smelting furnace slag, and for example magnesium and arsenic also are problems to process some trace (minor) element in the concentrate.
Lean ore brings challenges to concentration technology.The concentrate of poor quality is difficult to refining and refining cost height in the pyrometallurgy method.When the high and corresponding iron level of Mg content in this class concentrate was low, especially difficulty was processed in the pyrometallurgy of this concentrate.In this case, low other difficulty that causes thereby the iron in the concentrate/magnesium ratio becomes.For example when the MgO of the slag that produces content surpasses 11%, thereby rising so high to hinder, the viscosity of slag from stove, removes slag in fusion process.The part of nickel impure metal remains in the slag when viscosity raises.In the arid region, must use salt solution to carry out wet separation, in this case, concentrate contains halogenide harmful in pyrometallurgical processes.
A lot of hydrometallurgy approach for the treatment of nickel sulfide concentrate have been described in the literature.Generally speaking art methods comprises grinding or the fine grinding of concentrate, processes sulfide afterwards in oxidative pressure leaches, in order to be leaching process processing sulfuric acid.
The Activox method of for example describing in EP patent 1303641 comprises nickel ore concentrate is ground to form very thin abrasive substance, under high pressure carry out afterwards Oxidation Leaching, so that nickel is separated in the sulfate liquor, remove impurity by known method subsequently, metallic nickel is reclaimed.
The shortcoming of above-mentioned Wet-process metallurgy method is that the most of sulphur that will contain in the sulfide is oxidized to sulfuric acid, and this causes the high expense that caused by neutralization reagent, and produces the waste that must remove in a large number, for example ammonium sulfate and gypsum.Can estimate when these two kinds of factors in conjunction with the time cause high expense so that described method is commercially not too attractive.
WO patent application 96/41029 " Chloride assisted hydrometallurgicalextraction of nickel and cobalt from sulphide ores ", described that the oxidative pressure of nickel and cobalt sulfide ore leaches under the condition that oxygen exists, also described the Ore Leaching that contains halogenide, copper and sulfate ion.The solution that obtains is carried out solid separate and solution purification, nickel and the cobalt hydroxide of mixing precipitate, and throw out leaches again in ammonia solution, extract separating metal by solution afterwards, and reclaim metal by electrolytic deposition.The method has to above-mentioned based on the similar restriction of the Wet-process metallurgy method of vitriol.
United States Patent (USP) 3,880,653 have described from containing the nickel impure metal recovery metallic nickel of copper and precious metal.With the leaching of following current process implementation nickel impure metal, wherein the nickel impure metal at first obtained by nickel electrowinning deposition and contain in the cupprous chloride soln and suspend.Chloride soln leaches step, also is provided at the chlorine that produces in the electrolysis in this step.Oxychlorination monovalence copper, the copper of oxidation and then dissolving nickel revert back simultaneously the monovalence form and precipitate with the copper sulphided form.The sulphur that contains in the sulfide of dissolving precipitates with the elementary sulfur form.Precious metal keeps insoluble in leaching.After the first leaching step, the slurry of all batches carries out second step, and wherein the cupric of dissolving precipitates in nickel impure metal mode.Solution is separated with solid material, and solution carries out the nickel electrowinning deposition.
JP patent application 10-140257 has described by chlorine and has leached and electrolysis mode reclaims nickel from material for example contains the nickel impure metal of nickel, cobalt, copper and sulphur.In following current is leached, the nickel impure metal leached into and contain in the cupprous chloride soln, in this solution, provide chlorine with leaching nickel and other metal.When providing chlorine in the first step at leaching process, the sulphur that contains in the nickel impure metal also is partly dissolved and forms sulfuric acid in solution.In the final step of leaching process, no longer provide chlorine and air is provided, this means in the end in the step, leach by oxygen and the sulfuric acid that contains in the air.The solution that contains nickelous chloride is carried out electrolysis to reclaim metallic nickel, and the chlorine that produces in the electrolysis is used for leaching raw material.The recirculation solution that obtains from electrolysis also is used for leaching raw material.
In aforesaid method, rear two kinds of methods are processed and are at first processed the nickel impure metal that nickel ore concentrate is produced in the pyrometallurgy mode.The shortcoming that pyrometallurgy is processed is to produce during the course a large amount of sulfurous gas, and sulfurous gas need to further be processed into sulfuric acid usually.The use of sulfuric acid and commercial distribution are difficult, particularly when the smelting furnace place away from should use the place of sulfuric acid the time.
WO publication WO2007/039665 discloses a kind of by Containing Sulfur nickel raw material nickel sulfide concentrate or ore or the waste material method of producing the nickel product for example.In the method, under condition of normal pressure, described raw material is leached in the aqueous solution of sodium-chlor and cupric chloride (II).Produce needed chlorine, hydrogen and sodium hydroxide in the method in the chloro-alkali electrolyzer of in as total method, integrating the treatment stage.The iron that the rich infusion solution of rich nickel is dissolved and the precipitation of vitriol, and throw out entered in the final step of leaching process.Nickel is settled out from rich infusion solution with hydroxide nickel (OH) 2 forms by means of sodium hydroxide.
WO publication WO2007/039664 discloses a kind of method of the salvage material nickel from Containing Sulfur nickel, and the method may further comprise the steps: the material that Containing Sulfur nickel is provided; In oxidizing atmosphere, contain under the normal atmosphere of rich infusion solution of nickel of dissolving and the temperature with the Leaching of sodium chloride solution that contains cupric muriate and hydrochloric acid in formation the material of Containing Sulfur nickel is carried out Oxidation Leaching; Process the described rich infusion solution that contains the nickel of dissolving and turn back at least in part leaching stage (b) with the separation copper and with it; By come the described rich nickel infusion solution of purifying to remove cobalt, zinc and residual copper with solvent extraction; Reclaim nickel to form poor nickel infusion solution from described rich infusion solution; And in chloric alkali electrolysis, process the infusion solution of described dilution to reclaim chlorine, hydrogen and sodium hydroxide with electrolysis mode.WO2007/039664 does not mention the possibility that reclaims nickel after the nickel solvent extraction stage in electrolytic metallurgy from sulfate liquor.
It is known carrying out the cobalt solvent extraction from chloride environment, extracts cobalt-chloride complex thereby wherein use the negatively charged ion extraction agent to extract cobalt from very high chloride environment.The positively charged ion extraction agent that extracts cobalt for the sulfate liquor from chloride also is known.Chloride concentration is relatively low in known application.
Goal of the invention
The objective of the invention is the Wet-process metallurgy method that overcomes the shortcoming of art methods and new and favourable production nickel metal is provided.
The invention provides and wherein utilize advantage that normal pressure leaches and arrange the chemicals recirculation of leaching and the method for regeneration by the electrolysis of chloro-alkali.The method is particularly suitable for reclaiming metal from poor nickel ore concentrate and ore.The recirculation of reactant is so that the method is advantageous particularly in the method.
Special advantage of the present invention is that it provides the Wet-process metallurgy method that reclaims metallic nickel, and wherein metallic nickel obtains from stannous sulphate electrolyte on the negative electrode of electrolytic metallurgy groove.
In addition, the invention provides the method for processing and reclaiming the impurity of raw material.This class impurity is magnesium and halogenide for example, and when processing according to the present invention, they can obtain processing in the situation that does not hinder nickel to reclaim.
Summary of the invention
The present invention relates to by Containing Sulfur nickel raw material, for example nickel sulfide concentrate or ore or waste material are produced the method for nickel metal.
The method according to this invention can successfully be processed nickeliferous charging for example concentrate and the ore of nickel sulfide concentrate or ore or waste material, particularly poor nickel.Can process even inferior grade nickel charging (Ni＜1-10%) and can in the situation that does not hinder nickel to reclaim, process many impurity for example cobalt, iron, magnesium, zinc, copper and arsenic.Usually the raw material that contains nickelous sulfide always contains a certain amount of copper, iron, cobalt and magnesium.
The method according to this invention may further comprise the steps:
(a) provide the material of Containing Sulfur nickel;
(b) in leaching stage, under normal atmosphere, with chloride leaching solution the material of Containing Sulfur nickel is leached to form nickel and the certain density muriatic rich infusion solution that contains dissolving;
(c) extract the nickel that dissolves contains single nickel salt with generation electrolytic solution with solvent-extraction process from described infusion solution;
(d) reclaim nickel in the metallurgical stage of nickel electrowinning from described electrolytic solution;
(e) in chloro-alkali electrolysis stage, make from processing step c)-the chloride mill solution regeneration of d) dilution turns back in the method so that chlorine, hydrogen and sodium hydroxide are reclaimed.
In based on the muriatic aqueous solution, carry out the leaching of nickel raw material.The leaching step of carrying out in the leaching stage produces and contains the very muriatic process liquid of a large amount.In the trace metal removal stage, use the positively charged ion extraction agent with solvent-extraction process cobalt and other trace metal to be isolated from the unusual chloride soln of high-content.Residual solution that to remove the stage from trace metal (MM SX) is given and to be entered the nickel solvent extraction stage (Ni SX), in this stage from very high chloride soln optionally extract nickel and with its back extraction to the vitriol liquid to form nickel sulfate electrolyte.Make nickel electrolyte carry out the metallurgical stage of nickel electrowinning.The chloro-alkali electrolysis of a step from be integrated into described method obtains in leaching stage and other treatment step needed reactant for example chlorine, hydrogen and sodium hydroxide.
According to the method, preferably under condition of normal pressure, raw material is leached in the aqueous solution that contains sodium-chlor and cupric chloride (II).To deliver to the solvent extraction stage from the rich infusion solution (PLS) of leaching stage.The chloride content of PLS surpasses 100g/l.
According to one embodiment of the invention, the production method of nickel product may further comprise the steps:
A) under condition of normal pressure, by containing the solution of sodium-chlor and cupric chloride (II), nickel-bearing raw material is leached in two or more steps in the counterflow leaching mode, so that the first leaching step that ought observe at the concentrate direct of travel is non-oxidizable, following step is oxidisability, form the rich infusion solution (PLS) of the nickelous chloride of rich nickel-sodium-chlor and leaching resistates
B) the rich infusion solution of rich nickel carried out liquid purifying so that iron and the sulfate precipitation of dissolving are given the final step that enters leaching process with throw out,
C) in cobalt solvent extraction unit with the positively charged ion extraction agent with cobalt and other trace metal (for example zinc and copper) from containing very high muriatic liquid separation out.The residual solution of poor cobalt is delivered to nickel solvent extraction (Ni SX) unit,
D) the aqueous solution, reclaim cobalt and make its precipitation from cobalt solvent extraction unit,
E) in nickel solvent extraction unit, from cobalt solvent extraction residual solution, extract nickel with the positively charged ion extraction agent,
F) nickel sulfate electrolyte from the nickel solvent extraction stage is transported to the nickel electrowinning metallurgical equipment, wherein obtains nickel at negative electrode,
G) sodium chloride solution of poor nickel carried out magnesium precipitate, wherein by sodium hydroxide, make magnesium from described solution with magnesium hydroxide Mg (OH)
2The form precipitation,
H) from NaCl solution, remove the dissolved impurity resistates of other divalence by ion-exchange method,
I) NaCl solution is concentrated,
J) concentrated NaCl solution is carried out the electrolysis of chloro-alkali, wherein a part of solution becomes chlorine, hydrogen and sodium hydroxide as the reactant in this method by electrochemical machining,
K) give the last leaching step that enters concentrate and/or ore with the NaCl solution of dilution in the electrolysis.
Preferably, divide two steps to contain the leaching of concentrate and/or the ore of nickelous sulfide.
Leach in the step first, (II) leaches raw material under non-oxide condition by cupric chloride, so that the partial vulcanization thing that contains in concentrate dissolving, copper precipitates with the cupric sulfide form.In the non-oxide leaching step of raw material, pH is in the scope of 0.5-3.0.
In the Oxidation Leaching step of raw material, advantageously leach raw material with dissolved sulfide by cupric chloride (II), and be dissolved as cupric chloride (II) so that leach the cupric sulfide that precipitates in the step first.In the Oxidation Leaching step, pH is adjusted at the 1.7-2.8 scope, preferably in the 2.0-2.5 scope.
According to an embodiment of present method, the oxidising agent that uses in the Oxidation Leaching step of concentrate and/or ore is oxygen-containing gas, and it is oxygen, oxygen-rich air or air, and hydrochloric acid is entered in the leaching process.
According to another embodiment of present method, the oxidising agent that uses in the Oxidation Leaching step of concentrate and/or ore is the chlorine that forms in the electrolysis of chloro-alkali.
According to an embodiment of present method, in the rich infusion solution of rich nickel, add calcium cpd and vitriol and the iron of sodium hydroxide to remove dissolving.Iron/the gypsum precipitate that generates is carried out last leaching step.
Preferred embodiment according to present method, remove cobalt with positively charged ion solvent extraction reagent from rich infusion solution, the residual solution that to extract from cobalt is wherein extracted nickel and is produced the nickel solution based on vitriol that is suitable as nickel electrowinning metallurgy stage electrolytic solution with the organic extraction agent of positively charged ion to entering the nickel solvent extraction.Give from the nickel electrolyte of nickel solvent extraction equipment to enter the nickel electrowinning metallurgical equipment, wherein obtain nickel at negative electrode in a usual manner.
Depend on impurity level in the nickel electrolyte and the quality requirements of Ni EW electrolytic solution, can for example carry out being further purified of nickel electrolyte with ion exchange method, wherein a small amount of for example copper, cadmium, iron and zinc can be removed from the electrolytic solution that previous (advance) produces.
According to the preferred embodiment of the method, the NaCl solution of poor nickel, the poor nickeliferous residual solution from the nickel solvent extraction that namely become was carried out magnesium that Mg precipitate remove dissolving to it at electrolytic metallurgy before the stage.Advantageously under the condition of pH value 9-10, carry out the precipitation of magnesium.
The hydrochloric acid that is used as the leaching reagent of raw material is advantageously made by the hydrogen and the chlorine that produce in the electrolysis of chloro-alkali.
Nickel-bearing raw material can contain gold and/or other precious metal (PGM).In this case, gold in the end leaches in the step dissolving and reclaims from the solution of last leaching step; When the concentrate direct of travel is observed, the solution that does not contain gold is transported in formerly the leaching step.From leach resistates, reclaim other precious metal.
According to an embodiment of present method, a part of barren solution that will produce in the dense contracting of sodium-chlor is transported in the concentrate leaching process.
The accompanying drawing catalogue
Fig. 1 represents the indicative flowchart of a preferred embodiment of the present invention, and
Fig. 2 represents the illustrative diagram of another embodiment of the invention.
Detailed Description Of The Invention
In this article, the concept that contains the raw material of nickelous sulfide mainly refers to nickel sulfide concentrate or ore, but also can refer to type of waste or impure metal.For easy, only mention concentrate in the literary composition.Each leaching step typically is made of a series of several reactors, and wherein the suspension of solution and solid is sent to next reactor with overflow type from a reactor.Reactor is equipped with agitator.Between processing step, carry out multiviscosisty so that in counterflow leaching with solution and Solid Conveying and Melting to different step.Specification sheets of the present invention has been described two step leaching process, but can adopt several steps in case of necessity.The implication of condition of normal pressure refers at environmental stress with at 90 ℃-solution boiling point and namely operates under the temperature in about 110 ℃ of scopes.Alkali metal chloride can be sodium-chlor or Repone K.
The method according to this invention is described with reference to the accompanying drawings.
In two or more steps, contain the leaching of the raw material (nickel ore concentrate among Fig. 1 and 2) of nickelous sulfide with counterflow leaching 11,21.
In one embodiment of the invention, raw material given enter first and leach in the step, and with the chloride soln that uses in the leaching process and oxidising agent to entering in the second step.Leach in the step first, regularization condition is so that because cupric impact, the part of nickel that contains in the raw material and dissolved ferric iron, and the monovalence copper that generates in leaching process is precipitated with the cupric sulfide form.Do not leach to first and add oxygen in the step and other oxygenant comes dissolved copper, but the first condition that leaches step is non-oxidizable.Leach in pH value 0.5-3.0 scope, this depends on concentrate.Can illustrate by the Leaching reaction of pentlandite the principal reaction that in this step, occurs:
2(Ni,Fe)
9S
8+18CuCl
2→9NiCl
2+9FeCl
2+9Cu
2S↓+7S
0(1)
Reaction (1) can be described as permutoid reaction, and wherein cupric is reduced to monovalence, dissolves simultaneously the iron and the nickel that contain in the concentrate.Other nickel and iron mineral, for example violarite, millerite and pyrrhotite also dissolve according to same principle, and cupric sulfide and element sulphur are precipitated respectively.The magnesium that contains in the nickel raw material is dissolved, thereby forms magnesium chloride.
The copper that contains in the raw material does not dissolve under the condition of the first leaching step, but only dissolves in second step, if when perhaps having several leaching step, only in the end dissolves in the step.If the copper content in the raw material is not enough to satisfy effectively and leaches, in some suitable modes more copper is introduced leaching process so, for example with copper ore concentrates or copper sulfate form.Advantageously, the copper content in the solution is the 5-50g/l order of magnitude.Suitable by in the above described manner condition being adjusted, copper nearly all in first step precipitates with sulphided form, and carries out next with throw out and leach step.Advantageously present method does not need independent settling step with separating copper from rich nickel solution, but precipitates with the leaching of nickel.If the amount of the copper that contains in the concentrate so can be to be fit to the mode remove portion copper of this purpose more than amount required in the leaching process.
From leaching step 11, the 21 rich nickel Cl that obtain
2-NaCl solution is PLS, contains iron and the vitriol of a certain amount of dissolving.In solution purification step 22, carry out the removal of iron and vitriol.Advantageously pass through calcium cpd for example Wingdale or other calcium cpd precipitated sulfur hydrochlorate, so that when calculating with sulphur, the sulphur content that leaves in the solution is 2g/l at the most.For iron being oxidized to the trivalent form, advantageously alkali lye (NaOH) is joined in the solution, in this case, iron is settled out from solution.The throw out foldback can be got back to the final step of concentrate leaching process, therefrom iron precipitate and gypsum are removed with the leaching resistates.
If the copper content of nickel ore concentrate is higher than required copper content in the leaching process, still contain cupric in the NaCl solution of so rich nickel.Can in independent copper recycling step, remove copper, this copper recycling step advantageously according to cobalt solvent extraction 12 of the present invention, 23 or trace metal remove 23.
The solvent extraction of trace metal (MM SX)
To join from the feedstock solution of solution purification phase in the solvent extraction process 12,23 (MM SX) of trace metal.In MM SX process, in very high chloride environment, extract trace impurity metal such as Co, Cu, Zn and Mn with the positively charged ion extraction agent from feedstock solution.Use a plurality of extraction stages.
Before the extraction stage, if need then independent organism can be installed and/or dregs (crud) are removed loop (circuit).Can carry out at mixing tank-settling vessel or in organic tank the combination that pH controls (pre-neutralization) or can use these neutralized systems.
Can wash (impurity atom removal) or eccysis (physical impurity removal) from organism nickel, muriate or some other impurity compositions to remove carrier band of the carrier band in the stage of extraction.For need to determining by the charging quality of going to MM SX process with from the required product quality of MMSX process of washing and/or eccysis stage.Can use one or more eccysis/washing stages.
To give from the organism of extraction or washing and/or the carrier band in eccysis stage and enter strip stages, wherein with acidic solution with metal from the organic phase back extraction to water.Can be from organic phase back extraction metal in one or more solution.Wherein produce the selectivity back extraction of two or more stripping workshops, normally preferred solution, this is because the selectivity back extraction has improved back extraction liquid quality.Yet, also can after MM SX process, for example be separated as carbonate, oxyhydroxide or sulfide with the selective precipitation process from the metal of single stripping workshop.Can use one or more strip stages.
The nickel solvent extraction
To be that MM SX residual solution is pumped into nickel solvent extraction process 13,24 from nickel solvent extraction (Ni SX) feedstock solution of MM SX process.Being entered Ni SX before the extraction stage from the solution of MM SX, must between MM SX and Ni SX, settle some organic entrainments (entrainment) to remove technology and equipment.This equipment generally includes thinner washing, settling vessel afterwards, carbon filter and storage tank.Can use all or any combination of this equipment.
After organic matter removal, give the nickel solvent extraction stage that enters with Ni SX feedstock solution.In the nickel solvent extraction, in very high chloride environment, with the positively charged ion extraction agent nickel is optionally extracted from described incoming flow.Can use a plurality of extraction stages.Can carry out at mixing tank-settling vessel or in organic tank the combination that pH controls (pre-neutralization) or can use these neutralized systems.
Can be with the impurity of carrier band such as muriate, magnesium and calcium from organism washing (impurity atom removal) or eccysis (physical impurity removal) from the carrier band in the stage of extraction.Can use one or more washings and/or eccysis stage.
To give from the organism of washing and/or the carrier band in eccysis stage and enter strip stages, wherein with acidic solution with nickel from the organic phase back extraction to water.The back extraction liquid that produces is previous electrolytic solution, as metallurgical (Ni EW) process 13 of nickel electrowinning, 26 feedstock solution.Employed acid can be sulfuric acid or hydrochloric acid.Usually in this stage, be converted into that vitriol is processed mutually and therefore use sulfuric acid to be used for back extraction based on muriatic processing.
Depend on impurity level in the previous electrolytic solution and the quality requirements of Ni EW electrolytic solution, can for example carry out being further purified of previous electrolytic solution with ion exchange method, wherein a small amount of for example copper, cadmium, iron and zinc can be removed from the electrolytic solution of previous generation.
The removal of magnesium
Magnesium is the objectionable impurities in the nickel electrowinning metallurgy 13,26.Magnesium is removed from nickel electrolyte in the removal stage 14,25 at magnesium.By make the product pH that obtains from the nickel solvent extraction be elevated to about 9 with alkali lye magnesium gone out (processing step 25 Fig. 2) from this solution precipitation, so that Mg is with magnesium hydroxide form precipitation, it also is commerical prod.
Usually the magnesium amount is maximum, according to the final solution purifying of Mg amount for example the scale of ion-exchange (dimensioning) become quite expensive.A kind of favorable method according to the present invention is by using the sodium hydroxide NaOH as precipitation reagent that forms in chloro-alkali electrolysis 8 to remove magnesium in Mg settling step 5 from solution.PH value of solution is elevated in the 9-10 scope, and in this case, Mg is with magnesium hydroxide Mg (OH)
2The form precipitation.Multiviscosisty is carried out in precipitation of hydroxide, and advantageously the underflow with multiviscosisty is recycled to settling step to improve the quality of precipitation.When reclaiming with independent magnesium when finishing hydrometallurgical process, might process detrimentally high concentrate for the concentrate pyrometallurgy to magnesium amount wherein and process.
When other impurity that leaves in the solution of removing at magnesium after 14,25 when for example the amount of zinc and nickel is the mg/litre order of magnitude, the favorable method of removing them is ion-exchange (brine purification 28 among Fig. 2).Preferably carry out ion-exchange by chelating ion exchange resin.Ion-exchange plays a role according to known technology, so that remove the impurity that is combined in the resin by hydrochloric acid, and make resin regeneration with NaOH solution.Therefore, advantageously obtain required reactant the ion-exchange from the chloro-alkali electrolysis of the part of forming process.
Can be 150-240g/L from the NaCl content of brine treatment 14, the 28 NaCl solution that obtain, the preferred 200g/L order of magnitude.Yet for the electrolysis of chloro-alkali, the NaCl content in the solution that is necessary to raise is until 160-300g/L, the preferred 280-300g/L order of magnitude.Increase content in some modes that are fit to, for example in evaporation step, pass through vacuum-evaporator or leach vaporizer.When in case of necessity, the useless NaCl solution that generates can be used for the leaching process (not shown) of concentrate in evaporation step.
Purifying and concentrated sodium chloride solution are carried out chloro- alkali electrolysis 14,29 with needed chlorine, hydrogen and sodium hydroxide in the different step that is created in the nickel production process.The electrolysis of chloro-alkali plays a role in known manner.The NaCl salt brine solution flows to anode one side in electrolysis, and electric current decomposes it at the anode place, thereby forms chlorine.Sodium ion at negative electrode place Current Decomposition water generates hydrogen, thereby forms sodium hydroxide by placing film between anode and negative electrode to negative electrode one side.The NaCl solution that carries out electrolysis consumes in electrolysis, and produces in proportion gas and alkali lye thus.The NaCl content of the solution that shifts out from electrolysis is 150-240g/L, and the preferred 200g/L order of magnitude is got back to the raw material leaching process with its recirculation.
Advocate that as above the sodium hydroxide that forms is used for the precipitation of magnesium hydroxide at least in chloro-alkali electrolysis 14,29.Also need sodium hydroxide in ion exchange regenerant, when in case of necessity, it also can be used for removing vitriol.
The favorable method that leaches nickel-bearing raw material is to provide oxygen to last leaching step, and by providing therein hydrochloric acid to regulate leaching condition according to reaction 3.Advantageously, required hydrochloric acid is made by the hydrogen that produces in the electrolysis of hydrochloric acid production process and chlorine.
Embodiment 1
Nickeliferous charging (for example nickel sulfide concentrate or ore or mainly contain nickel sulfide and Lumpy concentrate, waste material or the impure metal of copper sulfide) is leached in containing the sodium chloride solution of bivalent cupric ion (50-200g/l NaCl).Leach in the stage at two or more counterflow leachings.The first leaching stage operates under non-oxide condition, and follow-up phase operates under oxidizing condition.
In the fs, charging is mixed with mill solution from the second leaching stage.According to reaction (1) leaching nickel sulfide.
2(Ni,Fe)
9S
8+18CuCl
2→9NiCl
2+9FeCl
2+9Cu
2S↓+7S
0(1)
Nickel and iron transfer in the solution and copper with solid phase precipitation.The sulphur of sulfide mainly is converted into elemental sulfur.In the solid-liquid separating step, process the slurry from the first leaching stage.Solid transfer to subsequently Oxidation Leaching stage and liquid reclaims as PLS, is sent to solution purification stage.Temperature in the first leaching stage and pH are respectively 80-110 ℃ and 0.5-3.0.
To further leach in the stage from the solid of the first leaching stage and from the mixed Oxidation Leaching that is incorporated in of the effluent brine of chloric alkali electrolysis.For example oxygen, air, oxygen-rich air or chlorine carry out Oxidation Leaching with hydrochloric acid and oxidizing gas.The cupric sulfide that consequently precipitates in the first leaching stage is leached.Copper is discharged in the solution with the bivalent cupric ion form, itself so that in leaching according to the reaction nickel sulfide of (2) and iron sulfide, be consumed.
2(Ni,Fe)
9S
8+36CuCl
2→9NiCl
2+9FeCl
2+36CuCl+16S
0(2)
Sulphur in the metallic sulfide mainly is converted into elemental sulfur again.
The cupric chloride (I) that produces in the reaction (2) reoxidizes according to reaction (3) and gets back to cupric chloride (II).
4CuCl+O
2+4HCl→4CuCl
2+2H
2O (3)
The hydrochloric acid that uses in the leaching is produced by chloric alkali electrolysis.
In the second leaching stage, the iron of leaching is oxidized and with the form of ferriferous oxide or oxyhydroxide precipitation.In reaction (4) and (5), shown as an example the iron oxidation and as the precipitation of pyrrhosiderite.
FeCl
2+2CuCl
2→FeCl
3+CuCl (4)
FeCl
3+2H
2O→FeOOH↓+3HCl (5)
After stage, solid-liquid mixtures is carried out the solid-liquid separating step at Oxidation Leaching, wherein iron and sulphur resistates are isolated from solution containing nickel.Resistates is delivered to mine tailing equipment.Can implement other resistates immobilization (stabilisation) step.To move on to from the liquid rotating of solid-liquid separating step the leaching stage of front.
If in charging, there is gold, then Oxidation Leaching in the stage with its leaching and recovery.
Iron and sulphur (as vitriol) during leaching process, have also been leached.In solution purification, remove de-iron and vitriol.In PLS, inject oxidizing gas (O
2, air, oxygen-rich air, chlorine) with the iron oxidation and with the pH of sodium hydroxide and/or calcium carbonate/calcium hydroxide regulator solution with iron as iron hydroxide and sulphur as gypsum deposition.The Oxidation Leaching stage is isolated and be recycled to the gained solid from PLS.The PLS that processes is transferred in the cobalt solvent extraction.
Embodiment 2
The method according to this invention leaches nickel sulfide concentrate.The major portion of the nickel that contains in the concentrate is with the combination of pentlandite form.Other essential mineral is antigorite, millerite and pyrrhotite.The chemical analysis of concentrate is:
Leach step 1
In solution (2500ml) nickel ore concentrate (690g) is leached, its initial content is:
Do not use oxygenant in leaching, the pH value of solution is 2-3 during leaching process.Copper from solution with copper glance Cu
2S form precipitation, simultaneously dissolved ferric iron.After leaching three hours under 95 ℃ the temperature, acquisition solution (leach product solution, PLS), its composition is:
After three hours, the solid composition is:
Leach step 2
Solid namely from the leaching resistates of the first leaching step, is containing 130g/l NaCl and 12g/l Cu
2+Solution in carry out Oxidation Leaching.Oxygen gas-supplying and hydrochloric acid in leaching process are so that the sulfide oxidation.The pH value remains in the scope of 2.0-2.5.Leaching process continues 8 hours, and the composition of solution and solid is afterwards:
Solution
Solid
The overall yield of the solution that is calculated by iron balance is (leach step 1+ and leach step 2):
Nickel 98.2%
Cobalt 97.2%
Claims (10)
- One kind by nickel-bearing raw material for example nickel sulfide concentrate or ore or waste material produce the Wet-process metallurgy method of metallic nickel, the method may further comprise the steps:(a) provide the material of Containing Sulfur nickel;(b) in leaching stage, under normal atmosphere, with chloride leaching solution the material of Containing Sulfur nickel is leached to form nickel and the certain density muriatic rich infusion solution that contains dissolving;(c) extract the nickel that dissolves contains single nickel salt with generation electrolytic solution with solvent-extraction process from described infusion solution;(d) reclaim nickel in the metallurgical stage of nickel electrowinning from described electrolytic solution;(e) in chloro-alkali electrolysis stage, make from processing step c)-the chloride mill solution regeneration of d) dilution turns back in the method so that chlorine, hydrogen and sodium hydroxide are reclaimed.
- 2. according to claim 1 method is characterized in that from leaching step b) infusion solution contain muriate greater than the dissolving of 100g/l.
- 3. according to claim 1 and 2 method is characterized in that containing the rich infusion solution (PLS) of nickelous chloride and the leaching resistates that in the aqueous solution of sodium-chlor and cupric chloride (II) nickel-containing material are leached to form rich nickel under condition of normal pressure.
- 4. according to claim 1 method is characterized in that from step b) the rich infusion solution of rich nickel leach so that the iron that dissolves and sulfate precipitation.
- 5. according to claim 1 method, it is characterized in that will be from step b) liquid supply in the solvent extraction process, wherein use the positively charged ion organic reagent with trace metal under very high chloride concentration, for example cobalt, copper, zinc and manganese are removed and are then carried out processing step c from this solution).
- 6. according to claim 1 method is characterized in that at nickel solvent extraction step c) in the positively charged ion extraction agent with nickel from solution extract and with its back extraction to sulfate liquor.
- 7. according to claim 1 method is characterized in that and will go to step e) the feed purification of chloro-alkali groove become not contain magnesium.
- 8. according to claim 1 method is characterized in that by ion-exchange the dissolved impurity resistates of other divalence being removed from the charging of chloro-alkali groove.
- 9. according to claim 1 method is characterized in that leaching in the step first, by cupric chloride (II) raw material is leached under non-oxide condition, so that a part of sulfide of this raw material dissolves, and copper is precipitated with the cupric sulfide form.
- 10. according to claim 9 method is characterized in that pH value in the non-oxide leaching step is in the scope of 0.5-3.0.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20100121A FI122188B (en) | 2010-03-18 | 2010-03-18 | Hydrometallurgical process for the production of metallic nickel |
| FI20100121 | 2010-03-18 | ||
| PCT/FI2011/050222 WO2011114000A1 (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
Publications (2)
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| CN102859012A true CN102859012A (en) | 2013-01-02 |
| CN102859012B CN102859012B (en) | 2015-11-25 |
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| CN201180020087.3A Expired - Fee Related CN102859012B (en) | 2010-03-18 | 2011-03-16 | The method of process nickel-bearing raw material |
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| EP (1) | EP2547802A4 (en) |
| CN (1) | CN102859012B (en) |
| AP (1) | AP3220A (en) |
| AU (1) | AU2011228956B2 (en) |
| BR (1) | BR112012023479A2 (en) |
| CA (1) | CA2792401C (en) |
| EA (1) | EA020759B1 (en) |
| FI (1) | FI122188B (en) |
| WO (1) | WO2011114000A1 (en) |
| ZA (1) | ZA201206935B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109321746A (en) * | 2018-12-03 | 2019-02-12 | 北京矿冶科技集团有限公司 | A method of nickel is extracted by copper nickel Whote-wet method |
| CN111867980A (en) * | 2017-11-22 | 2020-10-30 | 内玛斯卡锂业有限公司 | Process for the preparation of hydroxides and oxides of various metals and their derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT2855735T (en) | 2012-05-30 | 2018-06-14 | Nemaska Lithium Inc | Processes for preparing lithium carbonate |
| FI125216B (en) | 2013-05-23 | 2015-07-15 | Outotec Finland Oy | Process for the recovery of metals |
| US10144990B2 (en) | 2013-10-23 | 2018-12-04 | Nemaska Lithium Inc. | Processes and systems for preparing lithium carbonate |
| AU2013263848B2 (en) * | 2013-11-29 | 2016-02-18 | Lifezone Limited | Treatment process for extraction of metals from ores |
| DK3110988T3 (en) | 2014-02-24 | 2019-07-29 | Nemaska Lithium Inc | METHODS FOR TREATING LITHIUM-CONTAINING MATERIALS |
| US12275650B2 (en) | 2019-05-22 | 2025-04-15 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
| WO2021105215A1 (en) * | 2019-11-28 | 2021-06-03 | Scanacon Ab | Metal recovery method |
| PE20231629A1 (en) * | 2020-11-26 | 2023-10-11 | Negative Emissions Mat Inc | INTEGRATION OF CARBON SEQUESTRATION WITH THE SELECTIVE HYDROMETALLURGICAL RECOVERY OF METALLIC VALUES |
| JP2024542277A (en) * | 2021-11-30 | 2024-11-13 | ユミコア | Selective leaching |
| CN114212806B (en) * | 2022-01-18 | 2023-08-18 | 贵州红星电子材料有限公司 | Recovery method of nickel-cobalt-manganese sulfide slag |
| WO2023213919A1 (en) | 2022-05-05 | 2023-11-09 | Umicore | Process for the oxidative leaching of a metal |
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- 2010-03-18 FI FI20100121A patent/FI122188B/en not_active IP Right Cessation
-
2011
- 2011-03-16 EA EA201290869A patent/EA020759B1/en not_active IP Right Cessation
- 2011-03-16 CA CA2792401A patent/CA2792401C/en not_active Expired - Fee Related
- 2011-03-16 AU AU2011228956A patent/AU2011228956B2/en not_active Ceased
- 2011-03-16 EP EP11755747.0A patent/EP2547802A4/en not_active Withdrawn
- 2011-03-16 WO PCT/FI2011/050222 patent/WO2011114000A1/en active Application Filing
- 2011-03-16 BR BR112012023479A patent/BR112012023479A2/en not_active IP Right Cessation
- 2011-03-16 CN CN201180020087.3A patent/CN102859012B/en not_active Expired - Fee Related
- 2011-03-16 AP AP2012006513A patent/AP3220A/en active
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2012
- 2012-09-14 ZA ZA2012/06935A patent/ZA201206935B/en unknown
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| CN1131199A (en) * | 1994-11-15 | 1996-09-18 | 奥托孔普工程承包商公司 | Method for leaching nickel-copper matte |
| CN1186524A (en) * | 1995-06-07 | 1998-07-01 | 康明柯工程服务有限公司 | Chloride assisted hydrometallurgical extraction of nickel and cobalt from sulfide minerals |
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| CN111867980A (en) * | 2017-11-22 | 2020-10-30 | 内玛斯卡锂业有限公司 | Process for the preparation of hydroxides and oxides of various metals and their derivatives |
| CN111867980B (en) * | 2017-11-22 | 2021-10-01 | 内玛斯卡锂业有限公司 | Process for the preparation of hydroxides and oxides of various metals and their derivatives |
| CN109321746A (en) * | 2018-12-03 | 2019-02-12 | 北京矿冶科技集团有限公司 | A method of nickel is extracted by copper nickel Whote-wet method |
Also Published As
| Publication number | Publication date |
|---|---|
| EA201290869A1 (en) | 2013-05-30 |
| AP3220A (en) | 2015-04-30 |
| AU2011228956A1 (en) | 2012-11-08 |
| WO2011114000A1 (en) | 2011-09-22 |
| EP2547802A4 (en) | 2016-07-13 |
| EP2547802A1 (en) | 2013-01-23 |
| CN102859012B (en) | 2015-11-25 |
| CA2792401A1 (en) | 2011-09-22 |
| BR112012023479A2 (en) | 2016-05-24 |
| AP2012006513A0 (en) | 2012-10-31 |
| EA020759B1 (en) | 2015-01-30 |
| FI20100121A0 (en) | 2010-03-18 |
| FI122188B (en) | 2011-09-30 |
| CA2792401C (en) | 2015-08-18 |
| AU2011228956B2 (en) | 2013-11-21 |
| ZA201206935B (en) | 2013-05-29 |
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