EP4337802A1 - Production of high purity nickel and cobalt compounds - Google Patents
Production of high purity nickel and cobalt compoundsInfo
- Publication number
- EP4337802A1 EP4337802A1 EP22806133.9A EP22806133A EP4337802A1 EP 4337802 A1 EP4337802 A1 EP 4337802A1 EP 22806133 A EP22806133 A EP 22806133A EP 4337802 A1 EP4337802 A1 EP 4337802A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- cobalt
- purified
- aqueous phase
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 620
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 302
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 150000001869 cobalt compounds Chemical class 0.000 title description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 272
- 229910017052 cobalt Chemical group 0.000 claims abstract description 269
- 239000010941 cobalt Chemical group 0.000 claims abstract description 269
- 238000000034 method Methods 0.000 claims abstract description 193
- 230000008569 process Effects 0.000 claims abstract description 179
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000000243 solution Substances 0.000 claims abstract description 88
- 229910052935 jarosite Inorganic materials 0.000 claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 claims abstract description 56
- 150000001768 cations Chemical class 0.000 claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000004411 aluminium Substances 0.000 claims abstract description 48
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims abstract description 48
- 239000012527 feed solution Substances 0.000 claims abstract description 47
- 229910052934 alunite Inorganic materials 0.000 claims abstract description 46
- 239000010424 alunite Substances 0.000 claims abstract description 46
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000000746 purification Methods 0.000 claims abstract description 36
- 150000001868 cobalt Chemical class 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims description 121
- 238000000638 solvent extraction Methods 0.000 claims description 115
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 113
- 229910052749 magnesium Inorganic materials 0.000 claims description 113
- 239000008346 aqueous phase Substances 0.000 claims description 105
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 98
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 82
- 239000012074 organic phase Substances 0.000 claims description 78
- 239000012535 impurity Substances 0.000 claims description 67
- 239000002253 acid Substances 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000000605 extraction Methods 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- 238000006386 neutralization reaction Methods 0.000 claims description 55
- 239000010949 copper Substances 0.000 claims description 53
- 239000011575 calcium Substances 0.000 claims description 52
- 229910052802 copper Inorganic materials 0.000 claims description 52
- 238000005201 scrubbing Methods 0.000 claims description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 49
- 239000011701 zinc Substances 0.000 claims description 46
- 239000011572 manganese Substances 0.000 claims description 45
- 229910052725 zinc Inorganic materials 0.000 claims description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 42
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 39
- 229910052791 calcium Inorganic materials 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 36
- 229910021529 ammonia Inorganic materials 0.000 claims description 35
- 229910052748 manganese Inorganic materials 0.000 claims description 35
- 230000001590 oxidative effect Effects 0.000 claims description 35
- 239000003153 chemical reaction reagent Substances 0.000 claims description 34
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 239000007800 oxidant agent Substances 0.000 claims description 27
- 239000001117 sulphuric acid Substances 0.000 claims description 26
- 235000011149 sulphuric acid Nutrition 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 239000000908 ammonium hydroxide Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 238000005342 ion exchange Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 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 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- 239000011133 lead Substances 0.000 claims description 18
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 16
- 239000003085 diluting agent Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 14
- 150000004679 hydroxides Chemical class 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 13
- -1 ammonium ions Chemical class 0.000 claims description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- 239000001166 ammonium sulphate Substances 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 claims description 2
- 208000032843 Hemorrhage Diseases 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 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 2
- 208000034158 bleeding Diseases 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 238000001556 precipitation Methods 0.000 description 56
- 238000000926 separation method Methods 0.000 description 44
- 229910001415 sodium ion Inorganic materials 0.000 description 31
- 238000002386 leaching Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 229910001710 laterite Inorganic materials 0.000 description 26
- 239000011504 laterite Substances 0.000 description 26
- 238000002425 crystallisation Methods 0.000 description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 238000007670 refining Methods 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- 235000015424 sodium Nutrition 0.000 description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 17
- 238000009826 distribution Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 13
- 238000010586 diagram Methods 0.000 description 13
- 238000004064 recycling Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 150000001340 alkali metals Chemical class 0.000 description 9
- 235000012245 magnesium oxide Nutrition 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 9
- 239000013067 intermediate product Substances 0.000 description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- 238000013459 approach Methods 0.000 description 7
- 229910052598 goethite Inorganic materials 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 229960005191 ferric oxide Drugs 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 5
- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KXZQYLBVMZGIKC-UHFFFAOYSA-N 1-pyridin-2-yl-n-(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CNCC1=CC=CC=N1 KXZQYLBVMZGIKC-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical class [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- CNJLMVZFWLNOEP-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[4.1.0]heptan-5-one Chemical class O=C1C(C)CCC2C(C)(C)C12 CNJLMVZFWLNOEP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DOIXGGGORNAJAT-UHFFFAOYSA-M [NH4+].[Ni+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Ni+].[O-]S([O-])(=O)=O DOIXGGGORNAJAT-UHFFFAOYSA-M 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- FWABRVJYGBOLEM-UHFFFAOYSA-N diazanium;azane;carbonate Chemical compound N.[NH4+].[NH4+].[O-]C([O-])=O FWABRVJYGBOLEM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- 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
- C22B23/0453—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
- C22B3/20—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
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- 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
-
- 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
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
- C01C1/028—Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Definitions
- the present disclosure relates to processes for obtaining high purity nickel and cobalt compounds from crude nickel and cobalt containing materials.
- Nickel sulphate and cobalt sulphate are important precursors in the formation of lithium battery cathodes which are typically formed of nickel-cobalt-manganese (NCM) and nickel- cobalt-aluminium (NCA).
- NCM nickel-cobalt-manganese
- NCA nickel- cobalt-aluminium
- NiS0 4 .6H 2 0 nickel sulphate hexahydrate having low levels of trace elements such as Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Na, Pb, Si, and Zn is shown in Table
- nickel sulphide has been an important starting material used in the production of battery grade nickel sulphate but as nickel sulphide deposits are being continually depleted, low grade nickel laterite deposits (accounting for 73% of world nickel resources) are becoming an increasingly important source of both nickel and cobalt for the battery industry.
- the profitable processing of these low-grade laterite ores to produce high purity, battery grade nickel sulphate and cobalt sulphate has been elusive.
- the existing refining processes for producing high purity, battery grade nickel sulphate and cobalt sulphate either require a costly step of physically extracting the major metal (i.e.
- nickel by solvent extraction (SX) from relatively small amounts of relevant impurities (typically, at a mass ratio of impurities to nickel ⁇ 1/15), or can only produce nickel liquors suited for producing other forms of nickel products, typically nickel cathode by electrowinning or nickel powder by hydrogen reduction. These forms of nickel products in turn need further refining processes to produce high purity, battery grade nickel sulphate.
- SX solvent extraction
- Nickel laterite ores are typically processed by direct acid leaching, followed by precipitation of major iron and aluminium impurities in the pregnant leach solution (PLS) by neutralisation or thermal hydrolysis.
- the nickel and cobalt are then usually recovered as intermediate products, either mixed sulphide precipitate (MSP), or mixed hydroxide precipitate (MHP) using a base chemical such as magnesia, lime, limestone or sodium hydroxide.
- MSP mixed sulphide precipitate
- MHP mixed hydroxide precipitate
- the MHP process is becoming increasingly popular because it eliminates the costly and undesirable H 2 S precipitation step associated with the MSP process, and it yields a product that is readily soluble in ammonia or acid which assists in the purification and recovery processes. Since the specifications for battery grade nickel sulphate and cobalt sulphate require very low levels of 4 impurities, the methods for separation and purification of these from the PLS formed via the dissolution of raw materials such as MHP are critical.
- a typical alkaline leaching process is the modified Caron process that uses ammonia- ammonium carbonate lixiviant and was previously employed at the Queensland Nickel Industries (QNI), and nickel and cobalt refinery at Cawse Nickel Operations (Fittock, 1992; Fittock et al., 1994; Price and Reid, 1987).
- the refinery sections of these plants re -leached MHP with ammonia under mildly reducing conditions, followed by solvent extraction with LIX® 84 ketoxime to isolate nickel (Virnig et al., 1997). This was precipitated from solution as the carbonate and calcined to nickel oxide, which was further processed into a range of products, such as nickel metal produced by hydrogen reduction.
- Cobalt was recovered from the nickel -depleted raffinate by precipitation of cobalt sulphide using sodium hydrosulphide. The cobalt product could be further treated to produce high purity cobalt products.
- HPAL high pressure acid leaching
- a problem with existing processes is that they are either unable to produce a qualified nickel liquor and/or cobalt liquor for direct crystallisation of high purity, battery grade nickel sulphate and/or cobalt sulphate, or the processes involve a costly step for extraction and separation of the major metal nickel from relatively small amounts of impurities in the PLS.
- MHP if sodium hydroxide or ammonium hydroxide is employed for neutralisation and precipitation of the MHP.
- An MHP after precipitation may be washed to remove partially soluble species.
- the washing of MHP is involved in the process as a step to remove or partially remove magnesium, calcium, sulphate, chloride, and sodium components from the MHP, but this is all for generally reduced level of soluble impurities in the leach liquor to meet the requirement for integration into the existing ammonia pressure leach processes to produce respective cobalt powder and nickel powder by pressure reduction with hydrogen.
- Solvent extraction with an organophosphinic acid is typically required for separation of cobalt from nickel, wherein a base reagent, typically sodium hydroxide and ammonia / ammonium hydroxide, is required for neutralisation of the equivalent amount of acid produced or for pH control during the SX process.
- a base reagent typically sodium hydroxide and ammonia / ammonium hydroxide
- the alkali metal ions and ammonium ions end up with nickel in the raffinate, together with some alkaline earth meals such as calcium and magnesium, resulting in contamination through the formation of double sulphate salts involving these impurities if the raffinate is directly used for the crystallisation of nickel sulphate.
- a problem in SX with a direct addition of ammonia to the concentrated nickel sulphate solution is the formation of nickel ammonium sulphate double salts. Attempts have been made in the prior art to deal with this problem by pre-neutralisation of the organophosphoric acid extractant and/or by preloading the organic phase with nickel.
- the present disclosure arises from the inventors’ research into processes for converting nickel / cobalt mixed hydroxide intermediates, such as MHP or other nickel bearing materials or solutions to high purity, battery grade nickel sulphate and cobalt sulphate.
- the processes described herein can generally be carried out in two phases.
- nickel laterite ores, other nickel bearing materials, intermediate products such as MHP or nickel bearing solutions are converted to a feed solution which is substantially free of alkali metal and monovalent cation species and is suitable for further purification processes to produce high purity, battery grade nickel sulphate.
- This first phase may involve improving existing upstream processing of nickel laterite ores or other nickel containing materials for efficient production of feed solution or MHP suitable for subsequent refining processes.
- a portion, or preferably a major portion, of manganese may be converted into stable Mn(III/IV) oxide in the MHP or in the leach slurry which is then separated to produce the feed solution with reduced manganese content for easy purification to produce high purity, battery grade nickel sulphate.
- a process for separating nickel and/or cobalt salts from crude nickel and/or cobalt bearing materials comprising: a) treating a crude nickel and/or cobalt bearing material with a salt of iron or aluminium under conditions to remove at least some of one or more alkali metal ion and/or monovalent cation species as a jarosite/alunite precipitate to provide a solution having a reduced content of one or more alkali metal ion and/or monovalent cation species; 7 b) subjecting the solution from step a) to increasing pH in a stepwise manner under conditions to provide a feed solution for further purification to produce nickel and/or cobalt salts suitable for the production of battery grade nickel or cobalt salts; wherein step b) removes at least some or any combination of any one or more of the following species: i. iron, ii. aluminium, iii. chromium, and iv. copper.
- the process of the first aspect further comprises treating a crude nickel and/or cobalt bearing material prior to step a) with an aqueous solution comprising water and/or sulfuric acid under conditions to remove at least some of the one or more alkali metal ion and/or monovalent cation species.
- the step of treating the crude nickel and/or cobalt bearing material with an aqueous solution comprising water and/or sulfuric acid may be carried out at pH 7 or greater.
- the feed solution is treated with an oxidant under conditions to oxidise any iron(II) to iron(III) and any manganese(II) to higher oxidation state manganese(IH/IV) to provide a feed solution containing nickel and/or cobalt and having reduced concentrations of any one or more of alkali metal ions, monovalent cation species, iron, aluminium, chromium, copper and manganese relative to the crude nickel and/or cobalt bearing material.
- the salt of iron or aluminium in step a) is a sulphate, carbonate, oxide or a hydroxide of iron and/or aluminium.
- novel solvent extraction (SX) processes with minimum SX systems and circuits for separation of impurities from cobalt and nickel, and separation of cobalt from nickel to produce cobalt liquors suitable for crystallisation of high purity, battery grade cobalt sulphate, cobalt chloride, cobalt nitrate or other cobalt products, if desired, and a raffinate nickel suitable for direct crystallisation of high purity, battery grade nickel sulphate or other nickel products, if desired, without the separation step of major metal nickel are provided.
- SX solvent extraction
- the processes of the second phase avoid contamination from the neutralisation with a base reagent such as sodium hydroxide, sodium carbonate, ammonia or ammonium hydroxide in the SX processes.
- a base reagent such as sodium hydroxide, sodium carbonate, ammonia or ammonium hydroxide in the SX processes.
- the processes of the second phase provide alternative processes to enable direct neutralisation during solvent extraction with ammonia / ammonium hydroxide and selective removal of the ammonium component from the final hydrated nickel sulphate as ammonia for recycling as a base reagent in the process.
- a process for obtaining purified nickel and cobalt from the feed solution obtained according to the first aspect comprising: 8 a) reducing the concentration of any zinc, calcium, manganese, copper, cadmium, lead or other metal impurities having higher affinity to an organic extractant than cobalt and nickel, in the feed solution by contacting it with an organophosphoric acid extractant in a hydrocarbon diluent, under solvent extraction conditions and separating the organic and aqueous phases to produce an aqueous raffinate comprising purified cobalt and nickel; b) contacting the aqueous raffinate comprising purified cobalt and nickel with a cobalt selective extractant in a hydrocarbon diluent, under solvent extraction conditions and separating organic and aqueous phases to produce an organic phase comprising purified cobalt and an aqueous phase comprising purified nickel, followed by selective scrubbing and stripping of the organic phase to obtain an a
- first and second phases described herein can be performed separately from one another, or they may be combined to provide an improved process for producing high purity, battery grade cobalt sulphate or other cobalt products and high purity, battery grade nickel sulphate from crude nickel and cobalt containing materials such as laterite ores.
- step b) comprises: a) (i) co-extracting both cobalt and magnesium in the aqueous raffinate from step a) into the organic phase; (ii) selectively scrubbing any co-extracted nickel from the organic phase with a scrub solution of sulphuric acid and/or cobalt sulphate at a relatively high equilibrium pH range to obtain the organic phase with nickel removed and a nickel rich scrub liquor (aqueous phase) which is recycled to step (i); (iii) further selectively scrubbing magnesium from the organic phase with a scrub solution of sulphuric acid and/or cobalt sulphate at a relatively low equilibrium pH range to obtain the organic phase with purified cobalt and a magnesium rich scrub liquor (aqueous phase); (iv) re-extracting any co scrubbed cobalt in the magnesium rich scrub liquor (aqueous phase) with a minor portion of the organic phase to obtain a minor portion of cobalt loaded
- the organophosphoric acid extractant has the formula (R0) 2 P0 2 H, wherein each R group, which may be the same or different, is an optionally substituted branched, straight chained or cyclic alkyl, alkenyl or alkynyl group.
- the organophosphoric acid extractant is di-2- ethylhexyl phosphoric acid (D2EHPA), or an organophosphoric acid having extraction characteristics similar to or the same as di-2-ethylhexyl phosphoric acid, such as mono-2 -ethylhexyl phosphoric acid (M2EHPA) or di-p-octylphenyl phosphoric acid (OPPA).
- D2EHPA di-2- ethylhexyl phosphoric acid
- M2EHPA mono-2 -ethylhexyl phosphoric acid
- OPPA di-p-octylphenyl phosphoric acid
- the cobalt selective extractant is an organophosphinic acid having the formula R 2 P0 2 H, in which the R groups, which may be the same or different, are selected from optionally substituted branched, straight chained or cyclic alkyl, alkenyl or alkynyl groups.
- the cobalt selective extractant is di-2,4,4- trimethylpentylphosphinic acid, or an organophosphinic acid having extraction characteristics similar to or the same as di-2,4,4-trimethylpentylphosphinic acid, such as di-2-ethylhexylphosphinic acid.
- di-2,4,4-trimethylpentylphosphinic acid is the functioning component in the commercial products Cyanex ® 272 and Ionquest ® 290.
- a phase modifier or modifiers may be present in the organic solutions.
- the modifier can be any suitable modifier that improves separation of the organic and aqueous phases, including, but not limited to, isodecanol, isotridecanol, 2-ethylhexanol and tri-n- butyl phosphate.
- the hydrocarbon diluent is an aliphatic or aromatic hydrocarbon solvent or a mixture thereof. In certain specific embodiments of the second aspect the hydrocarbon diluent is kerosene. 10
- the step c) purifying the aqueous phase comprising purified cobalt comprises: contacting the aqueous phase comprising purified cobalt with an ion exchange (IX) resin under conditions to selectively bind impurities to the resin to form a loaded resin, washing the loaded resin with an aqueous solution of water and/or an acid to recover co-loaded cobalt.
- the step c) further comprises eluting the loaded resin with an acid to remove the impurities and regenerate the resin.
- the step c) of purifying the aqueous phase comprising purified cobalt further comprises removing at least some of any copper from the aqueous phase comprising purified cobalt.
- the step of removing at least some of any copper from the aqueous phase comprising purified cobalt may comprise contacting the aqueous phase comprising purified cobalt with an iminodiacetic resin under conditions to bind copper and separating the copper loaded resin from the aqueous phase.
- the step c) of purifying the aqueous phase comprising purified cobalt further comprises removing at least some of any zinc from the aqueous phase comprising purified cobalt.
- the step of removing at least some of any zinc from the aqueous phase comprising purified cobalt may comprise contacting the aqueous phase comprising purified cobalt with a D2EHPA impregnated resin under conditions to bind zinc and separating the zinc loaded resin from the aqueous phase.
- the step c) of purifying the aqueous phase comprising purified cobalt optionally comprises simultaneously removing at least some of any zinc and at least some of any copper from the aqueous phase comprising purified cobalt.
- the step of simultaneously removing at least some of any zinc and at least some of any copper from the aqueous phase comprising purified cobalt may comprise contacting the aqueous phase comprising purified cobalt with an aminophosphonic acid resin under conditions to bind zinc and copper and separating the copper and zinc loaded resin from the aqueous phase.
- the step c) of purifying the aqueous phase comprising purified cobalt further comprises removing at least some of any manganese from the aqueous phase comprising purified cobalt.
- the step of removing at least some of any manganese from the aqueous phase comprising purified cobalt may comprise contacting the aqueous phase comprising purified cobalt with an oxidant under conditions to oxidise any manganese(II) to higher oxidation state manganese(III/IV) and separating the solid manganese(III/IV) oxide from the aqueous phase.
- the oxidant may be selected from the group consisting of ozone, a mixture of S0 2 /0 2 (air) at a ratio functioning as an oxidant, peroxymonosulfuric acid (Caro’s acid) and peroxydisulfuric acid, if the aqueous phase 11 comprising purified cobalt is sulphate, or selected from other groups of oxidants (e.g. chloride or nitrate) identical to the aqueous phase comprising purified cobalt.
- oxidants e.g. chloride or nitrate
- the step c) of purifying the aqueous phase comprising purified cobalt optionally comprises removing at least one of one or more of zinc, calcium, manganese, copper, cadmium, lead or other metal impurities in the aqueous phase comprising purified cobalt by contacting it with an organophosphoric acid extractant in a hydrocarbon diluent, optionally in the presence of a phase modifier, under solvent extraction conditions and separating the organic and aqueous phases to produce a further aqueous phase comprising purified cobalt.
- the step of recovering nickel from the aqueous phase comprising purified nickel comprises crystallising nickel sulphate from the aqueous phase comprising purified nickel.
- the process step a) further comprises scrubbing at least some of any co-extracted cobalt and nickel with a scrub solution containing water and/or sulphuric acid and/or metal sulphates from the organic phase to aqueous phase which is recycled to the extraction.
- the process further comprises stripping at least some of any one or more of zinc, calcium, manganese and copper, and other loaded impurities having higher affinity to the organic extractant than cobalt and nickel present in the organic phase obtained in step a) by either (a) treating the organic phase with sulfuric acid through control of the calcium concentration below its saturation to avoid gypsum formation, or (b) treating the organic phase with hydrochloric acid, if the calcium concentration in the system is relatively high with a risk of forming gypsum.
- the process further comprises periodically bleeding treatment of the organic phase in step a) by contacting the organic phase with a solution of hydrochloric acid (typically 6 molar HC1) to remove some of any one or more of iron, aluminium and other strongly binding metal ions from the organic phase.
- a solution of hydrochloric acid typically 6 molar HC1
- the step b), wherein selectively scrubbing the extracted nickel from the organic phase comprising purified cobalt is performed in a relatively high equilibrium pH range, preferably in equilibrium pH range of 4.5 - 6.5, and selectively scrubbing the extracted magnesium from the organic phase comprising purified cobalt in a relatively low equilibrium pH range, preferably in the equilibrium pH range of 3 - 5.
- the scrubbing of nickel and magnesium may be performed successively in a higher pH range for removal of nickel and then in a lower pH range for 12 removal of magnesium to obtain two separate scrub liquors, or concurrently in a lower pH range for removal of both nickel and magnesium.
- step b) further comprises co-extracting any magnesium present in the raffinate comprising purified cobalt and nickel into the organic phase.
- Magnesium may be separated from cobalt by further scrubbing the co-extracted magnesium with sulphuric acid at a preferable equilibrium pH range of 3 - 5, and selectively re -extracting the co-scrubbed cobalt from the magnesium rich scrub liquor into a portion of the organic phase which may be recycled and merged into the main portion of the organic phase at the point of scrubbing of the magnesium.
- the step b) purifying the organic phase comprising purified cobalt by scrubbing both co-extracted nickel and magnesium from the organic phase with a scrub solution of sulphuric acid and/or cobalt sulphate to obtain a nickel rich scrub liquor which may be recycled to the extraction step b) for recovering nickel.
- step b) further comprises extracting any magnesium present in the raffinate comprising purified nickel with a portion of the organic, followed by scrubbing with sulphuric acid under conditions to remove the co-extracted nickel which is recycled to the extraction step b).
- the scrubbed organic is stripped with sulphuric acid to regenerate the organic and to produce the magnesium enriched aqueous phase for further recovery of magnesium by-products.
- the process further comprises preloading one or more organic solution used in the process with sulphate, carbonate, oxide or hydroxide salts of nickel, cobalt and/or magnesium.
- the process may comprise preloading one or more organic solution used in the process with nickel sulphate.
- the process may further comprise treating with a base reagent such as nickel hydroxide, sodium hydroxide or carbonate, ammonia, ammonium hydroxide or carbonate and magnesium oxide / hydroxide or carbonate for neutralisation or pH control in the preloading.
- the process may further comprise pre-neutralising the organic solution with a base reagent to produce the pre neutralised organic for preloading of nickel by exchange.
- the base reagent may be selected from the group consisting of sodium hydroxide, sodium carbonate, ammonia, ammonium hydroxide or ammonium carbonate.
- the process may further comprise washing the organic solutions preloaded with nickel sulphate with a scrub solution containing water and/or sulfuric acid and/or nickel sulphate to remove entrained and extracted sodium or ammonium ions.
- the process further comprises directly neutralising acid produced during the solvent extraction with ammonia, ammonium hydroxide or carbonate under conditions to avoid formation of nickel ammonium double salts, or ammonium sulphate salt and subsequently thermally decomposing the ammonium component in the hydrated nickel sulphate. 13
- the process comprises one or more stages of any extraction step, any scrubbing step and any stripping step in solvent extraction, and any loading step, any washing step and any elution step in ion exchange which may operate countercurrent mode or concurrent mode or the combination of the two modes.
- a third aspect provided herein is a high purity nickel sulphate obtained by the process of the first aspect and/or the second aspect.
- Figure 1 shows a schematic flowsheet of embodiments of the present disclosure with schemes and methods for treatment of MHP and or/PLS to produce final feed solution which is substantially free of alkali metal ion (Na + and K + ) and monovalent cation species (NH 4 + ), iron, aluminium and cromium with an optional removal of a portion of manganese.
- alkali metal ion Na + and K +
- monovalent cation species NH 4 +
- iron, aluminium and cromium with an optional removal of a portion of manganese.
- Figure 2 shows a schematic flowsheet of embodiments of the present disclosure with schemes and methods for processing of nickel laterite ores or nickel bearing materials and solutions for producion of an MHP with optimum ratios of iron and aluminium to the total amount of alkali metal ion (Na + and K + ) and monovalent cation species (NH 4 + ) favorable for increased processing efficiency and subsequent refining processes shown in Figure 1 , or alternatively for production of feed solution or MHP which is vritually free of alkali metal ion (Na + and K + ) and monovalent cation species (NH 4 + ) and iron, aluminium and cromium with an optional removal of a portion of manganese.
- alkali metal ion Na + and K +
- NH 4 + monovalent cation species
- FIG. 3 shows a flowsheet of embodiments of the present disclosure with schemes and methods for purification of the feed solution produced from the processes shown in Figure 1 and Figure 2 by SX and IX, featuring (i) organic preloading; (ii) SX for removal of one or more impurities from the group of zinc, calcium, manganese, cadmium, copper, lead and any other impurities having higher affinity to the organic extractant than cobalt and nickel; (iii) one SX circuit for extraction of both cobalt and magnesium from nickel and then separation of magnesium from cobalt within the SX circuit; (iv) direct crystallisation of nickel sulphate from the final SX raffinate; (v) purification of the aqueous phase comprising purified cobalt from step (iii); and (vi) crystallisation of cobalt sulphate or other cobalt salts from the aqueous phase comprising purified cobalt from step (v). 14
- FIG 4 shows a flowsheet of embodiments of the present disclosure for purification of the feed solution produced from the processes shown in Figure 1 and Figure 2 by SX and IX, featuring (i) direct neutralisation with ammonia/ammonium hydroxide in SX, (ii) SX for removal of one or more impurities from the group of zinc, calcium, manganese, copper, cadmium, lead and any other impurities having higher affinity to the organic extractant than cobalt and nickel, (iii) one SX circuit for extraction of both cobalt and magnesium from nickel and then separation of magnesium from cobalt within the SX circuit,
- step (iv) direct crystallisation of nickel sulphate from the final SX raffinate, (v) thermal decomposition of ammonium sulphate component in the hydrated nickel sulphate to remove ammonium component as ammonia for recycling use as the base reagent, (vi) purification of the aqueous phase comprising purified cobalt from step (iii), and (vii) crystallisation of cobalt sulphate or orther cobalt salts from the aqueous phase comprising purified cobalt from step (vi).
- Figure 5 shows a flowsheet of embodiments of the present disclosure for the purification of the feed solution produced from the processes shown in Figure 1 and Figure 2 by SX and IX, featuring (i) organic preloading, (ii) SX for removal of one or more impurities from the group of zinc, calcium, manganese, copper, cadmium, lead and any other impurities having higher affinity to the organic extractant than cobalt and nickel, (iii) two separate SX circuits for separation of cobalt from magnesium and then magnesium from nickel, (iv) direct crystallisation of nickel sulphate from the final SX raffinate,
- step (v) purification of the aqueous phase comprising purified cobalt from step (iii), and (vi) crystallisation of cobalt sulphate or other cobalt salts from the aqueous phase comprising purified cobalt from step (v).
- Figure 6 shows a flowsheet of embodiments of the present disclosure for the purification of feed solution produced from the processes shown in Figure 1 and Figure 2 by SX and IX, featuring (i) direct neutralisation with ammonia/ammonium hydroxide in SX, (ii) SX for removal of one or more impurities from the group of zinc, calcium, manganese, copper, cadmium, lead and any other impurities having higher affinity to the organic extractant than cobalt and nickel, (iii) two separate SX circuits for the separation of cobalt from magnesium, and magnesium from nickel, (iv) direct crystallisation of nickel sulphate in the final SX raffinate, (v) thermal decomposition of ammonium sulphate component in the hydrated nickel sulphate to remove ammonium component as ammonia for recycling use as the base reagent, (vi) purification of the aqueous phase comprising purified cobalt from step (iii), and (vii) crystallisation of cobalt s
- Figure 7 compares the conversion efficiency of Mn(II) to stable Mn(IH/IV) oxide with air only and the mixture of S0 2 /air.
- Figure 8 shows the nickel preloading isotherms with 10% D2EHPA and 62 g/L nickel (sulphate) solution at pH ⁇ 5 and 50 °C. 15
- Figure 9 shows the scrubbing isotherms of sodium from the preloaded 10% D2EHPA with 64.7 g/L nickel (sulphate) solution at pH 3.6 and 50 °C.
- Figure 10 shows the extraction distribution isotherm with the Ni-preloaded 10% D2EHPA at pH 3.1 and 40 °C.
- Figure 11 shows the McCabe-Thiele diagrams for extraction of Zn(II) and Cu(II) with the Ni- preloaded 10% D2EHPA at pH 3.1 and 40 °C.
- Figure 12 shows the McCabe-Thiele diagrams for extraction of Mn(II) and Ca(II) with the Ni- preloaded 10% D2EHPA at pH 3.1 and 40 °C.
- Figure 13 shows the nickel preloading isotherms with 25% Cyanex ® 272 and 60 g/L nickel (sulphate) solution at 50 °C and pH 6.8 - 7.0.
- Figure 14 shows the scrubbing isotherms of sodium from the preloaded 25% Cyanex ® 272 at pH 5.5 and 50 °C.
- Figure 15 shows the extraction distribution isotherms of Ni(II), Co(II) and Mg(II) with the Ni(II)-preloaded 25% Cyanex ® 272 at 40 °C.
- Figure 16 shows the McCabe-Thiele diagrams for extraction of Co(II) and Mg(II) with the Ni(II)-preloaded 25% Cyanex ® 272 at 40 °C.
- Figure 17 shows McCabe-Thiele diagrams for nickel scrubbing from the loaded 25% Cyanex ® 272 at pH ⁇ 4.2 and pH ⁇ 5 and 40 °C.
- Figure 18 shows McCabe-Thiele diagrams for magnesium scrubbing from the loaded 25% Cyanex ® 272 at pH ⁇ 3.5 and pH ⁇ 4.2 and 40 °C.
- purified in the context of the present disclosure, the terms “purified”, “purity” and related terms are intended to mean a composition, compound or material that has had some of the impurities or substances that adulterate or contaminate a substance removed.
- the term purified is a relative term and does not require absolute purity.
- a purified compound is one in which the compound is more enriched than the compound is in its natural environment or preceding any purifying treatment.
- the terms “high purity” and “battery grade” when used in reference to nickel salts or cobalt salts means that the material has a minimum level of nickel or cobalt and/or low levels of trace elements such as Al, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Na, Pb, Si, and Zn that make them suitable for battery applications.
- a “high purity” and/or “battery grade” nickel salt may have a nickel content of at least 21 wt%, such as from about 22 wt% to about 23 wt%.
- a nickel salt such as nickel sulphate hexahydrate: NiS0 4 -6H 2 0 having a nickel content of 22.0 wt%, 22.1 wt%, 22.2 wt%, 22.3 wt%, 22.4 wt%, 22.5 wt%, 22.6 wt%, 22.7 wt%, 22.8 wt%, 22.9 wt% or 23.0 wt% is considered high purity or battery grade.
- a “high purity” and/or “battery grade” cobalt salt may have a cobalt content of at least 20 wt%, such as at least 21 wt% or such as from about 20 wt% to about 22 wt%.
- a cobalt salt (such as cobalt sulphate heptahydrate: CoS0 4 -7H 2 0) having a cobalt content of 20.0 wt%, 20.1 wt%, 20.2 wt%, 20.3 wt%, 20.4 wt%, 20.5 wt%, 20.6 wt%, 20.7 wt%, 20.8 wt%, 20.9 wt%, 21.0 wt%, 21.1 wt%, 21.2 wt%, 21.3 wt%, 21.4 wt%, 21.5 wt%, 21.6 wt%, 21.7 wt%, 21.8 wt%, 21.9 wt% or 22.0 wt% is considered high purity or battery grade.
- soluble is intended to mean capable of becoming molecularly or ionically dispersed in a solvent to form a homogeneous solution. Solubility can be determined by visual inspection, by turbidity measurements or by dynamic light scattering.
- processes whereby high purity cobalt sulphate and high purity (battery grade) nickel sulphate can be produced from nickel and cobalt containing crude feedstocks, such as mixed hydroxide precipitate (MHP), without requiring the costly nickel extraction step via SX, resulting in an economic advantage.
- the processes described herein comprise one or more of the following steps: a) Washing a nickel / cobalt MHP or other nickel containing material to remove most or substantially all of the alkali metal ion (e.g. Na + and K + ) and monovalent cation species (e.g.
- This removal step can be performed either concurrently or successively; c) Neutralisation of the leach solution to precipitate the remaining iron and aluminium as goethite, alumina or hydroxides, together with chromium hydroxide and partial copper hydroxides, and optional oxidative precipitation of Mn(IV) oxides with an oxidant to provide a feed solution; d) Solid / liquid separation to obtain nickel and cobalt pregnant leach solution (PLS) containing nickel, cobalt, zinc, calcium, manganese (minor), copper, magnesium, and being substantially free of alkali metals and monovalent cation species, and iron, aluminium and chromium; e) SX-based extraction and thus separation of zinc, manganese, copper and calcium and other impurities (e.g.
- cadmium, lead having higher affinities to the organic extractant than cobalt and nickel from the PLS using an organophosphoric acid extractant (e.g. D2EHPA), leaving a PLS containing cobalt, nickel and magnesium in the raffinate; f) SX-based extraction of both cobalt and magnesium, either successively or concurrently, from the PLS using an organophosphinic acid extractant (e.g.
- the processes described herein can be retrofitted to conventional and existing commercial processes for production of improved intermediate products or solutions suitable for subsequent refining processes as described herein. Furthermore, the processes described herein provide a great potential to expand existing operations or justify investment in green field operations and revitalise nickel laterite industries.
- a process for separating nickel and/or cobalt salts from crude nickel and/or cobalt bearing materials comprising: a) treating a crude nickel and/or cobalt bearing material with a salt of iron or aluminium under conditions to remove at least some of one or more alkali metal ion and/or monovalent cation species as a jarosite /alunite precipitate to provide a solution having a reduced content of one or more alkali metal ion and/or monovalent cation species; b) subjecting the solution from step a) to increasing pH in a stepwise manner under conditions to provide a feed solution for further purification to produce nickel and/or cobalt salts suitable for the production of battery grade nickel or cobalt salts; wherein step b) removes at least some or any combination of any one or more of the following species: 19 l. iron, ii. aluminium, iii. chromium, and
- the processes of this first aspect include jarosite / alunite precipitation to remove alkali metal ions and monovalent cation species ( Figure 1 and Figure 2).
- Jarosite / alunite precipitation is used for a deep removal of the alkali metal ion (Na + , K + ) and monovalent cation (NH 4 + ) species, which can be used alone or in successive steps after the washings.
- the schemes of the treatment processes described herein include only washing, only jarosite / alunite treatment and an optimum combination of washing with jarosite / alunite, depending on specific conditions associated with cost effective factors such as the contents of the alkali metal ions and monovalent cation species, water balance from washings, available solid / liquid separation facilities of high efficiency, contents of iron and aluminium in the MHP and/or available iron and aluminium forms / sources suitable for jarosite / alunite precipitation.
- the jarosite / alunite precipitation can be performed in leaching concurrently or successively after the leaching. If needed, various iron and aluminium forms, preferably their sulphates or carbonate and oxides or hydroxides, can be added to obtain an optimum ratio to the alkali metal ion and monovalent cation species for efficient jarosite / alunite precipitation.
- An oxidant may be present to oxidise iron(II) to iron (III), which may also oxidise manganese(II) to stable manganese(IV) oxides.
- a typical nickel laterite ore contains rich iron and aluminium, which partially enters the PLS and are removed as hydroxides by neutralisation prior to the precipitation of the MHP. A portion of the iron and aluminium hydroxides could be utilised as a source of iron for the jarosite process, if desired.
- a known issue of the iron and aluminium hydroxide precipitation in a conventional process is the co-precipitation of nickel and cobalt which becomes significant at a higher pH for more complete removal of iron and aluminium to meet the standard specification of the MHP.
- staged precipitations of the iron and aluminium and recycling the last stage precipitate to leaching is conventionally employed, but heavy recycling loads would significantly decrease the process efficiency and increase the operating costs.
- the presently disclosed processes not only provide schemes for treating an intermediate product, e.g. MHP, but they are also useful and beneficial for improving the overall nickel laterite ore process. With the present processes, it is not necessary to deep remove iron and aluminium, as the presence of stoichiometric amounts of iron and aluminium species relative to the alkali metal ions (Na + , 20
- an MHP can contain a desirable ratio of the iron / aluminium to the total of alkali metal and monovalent cation components for subsequent the jarosite / alunite precipitation.
- the jarosite / alunite process is applicable for removal of alkali metal ion (Na + ,
- a stoichiometric portion of the MHP with respect to that of total alkali metal ion (Na + , K + ) and monovalent cation (NH 4 + ) species can be utilised for neutralisation of the acid produced during the jarosite / alunite precipitation, or in other words, the acid produced is simultaneously utilised for dissolving equivalent amount of the MHP without need for addition of other base reagents to avoid introduction of impurities.
- a portion of the jarosite can be recycled to seed the solution at a proper dose to improve the kinetics of jarosite precipitation.
- the slurry pH is raised, preferably in stages from lower to higher pH to precipitate a major portion of the remaining iron(III) as well crystalline forms such as goethite so as to minimise the loss of nickel and cobalt, and similarly the remaining aluminium as alunite / alumina versus iron and aluminium hydroxides.
- a base reagent preferably nickel hydroxide, magnesium oxide / hydroxide, limestone / lime, can be added for the neutralisation process. The neutralisation process would also remove chromium and a portion of copper as hydroxides.
- the processes of this first aspect can also comprise a washing step to remove alkali metal ions and monovalent cation species ( Figure 1 and Figure 2).
- the process may further comprise treating the crude nickel and/or cobalt bearing material prior to step a) with an aqueous solution comprising water or dilute sulfuric acid under conditions to remove at least some of one or more alkali metal ion and monovalent cation species.
- washing of an MHP may be involved in the conventional and existing refining processes, it is not specially designed for the removal of a substantial portion, or preferably substantially all the alkali metal ion (Na + , K + ) and monovalent cation (NH 4 + ) species.
- Washing is the first step of the present process for the treatment of an MHP, wherein the MHP is repulped with a wash solution containing water and/or sulphuric acid to remove a substantial portion or preferably substantially all the alkali metal ions (Na + , K + ), monovalent cation species (NH 4 + ) with minimum dissolution of nickel and cobalt.
- the washing step may be carried out at a pH of 7 or greater.
- washings may be performed to achieve a desirable degree of washing efficiency.
- the washings would simultaneously remove significant portions of other soluble species such as calcium and magnesium as an additional benefit favourable for subsequent purification by SX. It is optional to simultaneously convert a portion, or preferably a major portion of Mn(II) into stable solid Mn(IV) oxide with an oxidant.
- the processes of this first aspect can also comprise oxidative conversion of divalent Mn(II) to stable Mn(III/IV) forms.
- the process may comprise treating the first nickel and/or cobalt bearing material extract, the second nickel and/or cobalt bearing material extract and/or the third nickel and/or cobalt bearing material extract with an oxidant under conditions to oxidise any iron(II) to iron (III) and any manganese(II) to manganese(III/IV) to provide a pregnant liquor solution containing nickel and/or cobalt and having reduced concentrations of any one or more of alkali metal ions, monovalent cation species, iron, aluminium, chromium, copper and manganese relative to the crude nickel and/or cobalt bearing material, wherein the pregnant liquor solution is suitable for further purification to produce high purity, battery grade nickel and/or cobalt salts.
- a proper oxidant may be optionally added in the above neutralisation process under controlled conditions, termed as oxidative neutralisation, to convert any iron(II) to iron(III) and Mn(II) into stable Mn(III/IV) oxide, if desired.
- oxidative neutralisation any iron(II) to iron(III) and Mn(II) into stable Mn(III/IV) oxide, if desired.
- An early rejection of a major portion of manganese is preferred to make the subsequent purification by solvent extraction easier.
- the feed solution produced is substantially free of alkali metal ion (Na + , K + ) and monovalent cation (NH 4 + ) species, iron, aluminium and chromium, with partially removed copper and manganese, which contains major metal - nickel, cobalt, zinc, remaining copper and manganese, calcium and magnesium in the feed solution for further purification.
- a process for obtaining purified nickel and cobalt from a feed solution produced according to the first aspect comprises: a) reducing the concentration of any zinc, calcium, manganese, copper, cadmium, lead or other metal impurities having higher affinity to an organic extractant than cobalt and nickel, in the feed solution by contacting it with an organophosphoric acid extractant in a 22 hydrocarbon diluent, under solvent extraction conditions and separating organic and aqueous phases to produce an aqueous raffinate comprising purified cobalt and nickel; b) contacting the aqueous raffinate with a cobalt selective extractant in a hydrocarbon diluent, under solvent extraction conditions and separating organic and aqueous phases to produce an organic phase comprising purified cobalt and an aqueous phase comprising purified nickel; c) selectively scrubbing and stripping the organic phase to obtain an aqueous phase comprising pur
- the feed solution produced in the process of the first aspect is further purified by SX and IX to separate impurities from cobalt, and cobalt from nickel, wherein cobalt rich liquor is further purified by ion exchange (IX) or SX to remove various minor impurities such as zinc and copper to generate purified cobalt liquor for crystallisation of cobalt sulphate, while the major metal nickel in the final SX raffinate is directly fed to the crystallisation to produce high purity nickel sulphate.
- IX ion exchange
- SX ion exchange
- the impurities of zinc, calcium, manganese and copper, cadmium, lead and other impurities having higher affinity to the organic extractant than cobalt and nickel in the feed solution are extracted and separated from cobalt and nickel with an organophosphoric acid (D2EF1PA) extractant in a hydrocarbon diluent such as Exxsol D80 and Escaid 110 and optionally in the presence of a phase modifier, leaving cobalt and nickel together with partial magnesium in the raffinate.
- D2EF1PA organophosphoric acid
- An organophosphinic acid e.g. Cyanex ® 272 or Ionquest ® 290
- a hydrocarbon diluent such as Exxsol D80 and Escaid 110
- a phase modifier e.g. Cyanex ® 272 or Ionquest ® 290
- Co and Mg SX Scheme Option 1 ( Figure 3, Figure 4):
- the cobalt and magnesium are co-extracted and separated from nickel, and the loaded magnesium is separated from cobalt by an internal scrubbing scheme within the SX circuit, wherein the coextracted nickel is first scrubbed from the loaded organic to obtain a nickel rich scrub liquor which is recycled to the extraction and then the extracted magnesium is scrubbed from the loaded organic to produce a magnesium rich liquor containing some co-scrubbed cobalt which is then extracted by a minor stream of the organic solution and recycled to the main scrubbing section.
- This scheme can separate respective magnesium and cobalt streams from nickel in just one SX circuit.
- Co and Mg SX Scheme Option 2 ( Figure 5, Figure 6):
- the cobalt is selectively extracted and the co-extracted nickel and magnesium are scrubbed and recycled to the extraction, and thus the cobalt is separated from magnesium and nickel.
- the magnesium in the raffinate is then extracted and separated from nickel using a portion of the same organic solution in a separate solvent extraction circuit.
- the cobalt loaded strip liquor is purified by ion exchange (IX) to remove minor impurities such as copper with an iminodiacetic type resin and zinc with D2EHPA impregnant resin, or alternatively, simultaneous removal of both copper and zinc with an aminophosphonic acid resin.
- Minor manganese can be selectively removed by oxidative precipitation with a suitable oxidant, such as ozone, the mixture of S0 2 /0 2 (air) at a ratio for functioning as an oxidant, or peroxymonosulfuric acid (Caro’s acid) and peroxydisulfuric acid.
- various minor impurities including zinc, copper, manganese, calcium, cadmium, and lead can be removed from the cobalt loaded strip liquor by SX with an organophosphoric acid (D2EHPA) extractant as described above, if desired.
- D2EHPA organophosphoric acid
- the purified cobalt liquor is fed to crystallisation to produce high purity cobalt sulphate or other cobalt salts.
- the stoichiometric amount of acid equivalent to the divalent metals extracted would be produced during the SX processes with an acidic extractant such as an organophosphoric acid (e.g. D2EHPA) and an organophosphinic acid (e.g. Cyanex ® 272). Therefore, it is critical for the SX schemes 24 to be able to produce the final high purity nickel sulphate product without contamination. Two approaches and schemes may be used.
- an organophosphoric acid e.g. D2EHPA
- an organophosphinic acid e.g. Cyanex ® 272
- Certain embodiments utilise a direct preloading of organic solutions with nickel sulphate available within the process.
- nickel sulphate available within the process.
- other metal sulphates, or carbonate, or oxide / hydroxide may be employed for the preloading such as cobalt sulphate and magnesium sulphate, or their oxide / hydroxide
- the nickel sulphate or carbonate, or oxide / hydroxide is preferred because any nickel introduced into the feed solution does not need further separation, compared to the cobalt or magnesium salts which need to be again separated in the subsequent SX schemes.
- a proper base reagent such as nickel hydroxide, sodium hydroxide or carbonate, ammonia / ammonium hydroxide or carbonate and magnesium oxide / hydroxide or carbonate can be used for neutralisation or pFl control in the preloading.
- the stripped organic can be pre-neutralised with a base reagent such as sodium hydroxide or carbonate, or ammonia / ammonium hydroxide or carbonate to produce the pre-neutralised organic for preloading of nickel by exchange.
- a base reagent such as sodium hydroxide or carbonate, or ammonia / ammonium hydroxide or carbonate to produce the pre-neutralised organic for preloading of nickel by exchange.
- the nickel preloaded organic solutions are then washed with a scrub solution containing water and/or sulfuric acid and/or nickel sulphate to remove the entrained and extracted sodium or ammonium ions to avoid contamination of the system.
- the scrubbed organic solutions are then fed to respective main SX circuits to extract the metal ions through exchange of the preloaded nickel with minimum or no pFl control.
- An alternative approach employs direct neutralisation of the acid produced during the SX with ammonia / ammonium hydroxide under controlled conditions to avoid formation of nickel ammonium double salt or ammonium sulphate salt, and subsequent selective thermal decomposition of the ammonium component in the hydrated nickel sulphate, preferably as ammonia which can be recycled in the process as the base reagent.
- the present disclosure also provides schemes for improving overall upstream processing of nickel laterite ores or other nickel containing materials or solutions, including the following schemes.
- Upstream Scheme 1 Controlled neutralisation of iron and aluminium precipitation to produce MF1P containing a desirable ratio of iron and aluminium to alkali metal ions (Na + and K + ) and monovalent 25 cation (NH 4 + ) species for subsequent jarosite / alunite precipitation in the refining processes described herein.
- Upstream Scheme 2 leaching and jarosite precipitation concurrently or successively followed by neutralisation and solid / liquid separation to produce a feed solution which is substantially free of alkali metal ions (Na + and K + ) and monovalent cation (NH 4 + ) species.
- This feed solution can be directly fed to the subsequent purification schemes by SX and IX described herein, or to the production of MHP which is substantially free of alkali metal ions (Na + and K + ) and monovalent cation (NH 4 + ) species for subsequent leaching option as illustrated in Figure 1.
- the methods for removing alkali metal ions (Na + , K + ) and monovalent cation (NH 4 + ) species include washing (105) and/or concurrent leaching - jarosite / alunite (119) or successive leaching (112) and jarosite / alunite (115). Washing (105) or jarosite / alunite (119, 112 and 115) can be used alone or in combination.
- washings can be performed in various ways, including single or multiple re pulping, rinsing the filter cakes, and a combination of these means, or continuous counter-current decantation in multiple stages.
- an oxidant (103) may be added to convert a portion, preferably a major portion of Mn(II) ions into stable solid Mn(IV) oxides.
- the oxidant may be selected from, but not limited, air, oxygen, ozone, oxides, persulphuric acid, peroxides, peroxymonosulphuric acid (Caro's Acid), the oxidising mixtures of sulphur dioxide (S0 2 ) with air or oxygen at a right ratio.
- the addition of an oxidant is controlled through monitoring the slurry potential and pH to minimise the oxidation of Co(II) and Ni(II) into Co(III) and Ni(III) oxides.
- An oxidant of week to medium oxidising power such as air, oxygen and their mixture with sulphur dioxide at a right ratio, and Caro's Acid are preferred for continuous addition and easy control to minimise the oxidation of Co(II) and Ni(II).
- the oxidation process is preferably performed under the condition that a substantial portion (> 95%) of the MHP is undissolved in the solid state to minimise the oxidation of Co(II) and Ni(II) into solid forms of Co(III) and Ni(III) oxides.
- the liquid and solid in the washings are separated (107) to produce the washed MHP (109) with desirable washing efficiency of alkali metal ion and monovalent cation species and reduced contents of other soluble species such as Ca(II), Mg(II), Mn(II), nitrate and chloride ions.
- an equivalent portion of the MHP is added to neutralise the acid produced during the jarosite / alunite precipitation (119) according to reaction (1) to control a pH range desirable for the jarosite / alunite precipitation (119) without need for use of other base reagents which may introduce more impurities.
- the acid produced is simultaneously utilised for dissolution of an equivalent portion of the MHP.
- the iron and aluminium hydroxides from the conventional upstream precipitate process are a potential iron and hydroxide source.
- An improved upstream processing of nickel laterite ores for controlled Fe/Al precipitation to allow the presence of desirable ratios of (Fe + Al) to (Na + + K + + NH 4 + ) in the feed solution and in the MHP is as shown in Figure 2, which will be described later.
- the jarosite precipitation can be operated in the range of 60 - 100 °C and pH 1.6 - 2.0, preferably at 85 - 95 °C and pH 1.8 - 2.0, and redox potential (Eh) at the stability region of jarosite formation. Recycle of a portion of jarosite as seed is preferred to promote the kinetics of jarosite / alunite precipitation. If needed, an oxidant may be added to oxidise any lower oxidation valance of iron species, e.g. Fe(II) to Fe(III).
- the alunite precipitation may be performed successively under the conditions of preferably 85 - 95 °C and pH 3.5 - 5.0 ranges, wherein the slurry pH is raised by neutralisation (122), preferable in stages, e.g. pH 2.5, pH 3.5 and pH 4 - 4.5 to precipitate the remaining iron(III) to goethite, oxide / hydroxide, and aluminium as alunite and alumina / hydroxide, while chromium and a portion of copper would be simultaneously precipitated as hydroxides.
- neutralisation 122
- oxidative neutralisation 122
- oxidative neutralisation 122
- Mn(II) oxidise Fe(II) to Fe(III) and/or a major portion of Mn(II) to solid Mn(III/IV) oxides.
- the slurry (123) from the neutralisation (122) is then transferred to the liquid and solid separation (124), to dispose the residue (125) containing jarosite, alunite, goethite, hydroxides of Fe(III), Al(III), Cr(III) and Cu(II), and optional manganese(III/IV) oxides, while the feed solution (126) obtained is substantially free of alkali metal ion (Na + , K + ) and monovalent cation (NH 4 + ) species as well as iron, aluminium, chromium, containing nickel (major), cobalt, zinc, calcium, manganese (minor) and partially reduced copper, and magnesium, which is suitable for subsequent purification processes described herein as shown in Figure 3, Figure 4, Figure 5 and Figure 6.
- the present disclosure not only provides the schemes as shown in Figure 1 for refining a MHP intermediate product from a conventional or existing nickel laterite process, but also provides schemes as shown in Figure 2 for upstream processing of nickel laterite ores or other nickel bearing materials and solutions to directly produce qualified feed solution suitable for subsequent purification processes (Figure 3, Figure 4, Figure 5 and Figure 6), or alternatively to produce a MHP (Figure 2) desirable for the refining 28 using the schemes described herein as shown in Figure 1.
- the scheme options for overall processing of nickel laterite ores or nickel bearing materials and solutions are described as follows:
- Jarosite / alunite precipitation was employed in prior arts for removal or control of iron and aluminium concentrations and/or for generation of acid, wherein alkali metal salts (Na 2 C0 3 or Na 2 S0 4 ) or ammonium salt such as (NH 4 ) 2 S0 4 are added.
- the present processes aim to utilise the jarosite / alunite precipitation for removal of alkali metal ions (Na + , K + ) or monovalent cation (NH 4 + ) species wherein preferably above the stoichiometric amounts of Fe 3+ and Al 3+ according to reaction (1) are required.
- Leaching with conventional leaching methods such as high-pressure acid leaching (F1PAL) and atmospheric leaching (AL) can be simultaneously performed with the jarosite / alunite precipitation in one step (156) or performed in successive steps of leaching (152) and jarosite / alunite (154) under the conditions as described above for step (115) ( Figure 1).
- F1PAL high-pressure acid leaching
- AL atmospheric leaching
- the slurry (155 or 157) is neutralised (158) with a base reagent (121) to remove remaining iron as goethite / hydroxide and aluminium as alumina / hydroxides, together with other metal hydroxides such as chromium and copper hydroxides.
- An oxidant (103) can be optionally added to oxidise any Fe(II) to Fe(III) and Mn(II) to stable solid Mn(IV) oxides under the conditions as described above for the neutralisation step (122) ( Figure 1).
- the slurry (159) from the neutralisation (158) goes through the solid / liquid separation (160) to obtain the feed solution (162) which is substantially free of monovalent cations (Na + , K + , NF1 4 + ), iron, aluminium and chromium and to dispose the residue (161) containing jarosite / alunite, goethite, alumina and hydroxides of iron, aluminium, chromium and copper, and Mn(III/IV) oxides.
- monovalent cations Na + , K + , NF1 4 +
- the feed solution (162) can be, if desired, fed to the subsequent purification schemes as shown in Figure 3, Figure 4, Figure 5 and Figure 6.
- the feed solution (162) may be concentrated by means of water separation, e.g. by membrane distillation, 29 before being fed to the subsequent purification schemes as shown in Figure 3, Figure 4, Figure 5 and Figure 6.
- the feed solution (162) goes through the mixed hydroxide precipitation (163) to produce MHP (164) which is then leached in step (112) ( Figure 1) to produce the feed solution (126) for further purification using the schemes shown in Figure 3, Figure 4, Figure 5 and Figure 6 to produce high purity, battery grade nickel sulphate and cobalt sulphate.
- the MHP feeding the flowsheet shown in Figure 1 allows the presence of iron and aluminium at a desirable ratio relatively to the alkali metal ions and monovalent cation species required for subsequent jarosite / alunite precipitation. Therefore, a deep removal of the iron and aluminium by primary neutralisation is not necessary, and the recycling of the last stage iron and aluminium hydroxide precipitate as practiced in the conventional process can be reduced or eliminated.
- Scheme Options 2 and principles for control of iron and aluminium contents in the MHP are described below.
- the PLS (183) is neutralised with a base reagent such as limestone or lime (185) to precipitate iron and aluminium (184) under controlled conditions to leave partial Fe(III) and Al(III) relative to monovalent cations (Na + + K + + NH 4 + ) in the PLS which is measured based on their ratios in the MHP (191), preferably in the range of (3 - 6): 1 , and more preferably at (4 - 5): 1.
- a base reagent such as limestone or lime (185) to precipitate iron and aluminium (184) under controlled conditions to leave partial Fe(III) and Al(III) relative to monovalent cations (Na + + K + + NH 4 + ) in the PLS which is measured based on their ratios in the MHP (191), preferably in the range of (3 - 6): 1 , and more preferably at (4 - 5): 1.
- the residue (188) is disposed, and the PLS (189) is fed to the mixed hydroxide precipitation (190) by addition of a base reagent such as magnesium oxide / hydroxide (14) to produce the MHP (191) with a desirable ratio of [Fe(III) + Al(III)] to (Na + + K + + NH 4 + ) for jarosite / alunite precipitation (115 or 119) to remove the monovalent cations (Na + + K + + NH 4 + ) in subsequent refining processes.
- a base reagent such as magnesium oxide / hydroxide (14)
- the stripped organic (211) is preloaded (212) with nickel sulphate (126 or 162, or 221 or 331) shown in Figure 3 and (419 or 503) shown in Figure 5 with a base reagent (213) such as sodium hydroxide or carbonate or ammonia / ammonium hydroxide to produce the nickel preloaded organic (216) and sodium sulphate or ammonium sulphate by-products (215).
- a base reagent such as sodium hydroxide or carbonate or ammonia / ammonium hydroxide
- the stripped organic can be pre-neutralised (222) with a base reagent (213) such as sodium hydroxide or carbonate or ammonia / ammonium hydroxide to produce the pre-neutralised organic (223) for preloading (212) of nickel by exchange.
- the preloaded organic (216) is scrubbed (217) with a scrub solution (218) containing water and/or dilute sulphuric acid and/or nickel sulphate to remove the extracted and entrained sodium or ammonium ions to scrub liquor (219) which is recycled to the preloading (212).
- the scrubbed / preloaded organic (220) is fed to Impurity Extraction (201), wherein the impurities of Zn(II), Mn(II), Cu(II) and Ca(II), Cd(II), Pb(II) and other impurities having higher affinities to the organic extractant than cobalt and nickel in the feed solution (126 or 162) are extracted into the organic phase by exchange of the preloaded nickel into the aqueous phase.
- Minimum pH control with sulphuric acid for maintaining a desirable pH profile for the multiple stages of extraction may be optionally employed, if desired.
- the loaded organic (202) is scrubbed (203) with a scrub solution (205) of water and/or sulphuric acid and/or metal sulphates to remove the extracted nickel and cobalt to the scrub liquor (204) which is recycled to the extraction (201).
- a scrub solution (205) of water and/or sulphuric acid and/or metal sulphates to remove the extracted nickel and cobalt to the scrub liquor (204) which is recycled to the extraction (201).
- the scrubbed organic (206) is stripped (207) with a strip solution (208) of sulphuric acid or hydrochloric acid (HC1) to regenerate the organic (211) for feeding the preloading (212) or optionally feeding the pre -neutralisation (222).
- a strip solution (208) of sulphuric acid or hydrochloric acid (HC1) to regenerate the organic (211) for feeding the preloading (212) or optionally feeding the pre -neutralisation (222).
- H 2 S0 4 or HC1 (208), for the stripping (207) depends on the concentration of calcium. If the calcium concentration is significantly below its saturation to form gypsum, sulphuric acid for stripping under controlled conditions to avoid formation of gypsum is 31 preferred due to the identical sulphate matrix. If the concentration of calcium is high, hydrochloric acid can be employed to avoid the formation of gypsum. If hydrochloric acid is used, washing stage(s) may be required to remove the entrained chloride ions in the organic phase before transferring the stripped organic (211) for preloading (212) or pre -neutralisation (222).
- the strip liquor (210) containing the impurities can be further treated to separate and recover specific metals of interest.
- the zinc can be separated from other impurities through selective stripping to produce a separate by-product, if desired.
- the present disclosure provides the SX scheme using an organophosphinic acid, e.g. bis(2,4,4- trimethylpentyl) phosphinic acid (Cyanex ® 272 or Ionquest ® 290) in a hydrocarbon diluent and optionally in the presence of an organic phase modifier to extract both cobalt and magnesium (301) from the raffinate (221) and separation of the magnesium from cobalt within the circuit.
- organophosphinic acid e.g. bis(2,4,4- trimethylpentyl) phosphinic acid (Cyanex ® 272 or Ionquest ® 290) in a hydrocarbon diluent and optionally in the presence of an organic phase modifier to extract both cobalt and magnesium (301) from the raffinate (221) and separation of the magnesium from cobalt within the circuit.
- This scheme comprises of the following steps:
- the stripped organic (324) is preloaded (325) with nickel sulphate (221 or 331) available within the process with a base reagent (213) such as ammonium hydroxide or carbonate, or sodium hydroxide for neutralisation to produce the nickel preloaded organic (326) and ammonium sulphate or sodium sulphate by-products (215).
- a base reagent such as ammonium hydroxide or carbonate, or sodium hydroxide for neutralisation to produce the nickel preloaded organic (326) and ammonium sulphate or sodium sulphate by-products (215).
- the stripped organic (324) can be pre -neutralised (332) with a base reagent (213) such as sodium hydroxide or carbonate, or ammonium hydroxide to produce the pre neutralised organic (333) for preloading (325) of nickel by exchange.
- the preloaded organic (326) is scrubbed (327) with a scrub solution (328) of water and/or sulphuric acid and/or nickel sulphate to remove the extracted and entrained sodium and ammonium ions from the organic phase into the scrub liquor (329) which is recycled to the preloading (325).
- a scrub solution 328
- sulphuric acid and/or nickel sulphate to remove the extracted and entrained sodium and ammonium ions from the organic phase into the scrub liquor (329) which is recycled to the preloading (325).
- the loaded organic (302) is firstly scrubbed (303) with a scrub solution (304) of water and/or sulphuric acid and/or cobalt sulphate to selectively remove the extracted nickel from the organic phase to the scrub liquor (305) which is recycled to the Co/Mg extraction (301).
- a scrub solution (304) of water and/or sulphuric acid and/or cobalt sulphate to selectively remove the extracted nickel from the organic phase to the scrub liquor (305) which is recycled to the Co/Mg extraction (301).
- the nickel scrubbed organic (306) is further scrubbed (307) with a scrub solution (308) of water and/or sulphuric acid and/or cobalt sulphate solution to remove the extracted magnesium from the organic phase to obtain the magnesium rich scrub liquor (309) with some co-scrubbed cobalt.
- a scrub solution (308) of water and/or sulphuric acid and/or cobalt sulphate solution to remove the extracted magnesium from the organic phase to obtain the magnesium rich scrub liquor (309) with some co-scrubbed cobalt.
- the co-scrubbed cobalt in the magnesium rich scrub liquor (309) is then extracted (310) with a minor portion of the stripped organic (321), wherein a base reagent (311) such as ammonia / ammonium hydroxide or sodium hydroxide or carbonate can be directly used for the neutralisation, if desired.
- a base reagent such as ammonia / ammonium hydroxide or sodium hydroxide or carbonate
- the stripped organic (321) can be preloaded (334) with a solution of magnesium sulphate (MgS0 4 ) (312) and a base reagent (311) for pH adjustment, preferably magnesium oxide / hydroxide and/or ammonia / ammonium hydroxide, or sodium hydroxide or carbonate, and then fed for the extraction of cobalt (310) through the exchange of the preloaded base metal.
- the entrained or extracted ammonium or sodium in the organic phase in the above steps (334 and 310) can be removed from the organic phase by a scrubbing step (314) to the scrub liquor (316) which is recycled to the extraction (310).
- the magnesium rich raffinate (312) can be further processed to produce magnesium sulphate, or magnesium oxide or hydroxide for recycling as a base (311) for preloading and neutralisation in the process.
- the minor stream of cobalt loaded organic (317) is merged with the main stream of nickel scrubbed organic (306) as the feed (318) for scrubbing of magnesium (307).
- the magnesium scrubbed organic (319) is stripped (320) with a strip solution (323) of sulfuric acid to obtain cobalt loaded strip liquor (322) and to regenerate the organic (321 and 324) which is recycled to the preloading (325 or 334).
- the cobalt can be stripped by other acids such as hydrochloride acid and nitric acid, respectively, for production of other salt products, wherein washing steps before and after the stripping may be needed to avoid cross contaminations by organic phase carrying-over.
- the cobalt loaded strip liquor (322) containing minor zinc and copper can be purified by IX (601) using a type of iminodiacetic acid resin such as Lewatit ® TP 207 for removal of copper, followed by zinc IX with a D2EHPA impregnated resin such as Lewatit ® VP OC 1026.
- a type of iminodiacetic acid resin such as Lewatit ® TP 207 for removal of copper
- a D2EHPA impregnated resin such as Lewatit ® VP OC 1026.
- 33 aminophosphonic acid chelating resin such as Purolite® S950 can be potentially employed for removal of both copper and zinc.
- nickel can be separated from cobalt by bis-picolylamine chelating resin such as Dowex® M4195.
- Minor manganese may also be present in the cobalt loaded strip liquor (322), which can be selectively precipitated as Mn(III/IV) oxide with an oxidant such as ozone, a mixture of SC C ⁇ air) at a ratio functioning as an oxidant, peroxymonosulfuric acid (Caro’s acid) and peroxydisulfuric acid.
- an oxidant such as ozone, a mixture of SC C ⁇ air
- the purified cobalt liquor (603) is fed to cobalt crystallisation (604) to produce high purity, battery grade hydrated cobalt sulphate (605).
- the cobalt loaded strip liquor (322) can be purified to remove various minor impurities such as zinc, copper, calcium, manganese, cadmium, lead and other impurities by SX with an orgnophosphoric acid (D2EHPA) extractant as described above, if desired.
- D2EHPA orgnophosphoric acid
- ammonium sulphate produced in the neutralisations will end up with nickel in the SX raffinate (331). Partial ammonium sulphate would be crystallised with the hydrated nickel sulphate (703) as ammonium nickel sulphate double salt.
- a thermal decomposition step (704 or 706) is designed to convert the double sulphate salt to nickel sulphate (708), wherein the ammonium sulphate can be decomposed into ammonia, sulphur trioxide and nitrogenous gases (705) at temperature above 280 °C. It is preferable to selectively 34 decompose only the ammonium component to ammonia (222) for recycling as the base regent, for which an oxide / hydroxide such as nickel oxide /hydroxide (707) may be added to form nickel sulphate (708). Nitrate, nitrite, nitrous components, if exists, would be at least partially removed in this step.
- the present disclosure provides alternative SX schemes to firstly extract cobalt from magnesium and nickel, and then to extract magnesium from nickel with the same Cyanex ® 272 as shown in Figure 5.
- the SX scheme for removal of the impurities typically Zn(II), Mn(II), Cu(II) and Ca(II)
- D2EFIPA are the same as that described above and shown in Figure 3.
- the stripped Cyanex ® 272 (410 and 511) is preloaded (411) with nickel sulphate (419 or 503) available within the process, which produces nickel loaded organic (413) and ammonium sulphate or sodium sulphate by-products (215) with a base reagent (213) such as sodium hydroxide or carbonate, or ammonia / ammonium hydroxide.
- a base reagent such as sodium hydroxide or carbonate, or ammonia / ammonium hydroxide.
- the stripped organic (410 and 511) can be pre -neutralised (420) with a base reagent (213) to produce the pre-neutralised organic (421) for preloading (411) of nickel by exchange.
- the preloaded organic (413) is scrubbed (414) with a scrub solution (415) of water and/or sulphuric acid, and/or nickel sulphate to remove the extracted and entrained sodium or ammonium ions from the organic phase into the scrub liquor (416) which is recycled to the preloading (411).
- a scrub solution (415) of water and/or sulphuric acid, and/or nickel sulphate to remove the extracted and entrained sodium or ammonium ions from the organic phase into the scrub liquor (416) which is recycled to the preloading (411).
- the cobalt loaded organic (402) is scrubbed (403) with a scrub solution (404) comprising water, and/or sulphuric acid, and/or cobalt sulphate to remove the extracted nickel and magnesium into the scrub liquor (405) which is recycled to the cobalt extraction (401).
- a scrub solution comprising water, and/or sulphuric acid, and/or cobalt sulphate to remove the extracted nickel and magnesium into the scrub liquor (405) which is recycled to the cobalt extraction (401).
- cobalt loaded strip liquor (409) containing minor zinc and copper is purified by IX (601) as described above. If needed, minor nickel can be removed by IX (601) using bis-picolylamine chelating resin and minor manganese can be removed by oxidation with an oxidant such as Caro’s acid.
- the cobalt loaded strip liquor (409) can be purified (601) to remove various minor impurities such as zinc, copper, calcium, manganese, cadmium, lead and other impurities by SX with an orgnophosphoric acid (D2EHPA) extractant as described above, if desired.
- D2EHPA orgnophosphoric acid
- the purified cobalt liquor (603) is fed to cobalt crystallisation (604) to produce high purity, battery grade hydrated cobalt sulphate (605).
- the magnesium loaded organic (504) is scrubbed (505) with a scrub solution (506) comprising water, and/or sulphuric acid to remove the extracted nickel into the scrub liquor (507) which is recycled to the magnesium extraction (501).
- a scrub solution 506 comprising water, and/or sulphuric acid to remove the extracted nickel into the scrub liquor (507) which is recycled to the magnesium extraction (501).
- the scrubbed organic (508) is stripped (509) with a strip solution (510) of sulfuric acid to obtain magnesium loaded strip liquor (512) and to regenerate the organic (511) which is recycled to the preloading (411).
- the magnesium loaded strip liquor (512) contain magnesium sulphate (513) can be crystallised to produce magnesium sulphate by-product or can be further processed to produce MgO / Mg(OH) 2 by products which can be used in the process as a base reagent.
- the raffinate (503) from the magnesium solvent extraction (501) containing nickel is directly fed to nickel crystallisation (701) to produce high purity, battery grade hydrated nickel sulphate (702).
- the present disclosure provides an alternative approach and scheme ( Figure 6) using direct neutralisation of the acid produced during the SX processes (201), (401) and (501) with ammonia / ammonium hydroxide (222), instead of the preloading approach and scheme as shown in ( Figure 5).
- the ratios of the aqueous to the organic (A/O) is chosen and controlled to avoid the formation of ammonium nickel sulphate double salt during the SX process.
- ammonium sulphate produced from the neutralisation of the acid in the SX processes (201, 401 and 501) end up with nickel in the final SX raffinate (503). Partial ammonium sulphate would be crystallised with nickel sulphate (703) as ammonium nickel sulphate double salt.
- a thermal decomposition step (704 or 706) is designed to convert the double sulphate salt to nickel sulphate (708), wherein the ammonium sulphate can be decomposed into ammonia, sulphur trioxide and nitrogenous gases (705) at a temperature above 280 °C. It is preferable to selectively decompose only the ammonium component to ammonia (222) for recycling as the base regent, for which an oxide / hydroxide such as nickel oxide /hydroxide (707) may be added to form nickel sulphate (708). Nitrate, nitrite, nitrous components, if existing, would be at least partially removed in this step.
- the ratios of Ni Na and Ni/K increased from 142 to 3929 and from 378 to 3522, respectively, corresponding to 25 ppm Na and less than 28 ppm K in the feed solution normalised to 100 g/L Ni, if the washed MHP is fully dissolved.
- the ratios of Ni/Na and Ni/K increased from 142 to 26281 and 378 to 12533, respectively, corresponding to less than 10 ppm Na and less than 20 ppm K in the final nickel sulphate product containing 22.3% Ni, assuming that all the Na and K enter the nickel sulphate product.
- This example presents the jarosite precipitation using a feed with the compositions shown in Table 6.
- the feed was heated to 95 °C with agitation and aeration, while 20 grams of jarosite seed produced from a previous jarosite precipitation was added.
- the slurry pH was adjusted and maintained in the pH range of 1.8 - 2.0 by addition of washed MHP obtained as described in Example 1.
- the slurry was filtered by vacuum using Macherey -Nagel MN615 filter paper.
- the compositions of the final solution and the washed solid are given in Table 6.
- the sodium in the solution decreased from the feed 118 mg/L to 3.1 mg/L, corresponding to 99.8% Na precipitation efficiency and an increase of the Ni/Na ratio from 770 to 31119.
- the nickel and cobalt in the jarosite precipitate were measured at 0.03% and 0.07%, respectively.
- This example shows the conversion of the soluble Mn(II) to stable solid Mn(IV) oxides in a MHP (44.46% Ni, 4.6% Co, 0.88% Mn) with air and S0 2 /air mixture.
- the MHP was repulped in deionised water at 29% (dry solid) pulp density and 60 °C.
- the slurry was constantly agitated with a continuous sparging of air or the mixture of sulphuric dioxide (S0 2 ) and air at 0.5 - 1% (v/v) S0 2 .
- Mn(II) In principle, a complete conversion of Mn(II) can be achieved, if desired. In this process, the complete conversion of Mn(II) is optional, as the remaining Mn(II) at a lower level can be removed by subsequent SX scheme with D2EHPA.
- the precipitated cobalt and nickel in the final solid residue were 0.88% and 0.08%, respectively, with air only for 90 minutes and 3.37% and 0.09%, respectively, with alternatively S0 2 /air mixture and air for 300 minutes. Therefore, the parameters for the conversion such as pH, flowrate, S0 2 /air(0 2 ) ratio, and residence time can be optimised for desirable conversion efficiency of Mn(II) with minimum conversion of nickel and cobalt.
- the McCabe-Thiele diagram constructed based on the data suggests two to three theoretical stages for scrubbing the loaded sodium at an operating A/O ratio of about 1:10.
- the scrubbing of the nickel was reasonably in the range of 10 - 15%, which is recycled to the preloading section in a continuous operation.
- the scrubbing conditions with respect to the composition of the scrub solution, scrubbing pH, A/O ratios and stages can be further optimised. In a continuous SX process with multiple stages, an optimum pH profile can be applied.
- This example presents the extraction distribution isotherms for extraction of the impurities (Zn(II), Cu(II), Mn(II) and Ca(II)) with the nickel (6.3 g/L) preloaded 10% (v/v) D2EHPA in Exxsol 40
- Portions of the nickel preloaded organic were separately contacted with respective portions of a synthetic PLS (g/L: 93.1 Ni, 9.23 Co, 2.80 Mg, 3.2 Zn, 0.08 Mn, 0.034 Ca and 0.087 Cu) at various A/O ratios, pH ⁇ 3.1 and 40 °C for 10 minutes with a constant mechanical stirring.
- a synthetic PLS g/L: 93.1 Ni, 9.23 Co, 2.80 Mg, 3.2 Zn, 0.08 Mn, 0.034 Ca and 0.087 Cu
- the metal distribution isotherms are shown in Figure 10.
- the negative extraction efficiency of nickel indicated that the metal impurities were extracted through the replacement of the preloaded nickel.
- the McCabe-Thiele diagrams shown in Figure 11 and Figure 12 suggest three theoretical extraction stages for extraction and separation of the impurities (Zn(II), Mn(II), Cu(II) and Ca(II)) from nickel and cobalt with 10% D2EHPA at an operating A/O ratio of 1.5.
- This example presents the preloading of 25% Cyanex ® 272 in Exxsol D80 with 56 g/L Ni (sulphate) at 50 °C and pH 6.8 - 7.0 with sodium hydroxide for neutralisation and pH control.
- the distribution isotherms and McCabe-Thiele diagram for nickel preloading are shown in Figure 13, predicting two to three theoretical stages for extraction of nickel at an operating A/O ratio of 1:4.
- This example demonstrates the scrubbing distribution isotherms for removal of the entrained and extracted sodium from the preloaded 25% Cyanex ® 272 in Exxsol D80 at pH 5.5 using a scrub solution of 65 g/L Ni (sulphate).
- the metal distribution isotherms and McCabe-Thiele diagram constructed based on the data are shown in Figure 14, suggesting two to three theoretical stages for scrubbing of the sodium at an operation A/O ratio of 1:15 with reasonable scrubbing of nickel which can be further minimised in multiple stage operation with an optimum pH profile.
- the scrub liquor can be recycled to the preloading section for recovery of nickel in a continuous operation.
- the present disclosure provides an SX scheme for extraction of both cobalt and magnesium and then separate the loaded magnesium from cobalt through a scrubbing scheme within the SX circuit.
- This example presents the metal distribution isotherms for the extraction of cobalt and magnesium and separation from nickel using the nickel preloaded (14.44 g/L Ni) organic solution of 25% (v/v) Cyanex ® 272 in Exxsol D80 and a synthetic solution containing (g/L) 103 Ni, 11.4 Co and 3.2 Mg.
- Example 10 Scrubbing nickel and magnesium from the loaded organic
- This disclosure provides a process to enable simple separation of alkali metals and monovalent cation species.
- This disclosure provides novel SX schemes for extraction and separation of respective cobalt and magnesium from nickel in one SX circuit, or in two separate SX circuits. Both schemes for separation of magnesium from nickel are novel and the former in one SX circuit offers minimum SX requirement and thus minimum capital and operating costs.
- This disclosure provides two approaches and schemes for neutralisation of the acid produced in the SX processes: (a) preloading the organic with nickel sulphate available 42 within the process to avoid contamination of the system from the base reagents, or (b) direct neutralisation with ammonia / ammonium hydroxide which is then removed from the final hydrated nickel sulphate by thermal decomposition preferably to ammonia for recycling as the base reagent in the process.
- This disclosure provides oxidative precipitation methods for conversion of the soluble divalent manganese ions, Mn(II), into stable solid Mn(III/IV) oxides with minimum loss of nickel and cobalt in washing stage, and/or in subsequent oxidative neutralisation step for early rejection of manganese favourable for easy separation in subsequent purification by SX.
- This disclosure relates to refining processes for production of high purity, battery grade nickel sulphate and cobalt sulphate products from a wide range of feed materials, including, but not limited to:
- Nickel laterite ores or other nickel and cobalt containing materials • Nickel laterite ores or other nickel and cobalt containing materials
- a single embodiment may, for succinctness and/or to assist in understanding the scope of the disclosure, combine multiple features. It is to be understood that in such a case, these multiple features may be provided separately (in separate embodiments), or in any other suitable combination. Alternatively, where separate features are described in separate embodiments, these separate features may be combined into a single embodiment unless otherwise stated or implied. This also applies to the claims which can be recombined in any combination. That is a claim may be amended to include a feature defined in any other claim. Further a phrase referring to “at least one of’ a list of items refers to any combination of those items, including single members. As an example, “at least one of: a, b, or c” is intended to cover: a, b, c, a-b, a-c, b-c, and a-b-c.
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JP5706457B2 (ja) * | 2013-02-27 | 2015-04-22 | Jx日鉱日石金属株式会社 | 金属混合溶液からの金属の分離回収方法 |
CN108517409B (zh) * | 2018-04-04 | 2019-11-29 | 长沙矿冶研究院有限责任公司 | 一种从废旧动力电池正极废料中回收有价金属的方法 |
CN109097570B (zh) * | 2018-09-25 | 2020-06-19 | 中国科学院长春应用化学研究所 | 含氨基酸性膦萃取剂用于萃取分离钴和镍的用途和方法 |
CN109234526B (zh) * | 2018-11-26 | 2020-11-03 | 中国恩菲工程技术有限公司 | 红土镍矿的处理方法 |
EP3670686A1 (en) * | 2018-12-21 | 2020-06-24 | A.C.N. 630 589 507 Pty Ltd | Battery recycling process |
CN112342393B (zh) * | 2020-10-29 | 2022-10-18 | 湖南邦普循环科技有限公司 | 采用萃取法除三元电池材料浸出液中铝的方法 |
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CN117642519A (zh) | 2024-03-01 |
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KR20240019147A (ko) | 2024-02-14 |
AU2022271919A1 (en) | 2023-11-23 |
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