CN115094229B - Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore - Google Patents
Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore Download PDFInfo
- Publication number
- CN115094229B CN115094229B CN202210163883.2A CN202210163883A CN115094229B CN 115094229 B CN115094229 B CN 115094229B CN 202210163883 A CN202210163883 A CN 202210163883A CN 115094229 B CN115094229 B CN 115094229B
- Authority
- CN
- China
- Prior art keywords
- leaching
- cobalt
- slurry
- nickel
- scandium
- 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.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 68
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 68
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 79
- 239000002002 slurry Substances 0.000 claims abstract description 63
- 230000009467 reduction Effects 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 33
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 27
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 7
- 239000011504 laterite Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 59
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 235000012245 magnesium oxide Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 abstract description 19
- 239000010941 cobalt Substances 0.000 abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 14
- 239000013049 sediment Substances 0.000 abstract description 10
- 229910006540 α-FeOOH Inorganic materials 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- -1 iron ions Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910018661 Ni(OH) Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GKSSSCZSUUFNLN-UHFFFAOYSA-H [Sc+3].[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [Sc+3].[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-] GKSSSCZSUUFNLN-UHFFFAOYSA-H 0.000 description 2
- BDEWFESBPPTDSN-UHFFFAOYSA-N [Sc].[Co].[Ni] Chemical compound [Sc].[Co].[Ni] BDEWFESBPPTDSN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 235000001055 magnesium Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229940083599 sodium iodide Drugs 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229960005349 sulfur Drugs 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 229940044609 sulfur dioxide Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling scandium in cobalt nickel hydroxide prepared from lateritic nickel ores. The recovery method comprises the following steps: step S1, slurrying cobalt nickel hydroxide prepared from laterite nickel ore to obtain slurry; s2, regulating the pH value of the slurry to 0.8-3.0, and then carrying out reduction leaching treatment to reduce and leach high-valence metal elements in cobalt nickel hydroxide to obtain reduction slurry; s3, carrying out solid-liquid separation on the reduction slurry to obtain solid slag and leaching liquid; and S4, deironing the leaching solution by using a goethite method to form goethite type sediment and nickel-cobalt-containing solution for adsorbing or doping scandium. Selective reduction leaching of the slurry, leaching scandium, nickel and cobalt into the liquid, and Fe 3+ Is reduced to Fe 2+ ，MnO 2 Is dissolved to avoid coating the surfaces of metals such as nickel, cobalt, scandium and the like. In step S4, scandium-containing goethite crystals are separated from nickel cobalt by forming a precipitate of alpha-FeOOH crystals adsorbed or doped with ScOOH.
Description
Technical Field
The invention relates to the technical field of refining of laterite-nickel ores, in particular to a method for recycling scandium in cobalt nickel hydroxide prepared from laterite-nickel ores.
Background
The laterite-nickel ore wet smelting process comprises the procedures of acid leaching, impurity removal, nickel cobalt precipitation and the like. Cobalt nickel hydroxide precipitation is a relatively popular intermediate product obtained by hydrometallurgical laterite nickel ores.
The cobalt nickel hydroxide needs to be refined to obtain a pure nickel cobalt product, and a great amount of nickel laterite ores contain scandium which is a harmful impurity in nickel cobalt smelting and is a rare earth resource. The purpose of the cobalt nickel hydroxide refining process is to remove impurities from the system to obtain nickel cobalt metal or compounds thereof. The practice shows that after long-time storage, part of transition metals such as iron and manganese are oxidized, and the cobalt nickel hydroxide contains higher-content high-valence manganese oxide and manganese dioxide and wraps other metals, so that the cobalt nickel hydroxide is not easy to dissolve when conventionally leached by sulfuric acid, and the metal recovery rate of nickel cobalt scandium is reduced. Another problem is that during the leaching of cobalt nickel hydroxide, sc may be present in the leaching solution 3+ But Sc 3+ The concentration of scandium is low, and when scandium is removed and recovered by a scandium precipitation method alone, the precipitation rate is low, and precipitation is not easy to settle. Since the solution also contains iron ions (mostly Fe 3+ The small part is Fe 2+ ) And Al 3+ In the ion, CN103468948 is prepared by co-precipitating scandium and iron-aluminum by adjusting pH to 3.0 or above and precipitating scandium as hydroxide to remove and recover scandium from nickel-cobalt solution. However, in practice, it is found that when hydroxide coprecipitation is formed, the reaction end point is difficult to judge due to the special property of dissolving aluminum hydroxide and scandium hydroxide in strong alkali, the end point pH is difficult to accurately control, the recovery rate of scandium is low due to the fact that the pH value is too low, colloidal precipitation is easy to occur due to the fact that the pH value is too high, and the filtering performance is affected. And the reaction is carried out at a higher pH value, so that the slag entering loss of nickel, cobalt and manganese is increased.
Disclosure of Invention
The invention mainly aims to provide a method for recycling scandium in cobalt nickel hydroxide prepared from laterite-nickel ore, which aims to solve the problems of difficult scandium hydroxide precipitation and filtration and large nickel-cobalt loss during scandium recycling in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a recovery method of scandium in cobalt nickel hydroxide produced from lateritic nickel ore, the recovery method comprising: step S1, slurrying cobalt nickel hydroxide prepared from laterite nickel ore to obtain slurry; s2, regulating the pH value of the slurry to 0.8-3.0, and then carrying out reduction leaching treatment to reduce and leach high-valence metal elements in cobalt nickel hydroxide to obtain reduction slurry; s3, carrying out solid-liquid separation on the reduction slurry to obtain solid slag and leaching liquid; and S4, deironing the leaching solution by using a goethite method to form goethite type sediment and nickel-cobalt-containing solution for adsorbing or doping scandium.
Further, in step S1, the slurry is preferably subjected to a slurry treatment by ultrasonic dispersion, wherein the liquid-solid ratio of the slurry is 10:1 to 2:1.
Further, in the step S2, the pH of the slurry is adjusted to 0.8 to 3.0, preferably to 2.0 to 2.8, using an inorganic acid, preferably a mixed acid of any one or more of sulfuric acid, hydrochloric acid, and nitric acid.
Further, in the step S2, the slurry solution with the pH value of 0.8-3.0 is subjected to a reduction leaching treatment by using a reducing agent, wherein the reducing agent comprises one or more of low-valence compounds, non-metal simple substances and metal simple substances, preferably one or more of low-valence compounds comprising sodium borohydride, hydrogen sulfide, sodium hydrosulfide, sulfur dioxide, sodium sulfite, sodium metabisulfite and sodium iodide, preferably one or more of non-metal simple substances comprising hydrogen, sulfur and iodine, and preferably one or more of metal simple substances comprising sodium, magnesium, aluminum, copper, iron and zinc.
Further, the molar ratio of the reducing agent to the higher valence metal element is 1.1-1.3:1, and the higher valence metal element comprises Mn in the form of manganese dioxide 4+ And ferric iron in the hydroxide form.
Further, in the reducing leaching process of the step S2, the liquid-solid ratio of the reducing leaching system is controlled to be 12:1-2.5:1, the pH value is controlled to be 0.8-3.0, and the pH value is preferably controlled to be 1.0-2.5; preferably, the temperature of the reduction leaching is 15-90 ℃, and more preferably, 25-75 ℃; preferably, the time of the reduction leaching is 5-200 min.
Further, the step S4 includes: an oxidizing agent is added to the leachate to form a goethite-type precipitate that adsorbs or is doped with scandium.
Further, the oxidant is selected from any one or more of air, oxygen, ozone, hydrogen peroxide, chlorine and potassium permanganate.
Further, in the process of step S4, a neutralizing agent is added to the leachate to control the pH of the leachate to be between 2.0 and 3.0, preferably between 2.5 and 3.0; preferably, in the implementation process of the step S4, the temperature of the leaching solution is controlled to be 40-95 ℃, preferably 60-90 ℃.
Further, the neutralizing agent comprises any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, ammonium carbonate, ammonium bicarbonate, magnesium oxide, calcium oxide and limestone.
Further, in the step S4, the leaching solution is stirred at a stirring speed of 100 to 800rpm, preferably 300 to 500rpm.
By applying the technical scheme of the invention, firstly, cobalt nickel hydroxide is pulped to ensure that solid is uniformly dispersed in liquid to obtain slurry, then, the slurry is subjected to selective reduction leaching under an acidic condition, and scandium, nickel and cobalt are leached into the liquid in the leaching process by the following principles of Sc (OH) 3 +3H + ＝Sc 3+ +3H 2 O、Ni(OH) 2 +2H + ＝Ni 2+ +2H 2 O，Co(OH) 2 +2H + ＝Co 2+ +2H 2 O; the reducing agent simultaneously reduces and leaches high-valence iron and high-valence manganese in the cobalt nickel hydroxide, and the specific principle is as follows Fe (OH) 3 +3H + +e - ＝Fe 2+ +3H 2 O and MnO 2 +4H + +2e - ＝Mn 2+ +2H 2 O, on the one hand, fe 3+ Is reduced to Fe 2+ Providing raw materials for subsequent goethite method scandium enrichment, on the other hand, mnO 2 The dissolution is avoided, the coating of the alloy on the surfaces of metals such as nickel, cobalt, scandium and the like is avoided, and the recovery of the nickel, cobalt, scandium is ensured. Furthermore, fe during scandium enrichment in goethite-based precipitate formation 2+ And Sc (Sc) 3+ At the same time 2Fe 2+ +3H 2 O+0.5O 2 ＝2FeOOH+4H + And Sc (Sc) 3+ +2H 2 O＝ScOOH+3H + And the reaction is carried out, and alpha-FeOOH crystal sediment adsorbed or doped with ScOOH is formed by adsorbing on the surface of goethite or co-crystallizing, so that the scandium-containing goethite crystal is separated from nickel and cobalt, and the formed goethite is easy to filter, so that the scandium recovery efficiency is greatly improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 shows a schematic flow chart of a method for recovering scandium in cobalt nickel hydroxide produced by lateritic nickel ores according to an embodiment of the present invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
In the prior art of nickel cobalt smelting, scandium precipitation is typically removed by raising the pH to 3.0 and above, as described in the background of the present application. However, the above-described process forms colloidal Fe (OH) upon too high a pH, on the one hand, because the pH is difficult to control 3 And Sc (OH) 3 And this mixture has poor filtration properties, resulting in a fraction of scandium ions that is difficult to effectively remove from the solution and recover by precipitation enrichment; on the other hand, the increase of the pH value when iron and aluminum are removed can increase the slag entering loss of nickel, cobalt and manganese. In addition, after long-time storage, high-valence manganese oxides generated by manganese impurities in nickel cobalt hydroxide can coat metals such as nickel and cobalt, are not easy to dissolve when conventional leaching is carried out by acid, and the metal recovery rate of the nickel and cobalt is reduced. In order to solve the above problems, the present application provides a method for recovering scandium in cobalt nickel hydroxide produced in lateritic nickel ore, as shown in fig. 1, the method comprising: step S1, slurrying cobalt nickel hydroxide prepared from laterite nickel ore to obtain slurry; and S2, adjusting the pH value of the slurry to 0.8-3.0, performing reduction leaching treatment to reduce and leach high-valence metal elements in the cobalt nickel hydroxide to obtain reduction slurry; s3, carrying out solid-liquid separation on the reduction slurry to obtain solid slag and leaching liquid; and S4, deironing the leaching solution by using a goethite method to form goethite type sediment and nickel-cobalt-containing solution for adsorbing or doping scandium.
The above-mentioned high-valence metallic element refers to a case where the valence state is higher among metallic elements, such as trivalent iron, tetravalent manganese.
In order to obtain better scandium removal and enrichment effects, the method is improved on the basis of the conventional acid leaching and iron and aluminum removal processes of cobalt nickel hydroxide in the prior art, and scandium removal is achieved by generating iron and aluminum scandium hydroxide through pH value coprecipitation in an iron and aluminum removal stage. Firstly slurrying cobalt nickel hydroxide to uniformly disperse solids in a liquid to obtain slurry, and then carrying out selective reduction leaching under acidic conditions, wherein scandium, nickel and cobalt are leached into the liquid by the following principles in the leaching process, sc (OH) 3 +3H + ＝Sc 3+ +3H 2 O、Ni(OH) 2 +2H + ＝Ni 2+ +2H 2 O，Co(OH) 2 +2H + ＝Co 2+ +2H 2 O; the reducing agent simultaneously reduces and leaches high-valence iron and high-valence manganese in the cobalt nickel hydroxide, and the specific principle is as follows Fe (OH) 3 +3H + +e - ＝Fe 2+ +3H 2 O and MnO 2 +4H + +2e - ＝Mn 2+ +2H 2 O, on the one hand, fe 3+ Is reduced to Fe 2+ Providing raw materials for subsequent goethite method scandium enrichment, on the other hand, mnO 2 The dissolution is avoided, the coating of the alloy on the surfaces of metals such as nickel, cobalt, scandium and the like is avoided, and the recovery of the nickel, cobalt, scandium is ensured. Furthermore, fe during scandium enrichment in goethite-based precipitate formation 2+ And Sc (Sc) 3+ At the same time generate 2Fe 2+ +3H 2 O+0.5O 2 ＝2FeOOH+4H + And Sc (Sc) 3+ +2H 2 O＝ScOOH+3H + The scandium-containing goethite crystals are separated from nickel cobalt by adsorbing on the goethite surface or co-crystallizing to form alpha-FeOOH crystal precipitate adsorbed or doped with ScOOHThe formed goethite is crystal and is easy to filter, so that scandium recovery efficiency is greatly improved.
In order that the cobalt nickel hydroxide may react sufficiently with the reagent during the reduction leaching process, as much metal as possible is dissolved in the solution, it is preferred that step S1 comprises: and mixing cobalt nickel hydroxide with water to obtain slurry, wherein the liquid-solid ratio of the slurry is 10:1-2:1. The dispersion degree of the nickel cobalt oxide slag in the slurry is improved by mixing the nickel cobalt hydroxide slag with more water, so that the subsequent leaching reaction is faster and more fully carried out. Preferably, the above-mentioned slurrying treatment is carried out by adopting ultrasonic dispersion, cobalt nickel hydroxide and water are mixed by utilizing the vibration and dispersion action of ultrasonic waves, and meanwhile, large solid particles in liquid slurry are smashed by utilizing the ultrasonic cavitation action of liquid, so that the dispersion degree of cobalt nickel hydroxide in the slurry is further improved, the subsequent leaching reaction rate is faster, and the leaching rate is higher.
The applicant finds that the leaching rate of scandium, nickel and cobalt can be improved by reducing the high-valence metal in the cobalt nickel hydroxide leaching reaction system, the principle of the method is related to the reduction and conversion of the high-valence oxide on the surface of cobalt nickel hydroxide solid particles into the low-valence compound which is easier to dissolve in water, and the speed of reduction leaching can be improved and the leaching rate of scandium, nickel and cobalt can be improved under the preferable acidity condition. In order to improve the leaching rate of nickel cobalt scandium, the acid leaching treatment is carried out by adopting acid commonly used in the prior art wet nickel cobalt smelting, preferably, in the step S2, the pH value of the slurry is adjusted to be 0.8-3.0 by adopting inorganic acid, and preferably, the pH value of the slurry is adjusted to be 2.0-2.8. In order to avoid the introduction of harmful impurities, it is preferable that the inorganic acid includes a mixed acid of any one or more of sulfuric acid, hydrochloric acid, and nitric acid. The acid is common inorganic acid, so that the recovery method has low cost and is easy to popularize.
In some embodiments, the slurry with pH value of 0.8-3.0 is preferably subjected to the reduction leaching treatment in the step S2 by using a reducing agent, wherein the reducing agent comprises one or more of low-valence compounds, non-metallic simple substances and metallic simple substances, and the low-valence compounds comprise sodium borohydride, hydrogen sulfide, sodium hydrosulfide and dioxygenOne or more of sulfur, sodium sulfite, sodium metabisulfite and sodium iodide, preferably the non-metallic element comprises one or more of hydrogen, sulfur and iodine, preferably the metallic element comprises any one or more of sodium, magnesium, aluminum, copper, iron and zinc. The reducing agent may be Fe (OH) 3 And MnO 2 Generating Fe (OH) 3 +3H + +e - ＝Fe 2+ +3H 2 O and MnO 2 +4H + +2e - ＝Mn 2+ +2H 2 O reacts, and other ions introduced do not affect the quality of the smelting products (for example, na + It is difficult to form a precipitate in an acidic environment).
Depending on the ratio of the metals in the cobalt nickel hydroxide and the theoretical ratio of reducing agent to tetravalent manganese and ferric iron when fully reacted in the reduction leaching treatment, it is preferred that the molar ratio of the reducing agent to the higher metal elements, including tetravalent manganese in the form of manganese dioxide and ferric iron in the form of hydroxide, be in the range of 1.1 to 1.3:1. In the above molar ratio, the metal ions can be dissolved as much as possible without wasting the reducing agent. Preferably, the liquid-solid ratio of the reduction leaching system is controlled to be 12:1-2.5:1, the pH value is controlled to be 0.8-3.0, and the pH value is preferably controlled to be 1.0-2.5 in the reduction leaching process of the step S2, so that the reaction can be performed more quickly and fully. The temperature of the reduction leaching is more preferably 15-90 ℃, and the temperature is more preferably 25-75 ℃; preferably, the time of the reduction leaching is 5 to 200min, so as to further improve the reaction progress.
The applicant has found through a great deal of research that scandium can form Scooh at a lower solution pH under specific concentration and temperature conditions, and forms goethite type eutectic precipitation with the simultaneously formed alpha-FeOOH, so that the precipitation rate and recovery rate of scandium are improved, and the formed precipitation has the effects of improving the filtration efficiency and increasing the separation coefficient of scandium and iron from nickel cobalt metal. The applicant has further studied to find that at a specific solution acidity, temperature, reaction time, anion and cation strength, and Fe 3+ And Sc (Sc) 3+ Under the condition of metal concentration, the goethite type alpha-FeOOH crystal sediment adsorbed or doped with the ScOOH can be formed. In some embodiments, it is preferred thatThe step S4 includes: adding an oxidant into the leaching solution to form a goethite type precipitate for adsorbing or doping scandium, controlling the oxidation speed of iron ions to be 20-200 mg/L/min, and controlling the concentration of ferric ions in the leaching solution to be less than or equal to 1g/L. By adding an oxidizing agent, fe can be made 2+ And Sc (Sc) 3+ At the same time generate 2Fe 2+ +3H 2 O+0.5O 2 ＝2FeOOH+4H + And Sc (Sc) 3+ +2H 2 O＝ScOOH+3H + And the coprecipitation reaction is carried out to form alpha-FeOOH crystal sediment doped with the ScOOH, so that the filtering difficulty is greatly reduced, and the scandium metal separation rate is improved. If Fe is 3+ When the concentration of ions is large, amorphous Fe (OH) which is not easy to filter is easily formed 3 The oxidation speed of ferric ions is controlled to be 20-200 mg/L/min by the addition speed, temperature and acidity of an oxidant, and the concentration of ferric ions in the leaching solution is controlled to be less than or equal to 1g/L, so that the condition that the Scooh cannot be adsorbed or doped or wrapped in time due to the fact that the goethite crystal grows too fast is avoided. Therefore, by controlling the adding speed of the oxidant, the removing rate of scandium from the solution is improved, and the enrichment and precipitation efficiency of scandium is improved.
The oxidizing agent of the present application may be selected among oxidizing agents commonly used in goethite process by those skilled in the art, and it is preferable that the above oxidizing agent is selected from any one or more of air, oxygen, ozone, hydrogen peroxide and potassium permanganate for the purpose of simplifying the system and saving costs. For example, the oxidation rate is controlled by controlling the flow rate of oxygen to be 1000 mL/min-2500 mL/min, preferably 1500-2000 mL/min.
The goethite method in the prior art needs to adjust pH and temperature to obtain alpha-FeOOH crystals. In order to make scandium removal effect and enrichment efficiency higher, it is preferable that a neutralizing agent is added to the leachate during the step S4 to control the pH value of the leachate to be 2.0-3.0, preferably 2.5-3.0; preferably, in the implementation process of the step S4, the temperature of the leaching solution is controlled to be 40-95 ℃, preferably 60-90 ℃.
The above neutralizing agent may be selected from neutralizing agents commonly used in goethite process, and in order to avoid the introduction of impurities, which may cause poor scandium precipitation and final smelting, it is preferable that the neutralizing agent includes any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, ammonium carbonate, ammonium bicarbonate, magnesium oxide, calcium oxide and limestone.
In one embodiment, the leaching solution is preferably stirred during step S4, at a stirring speed of 100 to 800rpm, preferably 300 to 500rpm. Through stirring, the continuous growth of alpha-FeOOH crystal grains can be further controlled, and the effect of co-precipitation formed by alpha-FeOOH doping or adsorption of ScOOH is ensured.
The beneficial effects of the present application are further illustrated below in conjunction with examples and comparative examples.
The method takes cobalt nickel hydroxide sediment which is obtained by carrying out sulfuric acid high-pressure acid leaching on a certain high-iron laterite nickel ore, removing impurities such as iron and aluminum from leaching liquid, adding alkali into impurity-removing purifying liquid for precipitation as an implementation object, and the main component of the cobalt nickel hydroxide sediment
As shown in table 1 (on a dry weight basis of cobalt nickel hydroxide precipitate).
TABLE 1
| Element(s) | Ni | Co | Mn | Sc | Fe | Al |
| Content% | 35.67 | 3.35 | 5.33 | 0.0085 | 0.526 | 0.411 |
Example 1
1) 314.3g (68.18% moisture content) of wet cobalt nickel hydroxide was slurried with water at a liquid to solid ratio of 5:1, performing ultrasonic dispersion at a frequency of 2 ten thousand hertz at a temperature of 20 ℃ for 10 minutes to obtain slurry.
2) Sulfuric acid with the concentration of 96.5% is added into the slurry, and the pH is adjusted to 2.0, so that acidified slurry is obtained.
3) Heating the acidified slurry to 70 ℃, adding 10% anhydrous sodium sulfite solution (serving as a reducing agent) into the acidified slurry to form a reduction leaching system, so that high valence metal ions (Mn) in the anhydrous sodium sulfite and cobalt nickel hydroxide 4+ Ferric iron) is 1.2:1, and keeping the liquid-solid ratio of the reduction leaching system to be 5:1, wherein the pH value of the reduction leaching system in the reaction process is 2.0. After reacting for 90min, a reduction slurry was obtained.
4) And (3) carrying out solid-liquid separation on the reduction slurry in a filtering mode to obtain solid slag and leaching liquid.
5) Heating the leaching solution to 70 ℃, introducing oxygen (serving as an oxidant) at a speed of 1500mL/min, adding a sodium carbonate solution (serving as a neutralizer) with a concentration of 10% to keep the pH value of the solution at 2.5, stirring at 400rpm for 200min, and controlling the oxidation speed of iron ions at 100mg/L/min to obtain the goethite type precipitate and nickel-cobalt-containing slurry for adsorbing or doping scandium.
6) And (3) carrying out solid-liquid separation on the slurry in the step (5) by adopting a filtering mode to obtain scandium-containing goethite type sediment solid slag and nickel-cobalt purifying liquid.
Example 2
The difference from example 1 is that in 3) the pH is adjusted to 1.0.
Example 3
The difference from example 1 is that in 3) the pH is adjusted to 1.5.
Example 4
The difference from example 1 is that in 3) the pH is adjusted to 2.5.
Example 5
The difference from example 1 is that in 3) the pH is adjusted to 3.0.
Example 6
The difference from example 1 is that the liquid-to-solid ratio in 1) is 10:1.
Example 7
The difference from example 1 is that the liquid-to-solid ratio in 1) is 2:1.
Example 8
The difference from example 1 is that in 2) the pH is adjusted to 0.8.
Example 9
The difference from example 1 is that in 2) the pH is adjusted to 2.8.
Example 10
The difference from example 1 is that in 2) the pH is adjusted to 3.0.
Example 11
The difference from example 1 is that the reducing agent in 3) is replaced by sulfur dioxide from an anhydrous sodium sulfite solution.
Example 12
The difference from example 1 is that the reducing agent in 3) is exchanged for iron powder from an anhydrous sodium sulfite solution.
Example 13
The difference from example 1 is that the reducing agent in 3) is replaced by zinc powder from an anhydrous sodium sulfite solution.
Example 14
The difference from example 1 is that in 3) anhydrous sodium sulfite is reacted with high valence metal ions (Mn) 4+ Ferric iron) is 1.1:1.
Example 15
The difference from example 1 is that in 3) anhydrous sodium sulfite is reacted with high valence metal ions (Mn) 4+ Ferric iron) is 1.3:1.
Example 16
The difference from example 1 is that in 3) anhydrous sodium sulfite is reacted with high valence metal ions (Mn) 4+ Ferric iron) is 0.8:1.
Example 17
The difference from example 1 is that 3) the liquid-to-solid ratio of the reduction leaching system is maintained at 12:1.
Example 18
The difference from example 1 is that 3) the liquid-to-solid ratio of the reduction leaching system is maintained at 7.5:1.
Example 19
The difference from example 1 is that 3) the liquid-to-solid ratio of the reduction leaching system is maintained at 2.5:1.
Example 20
The difference from example 1 is that in 3) the acidified slurry is heated to 90 ℃.
Example 21
The difference from example 1 is that in 3) the acidified slurry temperature is maintained at 50 ℃.
Example 22
The difference from example 1 is that in 3) the acidified slurry temperature is maintained at 25 ℃.
Example 23
The difference from example 1 is that the reaction time in 3) is 5min.
Example 24
The difference from example 1 is that in 5) oxygen is introduced at a rate of 1000 mL/min.
Example 25
The difference from example 1 is that in 5) oxygen is introduced at a rate of 2000 mL/min.
Example 26
The difference from example 1 is that in 5) oxygen is introduced at a rate of 2500 mL/min.
Example 27
The difference from example 1 is that hydrogen peroxide with a concentration of 30% is added in 5) at a rate of 15 mL/min.
Example 28
The difference from example 1 is that 5) an aqueous potassium permanganate solution having a concentration of 3mol/L was added at a rate of 10 mL/min.
Example 29
The difference from example 1 is that the hot tapping in 5) is heated to 60 ℃.
Example 30
The difference from example 1 is that the hot-tapping is heated to 80℃in 5).
Example 31
The difference from example 1 is that the heating of the effluent to 90℃is carried out in 5).
Example 32
The difference from example 1 is that in 5) the solution pH is kept at 2.8.
Example 33
The difference from example 1 is that in 5) the solution pH is kept at 2.0.
Example 34
The difference from example 1 is that in 5) the solution pH is kept at 1.5.
Example 35
The difference from example 1 is that in 5) the solution pH is kept at 1.0.
Example 36
The difference from example 1 is that 5) the neutralizing agent is sodium hydroxide solution with a concentration of 15%.
Example 37
The difference from example 1 is that 5) the neutralizing agent is an ammonium carbonate solution with a concentration of 10%.
Example 38
The difference from example 1 is that 5) the neutralizing agent is calcium oxide.
Example 39
The difference from example 1 is that 5) the neutralizing agent is magnesium oxide.
Example 40
The difference from example 1 is that in 5) stirring is carried out at 300 rpm.
Example 41
The difference from example 1 is that in 5) stirring is carried out at 500rpm.
Comparative example 1
1) 314.3g (68.18% moisture content) of wet cobalt nickel hydroxide was slurried with water at a liquid to solid ratio of 5:1, performing ultrasonic dispersion at a frequency of 2 ten thousand hertz at a temperature of 20 ℃ for 10 minutes to obtain slurry.
2) Adding sulfuric acid with the concentration of 96.5% into the slurry to adjust the pH to 2.0, and obtaining acidified slurry.
3) And (3) carrying out solid-liquid separation on the acidified slurry in a filtering mode to obtain solid slag and an acidified solution.
4) The acidified solution was heated to 70℃and 10% strength sodium carbonate (neutralizer) solution was added to maintain a pH of 5.5 and stirred at 400rpm for 200min to obtain scandium-adsorbed or doped ferric hydroxide precipitate and a nickel cobalt-containing solution.
5) And (3) carrying out solid-liquid separation on the slurry in the step (4) in a filtering mode to obtain scandium-containing precipitation solid slag and nickel-cobalt-containing solution, drying the precipitation, and then sampling and analyzing, wherein the content of the metal element is analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES), and the content of the metal element in the precipitation is calculated according to the content of the metal element.
Comparative example 2
The difference from comparative example 1 is that the pH was adjusted to 2.5 in 3).
Comparative example 3
The difference from comparative example 1 is that the pH was adjusted to 3.5 in 3).
Comparative example 4
The difference from comparative example 1 is that the pH was adjusted to 4.5 in 3).
Comparative example 5
1) 314.3g (68.18% moisture content) of wet cobalt nickel hydroxide was slurried with water at a liquid to solid ratio of 5:1, performing ultrasonic dispersion at a frequency of 2 ten thousand hertz at a temperature of 20 ℃ for 10 minutes to obtain slurry.
2) Adding sulfuric acid with the concentration of 96.5% into the slurry to adjust the pH to 2.0, and obtaining acidified slurry.
3) Heating the acidified slurry to 70 ℃, adding 10% anhydrous sodium sulfite solution (serving as a reducing agent) into the acidified slurry to form a reduction leaching system, so that high valence metal ions (Mn) in the anhydrous sodium sulfite and cobalt nickel hydroxide 4+ Iron (iii) mole)The ratio is 1.2:1, and keeping the liquid-solid ratio of the reduction leaching system to be 5:1, and the pH value of the reduction leaching system to be 2.0. After reacting for 90min, a reduction slurry was obtained.
4) And carrying out solid-liquid separation on the reduction slurry to obtain solid slag and leaching liquid.
5) Heating the leaching solution to 70 ℃, adding 10% sodium carbonate solution (serving as a neutralizer) to keep the pH at 5.5, and stirring at 40rpm for 200min to obtain scandium-adsorbed or doped ferric hydroxide precipitate and nickel-cobalt-containing solution (under the high pH condition, ferrous ions are oxidized into ferric ions by air).
6) And (3) carrying out solid-liquid separation on the slurry in the step (5) in a filtering mode to obtain scandium-containing precipitation solid slag and nickel-cobalt-containing solution, drying the precipitation, and then sampling and analyzing, wherein the content of the metal element is analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES), and the content of the metal element in the precipitation is calculated according to the content of the metal element.
Comparative example 6
The difference from comparative example 5 is that the pH was adjusted to 2.5 in 3).
Comparative example 7
The difference from comparative example 5 is that the pH was adjusted to 3.5 in 3).
Comparative example 8
The difference from comparative example 5 is that the pH was adjusted to 4.5 in 3).
The precipitates of each of examples and comparative examples were subjected to post-drying sampling analysis in which the content of the metal element was analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES), and calculated from the content of the metal element in the precipitates.
The final test results are shown in table 2.
TABLE 2
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
in order to obtain better scandium removal and enrichment effects, the method is improved on the basis of the conventional acid leaching and iron and aluminum removal processes of cobalt nickel hydroxide in the prior art, and scandium removal is achieved by generating iron and aluminum scandium hydroxide through pH value coprecipitation in an iron and aluminum removal stage. Firstly slurrying cobalt nickel hydroxide to uniformly disperse solids in a liquid to obtain slurry, and then carrying out selective reduction leaching under acidic conditions, wherein scandium, nickel and cobalt are leached into the liquid by the following principles in the leaching process, sc (OH) 3 +3H + ＝Sc 3+ +3H 2 O、Ni(OH) 2 +2H + ＝Ni 2+ +2H 2 O，Co(OH) 2 +2H + ＝Co 2+ +2H 2 O; the reducing agent simultaneously reduces and leaches high-valence iron and high-valence manganese in the cobalt nickel hydroxide, and the specific principle is as follows Fe (OH) 3 +3H + +e - ＝Fe 2+ +3H 2 O and MnO 2 +4H + +2e - ＝Mn 2+ +2H 2 O, on the one hand, fe 3+ Is reduced to Fe 2+ Providing raw materials for subsequent goethite method scandium enrichment, on the other hand, mnO 2 The dissolution is avoided, the coating of the alloy on the surfaces of metals such as nickel, cobalt, scandium and the like is avoided, and the recovery of the nickel, cobalt, scandium is ensured. Furthermore, fe during scandium enrichment in goethite-based precipitate formation 2+ And Sc (Sc) 3+ At the same time generate 2Fe 2+ +3H 2 O+0.5O 2 ＝2FeOOH+4H + And Sc (Sc) 3+ +2H 2 O＝ScOOH+3H + And the reaction is carried out, and alpha-FeOOH crystal sediment adsorbed or doped with ScOOH is formed by adsorbing on the surface of goethite or co-crystallizing, so that the scandium-containing goethite crystal is separated from nickel and cobalt, and the formed goethite is easy to filter, so that the scandium recovery efficiency is greatly improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (25)
1. A method for recycling scandium in cobalt nickel hydroxide prepared from lateritic nickel ore, which is characterized by comprising the following steps:
step S1, slurrying cobalt nickel hydroxide prepared from laterite nickel ore to obtain slurry;
s2, adjusting the pH value of the slurry to 0.8-3.0, and then performing reduction leaching treatment to obtain reduction slurry by reducing and leaching high-valence metal elements in the cobalt nickel hydroxide;
s3, carrying out solid-liquid separation on the reduction slurry to obtain solid slag and leaching liquid;
and S4, deironing the leaching solution by using a goethite method to form goethite type precipitation and nickel-cobalt-containing solution for adsorbing or doping scandium.
2. The recycling method according to claim 1, wherein in the step S1, the liquid-solid ratio of the slurry is 10:1 to 2:1.
3. The recycling method according to claim 1 or 2, characterized in that in the step S1, the slurrying treatment is performed using ultrasonic dispersion.
4. The recycling method according to claim 1, wherein the step S2 is performed by adjusting the pH of the slurry to 0.8-3.0 with an inorganic acid.
5. The recycling method according to claim 4, wherein the pH of the slurry is adjusted to 2.0-2.8.
6. The method according to claim 4 or 5, wherein the inorganic acid comprises a mixed acid of any one or more of sulfuric acid, hydrochloric acid, and nitric acid.
7. The recovery method according to claim 1, wherein the step S2 is characterized in that the slurry with the pH value of 0.8-3.0 is subjected to a reduction leaching treatment by using a reducing agent, and the reducing agent includes one or more of a low-valence compound, a non-metal simple substance and a metal simple substance.
8. The recovery method of claim 7, wherein the low valence compound comprises one or more of sodium borohydride, hydrogen sulfide, sodium hydrosulfide, sulfur dioxide, sodium sulfite, sodium metabisulfite, and sodium iodide.
9. The recovery method of claim 7, wherein the non-metallic element comprises one or more of hydrogen, sulfur, and iodine.
10. The recovery method of claim 7, wherein the elemental metal comprises any one or more of sodium, magnesium, aluminum, copper, iron, and zinc.
11. The recovery method according to claim 7, characterized in that the molar ratio of the reducing agent to the higher metal element including tetravalent manganese in the form of manganese dioxide and trivalent iron in the form of hydroxide is 1.1 to 1.3:1.
12. The recovery method according to any one of claims 7 to 11, wherein the liquid-solid ratio of the reduction leaching system is controlled to be 12:1 to 2.5:1 and the pH value is controlled to be 0.8 to 3.0 in the reduction leaching process of step S2.
13. The recovery method of claim 12, wherein the pH of the reducing leaching system is 1.0 to 2.5.
14. The recovery method according to any one of claims 7 to 11, wherein the temperature of the reductive leaching is 15-90 ℃.
15. The recovery method of claim 14, wherein the temperature of the reductive leaching is 25-75 ℃.
16. The recovery method according to any one of claims 7 to 11, characterized in that the time of the reductive leaching is 5 to 200min.
17. The recycling method according to claim 1, wherein the step S4 comprises:
an oxidizing agent is added to the leachate to form a goethite-type precipitate that adsorbs or is doped with scandium.
18. The recovery method according to claim 17, wherein the oxidizing agent is selected from any one or more of air, oxygen, ozone, hydrogen peroxide, chlorine, and potassium permanganate.
19. The method according to claim 17, wherein the step S4 is performed by adding a neutralizing agent to the leachate to control the pH of the leachate to be 2.0-3.0.
20. The method according to claim 19, wherein the step S4 is performed by adding the neutralizing agent to the leachate to control the pH of the leachate to be 2.5-3.0.
21. The method according to claim 17, wherein the temperature of the leaching solution is controlled to be 40-95 ℃ during the step S4.
22. The recovery method according to claim 21, wherein the temperature of the leachate is 60-90 ℃.
23. The recovery method of claim 19, wherein the neutralizing agent comprises any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, ammonium carbonate, ammonium bicarbonate, magnesium oxide, calcium oxide, and limestone.
24. The method according to claim 17, wherein the leaching solution is stirred at a stirring speed of 100 to 800rpm during the step S4.
25. The recycling method according to claim 24, wherein the stirring speed is 300 to 500rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210163883.2A CN115094229B (en) | 2022-02-22 | 2022-02-22 | Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210163883.2A CN115094229B (en) | 2022-02-22 | 2022-02-22 | Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115094229A CN115094229A (en) | 2022-09-23 |
| CN115094229B true CN115094229B (en) | 2024-02-27 |
Family
ID=83287970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210163883.2A Active CN115094229B (en) | 2022-02-22 | 2022-02-22 | Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115094229B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464344A (en) * | 1979-05-25 | 1984-08-07 | Saikkonen Pekka J | Process for recovering non-ferrous metal values from ores, concentrates, oxidic roasting products or slags |
| US4816233A (en) * | 1987-09-11 | 1989-03-28 | Gte Laboratories Incorporated | Ion exchange method for the recovery of scandium |
| JPH06340426A (en) * | 1993-04-07 | 1994-12-13 | Fuji Photo Film Co Ltd | Production of hematite particle and production of ferromagnetic powder for magnetic recording using the same and magnetic recording medium |
| JP2002151068A (en) * | 2000-04-19 | 2002-05-24 | Japan Storage Battery Co Ltd | Positive electrode active material for secondary battery and its manufacturing method and non aqueous electrolyte secondary battery equipped with it |
| CN102030355A (en) * | 2010-10-27 | 2011-04-27 | 攀枝花市硕盛工贸有限公司 | Process for extracting discandium trioxide by utilizing waste acid from titanium dioxide plants |
| WO2015071848A1 (en) * | 2013-11-18 | 2015-05-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recovering metals contained in an ni-mh battery |
| CN112210679A (en) * | 2020-10-23 | 2021-01-12 | 中国恩菲工程技术有限公司 | Method for preparing nickel sulfate from nickel hydroxide cobalt |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2015252121B2 (en) * | 2014-11-05 | 2020-10-22 | Scandium International Mining Corporation | Systems and methodologies for direct acid leaching of scandium-bearing ores |
-
2022
- 2022-02-22 CN CN202210163883.2A patent/CN115094229B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464344A (en) * | 1979-05-25 | 1984-08-07 | Saikkonen Pekka J | Process for recovering non-ferrous metal values from ores, concentrates, oxidic roasting products or slags |
| US4816233A (en) * | 1987-09-11 | 1989-03-28 | Gte Laboratories Incorporated | Ion exchange method for the recovery of scandium |
| JPH06340426A (en) * | 1993-04-07 | 1994-12-13 | Fuji Photo Film Co Ltd | Production of hematite particle and production of ferromagnetic powder for magnetic recording using the same and magnetic recording medium |
| JP2002151068A (en) * | 2000-04-19 | 2002-05-24 | Japan Storage Battery Co Ltd | Positive electrode active material for secondary battery and its manufacturing method and non aqueous electrolyte secondary battery equipped with it |
| CN102030355A (en) * | 2010-10-27 | 2011-04-27 | 攀枝花市硕盛工贸有限公司 | Process for extracting discandium trioxide by utilizing waste acid from titanium dioxide plants |
| WO2015071848A1 (en) * | 2013-11-18 | 2015-05-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recovering metals contained in an ni-mh battery |
| CN112210679A (en) * | 2020-10-23 | 2021-01-12 | 中国恩菲工程技术有限公司 | Method for preparing nickel sulfate from nickel hydroxide cobalt |
Non-Patent Citations (2)
| Title |
|---|
| Petrology and geochemistry of scandium in New Caledonian Ni-Co laterites;Teitler, Y 等;Journal of Geochemical Exploration;第131-155页 * |
| 含钴高温合金废料的综合利用;蔡传算等;中国有色金属学报(第01期);第49-52页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115094229A (en) | 2022-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5652503B2 (en) | Scandium recovery method | |
| CA2938134C (en) | Scandium recovery method | |
| WO2011111407A1 (en) | Method for wastewater treatment for wastewater containing aluminum, magnesium and manganese | |
| CN110114482B (en) | Process for the recovery of nickel and cobalt from a feedstock containing nickel, iron and cobalt | |
| CA2980523C (en) | Method for manufacturing nickel and cobalt mixed sulfide and nickel oxide ore hydrometallurgical method | |
| CA2878528C (en) | Recovering metal values from oxides of manganese-containing materials | |
| CN110541081A (en) | method for treating laterite-nickel ore | |
| CA2667033A1 (en) | Recovering metal values from a metalliferrous material | |
| WO2018101039A1 (en) | Ion exchange processing method, and scandium recovery method | |
| WO2017146034A1 (en) | Method for recovering scandium | |
| Sheng et al. | Preparation of electronic grade manganese sulfate from leaching solution of ferromanganese slag | |
| CN113403486B (en) | Iron removal process of nickel sulfide concentrate leaching solution by goethite method | |
| WO2016139858A1 (en) | Method for producing nickel sulfide and hydrometallurgical method for nickel oxide ore | |
| US9926206B2 (en) | Treatment of manganese-containing materials | |
| CN115094229B (en) | Method for recovering scandium in cobalt nickel hydroxide prepared from lateritic nickel ore | |
| Hosseini Nasab et al. | Selective precipitation of iron from multi-element PLS produced by atmospheric leaching of Ni-Co bearing laterite | |
| JPH06212304A (en) | Method for smelting zinc | |
| JP6724351B2 (en) | How to remove sulfiding agent | |
| WO2021059940A1 (en) | Method for recovering scandium, and ion exchange method | |
| CN112777642A (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag | |
| JPS6032698B2 (en) | Method for recovering copper, nickel and cobalt in sulfuric acid leaching solution of manganese nodule | |
| CN113528815B (en) | Method for recovering valuable metals from cobalt-manganese polymetallic oxide ore and application thereof | |
| CN117604278A (en) | Method for separating manganese from crude metal hydroxide, manganese-silicon composite material and application thereof | |
| CN115180639A (en) | Method for purifying lithium sulfate solution to remove impurities and producing lithium carbonate | |
| CN116891942A (en) | Recycling treatment method of low nickel matte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |