CN111455174A - Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt - Google Patents
Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt Download PDFInfo
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- CN111455174A CN111455174A CN202010519493.5A CN202010519493A CN111455174A CN 111455174 A CN111455174 A CN 111455174A CN 202010519493 A CN202010519493 A CN 202010519493A CN 111455174 A CN111455174 A CN 111455174A
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- nickel
- cobalt
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- 238000000034 method Methods 0.000 title claims abstract description 49
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 38
- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 28
- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 28
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 28
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 title claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 89
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011575 calcium Substances 0.000 claims abstract description 51
- 238000000605 extraction Methods 0.000 claims abstract description 50
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 43
- 239000011777 magnesium Substances 0.000 claims abstract description 41
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 24
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000004090 dissolution Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims abstract description 3
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims abstract description 3
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims abstract description 3
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 46
- 239000000344 soap Substances 0.000 claims description 40
- 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 30
- 239000011734 sodium Substances 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 16
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000003350 kerosene Substances 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- -1 nickel-cobalt-iron-aluminum Chemical compound 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 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
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 16
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002386 leaching Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- GIKNHHRFLCDOEU-UHFFFAOYSA-N 4-(2-aminopropyl)phenol Chemical compound CC(N)CC1=CC=C(O)C=C1 GIKNHHRFLCDOEU-UHFFFAOYSA-N 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
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- Geochemistry & Mineralogy (AREA)
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Abstract
A method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel cobalt hydroxide belongs to the technical field of nickel cobalt hydrometallurgy. The mixed nickel cobalt hydroxide is leached by sulfuric acid, then, a nickel/cobalt/manganese-based neutralizer is adopted to remove iron and aluminum in the solution, liquid-solid separation is carried out to obtain iron-removed slag, acid dissolution is carried out to recover nickel and cobalt, and precipitator (one or more of nickel fluoride, cobalt fluoride and manganese fluoride) is added into the iron-removed slag to remove calcium and magnesium ions in the system. Removing impurities such as Mn, Cu, Zn and the like from the solution after calcium and magnesium removal by using a saponified P204 extraction agent, separating nickel and cobalt from the P204 raffinate by using a saponified P507 extraction agent to obtain battery-grade nickel sulfate and cobalt sulfate solutions, and evaporating and crystallizing to obtain the product. The method greatly reduces the using amount of calcium oxide, the amount of calcium ions introduced into the system and the corresponding loss of nickel and cobalt, avoids the influence of calcium sulfate crystallization on extraction, reduces the P507 extraction operation amount, and reduces the purification cost.
Description
Technical Field
The invention belongs to the technical field of nickel-cobalt hydrometallurgy, and relates to a method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel-cobalt hydroxide.
Background
With the exhaustion of the mining of nickel sulfide ores and the increasing demand for nickel, the attention is paid to the extraction of nickel and cobalt from laterite-nickel ores with abundant reserves. At present, the whole wet treatment process of the laterite-nickel ore is mainly a high-pressure acid leaching method. In order to facilitate transportation and save cost, laterite-nickel ore is often processed into a mixed nickel-cobalt hydroxide (MHP) intermediate product, which is obtained by high-pressure acid leaching, impurity removal, neutralization and precipitation, and the mixed nickel-cobalt hydroxide is an important production raw material for producing products such as battery-grade nickel sulfate, battery-grade cobalt sulfate and the like.
The mixed nickel hydroxide and cobalt hydroxide is used to produce battery-grade nickel sulfate and battery-grade cobalt sulfate mostly by a hydrometallurgical process, and the procedures generally comprise sulfuric acid leaching, neutralization and iron and aluminum removal, extraction and impurity removal, nickel and cobalt separation and other processes, for example, the method is adopted by companies such as Jiangxi river tungsten, Jinchuan and Hua Yong cobalt industries. Because the components of the mixed cobalt hydroxide are complex, the requirements of battery-grade nickel sulfate and cobalt sulfate on impurities are extremely strict, and the impurity removal and separation processes of the leachate are not complete. The mixed nickel cobalt hydroxide sulfuric acid leaching solution contains elements such as Fe, Al, Ca, Mg, Cr, Cu, Mn, Zn and the like besides Ni and Co. A large amount of common impurity ions can be removed by an oxidation neutralization method, a replacement method, a sulfide method, a fluoride method, an extraction method and the like.
At present, the method for removing iron and aluminum from an acidic nickel-cobalt solution obtained by mixing nickel-cobalt hydroxide mainly adopts a calcium oxide slurry neutralization method. The process is widely adopted, but has the problems that calcium oxide neutralizes and removes iron and aluminum to obtain a large amount of iron and aluminum slag, the nickel content is 6-12%, the nickel cannot be recovered to cause a large amount of nickel loss, and the nickel loss rate is about 1.5%. On the other hand, the added calcium oxide introduces Ca ions into the system, the Ca ions in the nickel-cobalt solution are in a saturated state, and the Ca ions precipitate a large amount of calcium sulfate crystals in the P204 extraction and back extraction to block pipelines and seriously hinder the extraction, so that the technical problem to be solved is urgently needed.
In the aspect of removing calcium and magnesium from a nickel-cobalt solution, a fluoride precipitation method, a solvent extraction method and the like are mainly adopted. Fluoride precipitation method using MgF2And CaF2And (3) adding NaF reagent to remove calcium and magnesium ions in the solution, wherein the solubility of the calcium and magnesium ions is very low. The disadvantage of this method is that a large amount of sodium ions is introduced into the solution. The solvent extraction method adopts P204 to extract and remove impurities such as Ca, Mn, Cu, Zn and the like, and P507 to separate nickel, cobalt and magnesium from P204 raffinate to produce battery-grade nickel sulfate and battery-grade cobalt sulfate products, which is also a commonly used method at present. The extraction method for removing calcium and magnesium has the following problems: the P204 is adopted for extraction and calcium removal, a large amount of calcium sulfate crystals block an extraction tank and a pipeline, and the calcium sulfate crystals need to be removed periodically; the P207 is adopted to separate magnesium, a long extraction stage number is needed, and the separation difficulty is also high.
People urgently need a new method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel cobalt hydroxide, solve the technical problem that the extraction is seriously hindered due to the blockage of a pipeline by calcium sulfate crystals in the prior art, and simultaneously improve the yield of nickel and cobalt and the production efficiency.
Disclosure of Invention
The invention adopts a novel neutralizer to remove iron and aluminum, iron-removed slag is sent to acid dissolution to recover nickel and cobalt, and the liquid after iron removal is sent to the next step for impurity removal and separation. And a novel precipitator is used for removing calcium and magnesium, and the liquid after calcium and magnesium removal is sent to the next step of P204 extraction for impurity removal and P507 nickel-cobalt separation. The solution impurity removal method adopted by the novel process does not introduce new impurity ions, greatly reduces the use amount of calcium oxide and the loss of nickel and cobalt in the process of removing aluminum, greatly lightens the influence of calcium sulfate crystallization on P204 extraction, reduces the operation amount of P507 extraction and magnesium separation, and is an efficient and green method for removing calcium and magnesium from a nickel and cobalt solution.
The invention provides a method for preparing battery-grade nickel sulfate and battery-grade cobalt sulfate from mixed nickel hydroxide and cobalt hydroxide. Sulfuric acid is used for leaching mixed nickel cobalt hydroxide, a novel neutralizer is used for neutralizing and removing iron and aluminum in the nickel cobalt sulfate solution, and a novel precipitator is added into the solution after iron removal to remove calcium and magnesium ions in the system. Removing impurities such as Mn, Cu, Zn and the like from the solution after calcium and magnesium removal by using a saponified P204 extraction agent, separating nickel and cobalt from the P204 raffinate by using a saponified P507 extraction agent to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution, and evaporating and crystallizing to obtain a battery-grade nickel sulfate product and a battery-grade cobalt sulfate product. According to the impurity removal and purification method, the mixed nickel cobalt hydroxide is used as a neutralizer for removing iron and aluminum, so that the using amount of calcium oxide can be reduced, the amount of calcium ions introduced into a system is reduced, and the loss of nickel and cobalt in the process of removing iron and aluminum is reduced; the novel precipitator is adopted to remove calcium and magnesium, so that the influence of calcium sulfate crystallization on extraction is avoided, the operation amount of P507 extraction is reduced, the purification cost is reduced, impurity ions in the nickel-cobalt solution are effectively removed, and nickel sulfate and cobalt sulfate products are obtained.
The technical scheme adopted by the invention is as follows:
a method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt comprises the following steps:
(1) acid dissolution: adding water into the mixed nickel cobalt hydroxide for slurrying, adding sulfuric acid for dissolving out, and performing liquid-solid separation to obtain manganese slag and a nickel cobalt sulfate solution;
(2) neutralizing and removing iron and aluminum: adding the nickel-cobalt sulfate solution obtained in the step (1) into a nickel/cobalt/manganese-based neutralizing agent for reaction, and performing liquid-solid separation to obtain nickel-cobalt-iron-aluminum slag and a liquid after iron and aluminum removal;
(3) secondary acid dissolution: adding water into the nickel-cobalt-iron-aluminum slag obtained in the step (2) for slurrying, adding sulfuric acid for dissolving out, and performing liquid-solid separation to obtain manganese slag and a nickel-cobalt sulfate solution;
(4) secondary neutralization for removing iron and aluminum: adding the nickel-cobalt sulfate solution obtained in the step (3) into calcium oxide slurry for reaction, and performing liquid-solid separation to obtain iron-aluminum slag and iron-aluminum-removed liquid;
(5) removing calcium and magnesium: combining the solutions obtained in the steps (2) and (4) after removing the aluminum, adding a precipitator for reaction, and performing liquid-solid separation to obtain calcium-magnesium slag and a solution after removing the calcium and the magnesium;
(6) p204 extraction and impurity removal: the calcium and magnesium removed liquid obtained in the step (5) is sent to P204 for extraction and impurity removal, copper, manganese, zinc and calcium impurities are removed, P204 raffinate is obtained, and the loaded organic phase is recycled through the steps of back extraction, iron stripping and chlorine washing;
(7) p507, nickel and cobalt extraction and separation: sending the P204 raffinate obtained in the step (6) to P507 for extracting and separating nickel and cobalt to obtain pure nickel sulfate and cobalt sulfate solution;
(8) evaporation and crystallization: evaporating and crystallizing pure nickel sulfate and cobalt sulfate solution to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate products.
The liquid-solid ratio in the invention is the mass ratio of liquid to solid.
Further, the nickel/cobalt/manganese-based neutralizing agent in step (2) is one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate, cobalt carbonate, basic nickel carbonate, basic cobalt carbonate, cobalt oxide, nickel oxide, manganese hydroxide, manganese carbonate, basic manganese carbonate and manganese oxide.
Further, the precipitating agent in the step (5) is one or more of nickel fluoride, cobalt fluoride and manganese fluoride.
Further, in the step (5), the adding amount of the precipitating agent is that the ratio of the amount of fluorine substances added into the precipitating agent to the amount of calcium and magnesium ions contained in the liquid after iron and aluminum removal is 2: 1.
Further, adding water for slurrying in the step (1) to control the liquid-solid ratio to be 2: 1-4: 1; the specific conditions for adding sulfuric acid for dissolution are as follows: adding sulfuric acid to control the pH value of the ore pulp to be 1.0-2.0, controlling the dissolution temperature to be 25-90 ℃, and controlling the dissolution time to be 1-3 h.
Further, the specific conditions for adding the neutralizing agent in the step (2) for reaction are as follows: controlling the end point pH value of the ore pulp to be 3.5-5.0, the reaction temperature to be 25-90 ℃, and the reaction time to be 2-5 h.
Further, adding water for slurrying in the step (3) to control the liquid-solid ratio to be 3: 1-4: 1; the specific conditions for adding sulfuric acid for dissolution are as follows: adding sulfuric acid to control the pH value of the ore pulp to be 1.0-2.0, controlling the dissolution temperature to be 25-90 ℃, and controlling the dissolution time to be 1-3 h.
Further, the specific conditions of the reaction of adding the calcium oxide slurry in the step (4) are as follows: controlling the end point pH value of the ore pulp to be 3.5-5.0, the reaction temperature to be 25-90 ℃, and the reaction time to be 2-5 h.
Further, in the step (6), the organic phase composition is 10-25% of P204+ sulfonated kerosene, sodium soap is carried out by using liquid alkali, the sodium soap rate is 30-60%, and the sodium soap is organically recycled by 10-30 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.1-0.5 mol/L H2SO4The stripping solution is 1.0-2.0 mol/L HCl, the iron-stripping solution is 4.5-6.0 mol/L HCl, and the chlorine-washing solution is 2-10 g/L H2SO4。
Further, in the step (7), the organic phase is 10-25% of P507+ sulfonated kerosene, sodium soap is carried out by using liquid alkali, the sodium soap rate is 30-60%, and the sodium soap is organically recycled by 10-30 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.1-0.5 mol/L H2SO4The stripping solution is 0.1-0.5 mol/L H2SO4The acid washing liquid is 2-10 g/L H2SO4。
The method provided by the invention relates to the following reaction principle:
when neutralizing and removing iron and aluminum, the added novel precipitator can decompose OH in a solution system-Or CO3 2-Mixing with residual acid in the leaching solution of nickel cobalt hydroxide and free H in the solution of nickel cobalt+With OH in the precipitant-Or CO3 2-After the reaction has taken place, free H+Decrease in OH-Become rich in Fe3+And Al3+Will react with OH-A precipitate was formed, which occurred as followsReaction:
Fe3++3OH-＝Fe(OH)3↓
Al3++3OH-＝Al(OH)3↓
thereby realizing the removal of iron and aluminum from the nickel-cobalt solution.
When calcium and magnesium are removed by a precipitation method, the added precipitator can decompose fluorine ions in a solution system. Calcium fluoride and magnesium fluoride are insoluble in water, and fluoride ions in the precipitator and calcium and magnesium ions in the nickel-cobalt-manganese solution are combined to generate precipitates to be removed. The process takes place as follows:
2F-+Ca2+＝CaF2↓
2F-+Mg2+＝MgF2↓
thereby realizing the removal of calcium and magnesium from the nickel-cobalt-manganese solution.
In the extraction process, an extracting agent and metal ions (Me) in the solution are utilizedn+) The extract is formed and enters the organic solvent (loaded with organic). The loaded organic and the stripping solution are mixed, and the metal ions are returned to the stripping solution. The removal of impurity ions and the separation of nickel and cobalt are realized by utilizing the difference of the extraction capacities of P204 and P507 to different metal ions. The extraction occurs:
Men++nHX＝MeXn+nH+
the innovation points and advantages of the invention are as follows:
(1) the adopted novel neutralizer for removing iron and aluminum preferably can use raw material mixed nickel cobalt hydroxide as a neutralizing reagent, can greatly reduce (more than 90%) the use amount of calcium oxide of the traditional neutralizer, greatly reduce (more than 90%) calcium ions introduced into a nickel cobalt solution system, and greatly reduce (more than 90%) the loss of nickel cobalt in the process of neutralizing and removing iron and aluminum.
(2) The novel precipitator is used for removing calcium and magnesium, new impurity ions are not introduced, the influence of calcium sulfate crystallization on P204 extraction can be greatly reduced, and the operation amount of P507 extraction and magnesium separation is reduced.
(3) The method has the advantages of simple process, strong operability and easy industrial realization.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Example 1
The main components of the mixed nickel cobalt hydroxide intermediate product obtained by carrying out high-pressure acid leaching, neutralization impurity removal and precipitation on laterite-nickel ore in a certain foreign factory are as follows:
| element(s) | Ca | Co | Ni | Cu | Fe | Mg | Mn | Si | Al | Zn |
| Content/% | 0.15 | 3.92 | 40.85 | 0.10 | 0.076 | 1.46 | 5.25 | 0.14 | 0.24 | 0.73 |
Adding water into the mixed nickel cobalt hydroxide for slurrying, controlling the liquid-solid ratio to be 4:1, adding sulfuric acid to control the pH value of ore pulp to be 1.5 at the temperature of 70 ℃, and dissolving out for 2 hours. Carrying out liquid-solid separation to obtain manganese slag and a nickel-cobalt sulfate solution, wherein the nickel-cobalt sulfate solution comprises the following components:
| element(s) | Al | As | Ba | Be | Bi | Ca | Cd | Co |
| content/(g/L) | 0.25 | <0.001 | <0.05 | <0.05 | <0.05 | 0.15 | <0.001 | 9.09 |
| Element(s) | Cr | Cu | Fe | Li | Mg | Mn | Ni | Pb |
| content/(g/L) | 0.025 | 0.24 | 0.045 | <0.05 | 1.56 | 3.54 | 95.7 | 0.01 |
| Element(s) | Sb | Sn | Sr | Ti | V | Zn | ||
| content/(g/L) | <0.05 | <0.05 | <0.05 | 0.033 | <0.05 | 1.73 |
Heating the solution 500m L to 70 ℃, adding mixed nickel cobalt hydroxide to adjust the pH value of the solution to 3.50, removing the aluminum for 3h, and carrying out liquid-solid separation to obtain aluminum-removed slag and a liquid after iron removal, wherein the liquid after iron removal comprises the following main components:
| element(s) | Al | Ca | Cr | Co | Cu | Fe |
| content/(g/L) | 0.064 | 0.67 | 0.0152 | 10.45 | 0.28 | 0.0045 |
| Element(s) | Mn | Mg | Ni | Zn | Si | Na |
| content/(g/L) | 4.69 | 1.80 | 110.22 | 2.63 | 0.041 | 0.03 |
Heating the solution 500m L to 70 ℃, adding 4.44g of nickel fluoride according to the theoretical amount calculation of calcium and magnesium, wherein the calcium and magnesium removal time is 6h, and performing liquid-solid separation to obtain calcium and magnesium slag and a liquid after calcium and magnesium removal, wherein the liquid after calcium and magnesium removal contains 0.01 g/L of calcium and 0.02 g/L of magnesium.
The solution after calcium and magnesium removal is sent to P204 for extraction and impurity removal, the organic phase composition is 20 percent of P204+80 percent of sulfonated kerosene, 32 percent of NaOH is adopted for sodium soap, the sodium soap rate is 60 percent, and the sodium soap is organically recycled by 20 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.5 mol/L H2SO4The back extraction solution is 2.0 mol/L HCl, the iron-back solution is 6.0 mol/L HCl, and the chlorine washing solution is 5 g/L H2SO4。
P204 raffinate is sent to P507 for extraction and separation of nickel and cobalt, the P507 extraction organic phase is 20 percent of P507+80 percent of kerosene, 32 percent of NaOH is used for carrying out sodium soap, the sodium soap rate is 30 percent, and the sodium soap is organic and is recycled by 20 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.1 mol/LH2SO4The back extraction solution is 0.5 mol/L H2SO4The acid washing liquid is 5 g/L H2SO4。
Obtaining nickel sulfate and cobalt sulfate solution, and sending to evaporation crystallization, washing and drying to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate products.
Example 2
A mixed nickel cobalt hydroxide intermediate product obtained by carrying out high-pressure acid leaching, neutralization impurity removal and precipitation on laterite-nickel ore in a certain foreign factory contains 65% of water, 35.0% of Ni, 4.0% of Co and 5.13% of Mn on a dry basis. Adding water into the mixed nickel cobalt hydroxide for slurrying, controlling the liquid-solid ratio to be 3.8:1, adding sulfuric acid to control the pH value of ore slurry to be 2.0 at the temperature of 25 ℃, and dissolving out for 3 hours. Carrying out liquid-solid separation to obtain manganese slag and a nickel-cobalt sulfate solution, wherein the nickel-cobalt sulfate solution comprises the following components:
| element(s) | Al | Ca | Mn | Ni | Co | Mg |
| content/(g/L) | 0.29 | 0.22 | 3.36 | 97.6 | 8.29 | 2.0 |
Heating the solution 500m L to 90 ℃, adding cobalt hydroxide to adjust the pH of the solution to 3.50, removing the aluminum for 3h, and carrying out liquid-solid separation to obtain aluminum-removed slag and a liquid after iron removal, wherein the liquid after iron removal comprises the following main components:
| element(s) | Al | Ca | Fe | Mn | Ni | Co | Mg |
| content/(g/L) | 0.034 | 0.23 | <0.001 | 3.36 | 98.2 | 8.35 | 2.0 |
Heating the solution 500m L to 70 deg.C, adding 1.50g nickel fluoride according to theoretical amount of calcium and magnesium, removing calcium and magnesium for 3 hr, separating liquid from solid to obtain calcium and magnesium residue and calcium and magnesium-removed liquid, wherein the calcium and magnesium-removed liquid contains calcium 0.08 g/L and magnesium 0.01 g/L.
The solution after calcium and magnesium removal is sent to P204 for extraction and impurity removal, the organic phase composition is 15 percent of P204+85 percent of sulfonated kerosene, 32 percent of NaOH is adopted for sodium soap, the sodium soap rate is 50 percent, and the sodium soap is organically recycled by 10 g/L Ni2+The nickel sulfate solution of (2) is subjected to nickel soap, and the washing liquid is 0.35 mol/L H2SO4The back extraction solution is 1.5 mol/L HCl, the iron-back solution is 5.0 mol/L HCl, and the chlorine washing solution is 8 g/L H2SO4。
P204 raffinate is sent to P507 for extraction and separation of nickel and cobalt, a P507 extraction organic phase is 15 percent of P507+85 percent of kerosene, 32 percent of NaOH is used for carrying out sodium soap, the sodium soap rate is 35 percent, and the sodium soap is organic and is recycled by 10 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.2 mol/L H2SO4The back extraction solution is 0.35 mol/L H2SO4The acid washing liquid is 8 g/L H2SO4。
Obtaining nickel sulfate and cobalt sulfate solution, and sending to evaporation crystallization, washing and drying to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate products.
Example 3
A mixed nickel cobalt hydroxide intermediate product obtained by carrying out high-pressure acid leaching, neutralization impurity removal and precipitation on laterite-nickel ore in a certain foreign factory contains 63.5% of water, 32.0% of Ni in dry basis, 3.8% of Co and 4.62% of Mn. Adding water into the mixed nickel cobalt hydroxide for slurrying, controlling the liquid-solid ratio to be 3.5:1, adding sulfuric acid to control the pH value of ore slurry to be 1.0 at the temperature of 90 ℃, and dissolving out for 1 hour. Carrying out liquid-solid separation to obtain manganese slag and a nickel-cobalt sulfate solution, wherein the nickel-cobalt sulfate solution comprises the following components:
| element(s) | Al | Ca | Mn | Ni | Co | Mg |
| content/(g/L) | 0.64 | 0.36 | 6.23 | 90.6 | 10.83 | 1.86 |
Heating the solution 500m L to 60 ℃, adding nickel carbonate to adjust the pH of the solution to 3.50, removing the aluminum for 4.0h, and carrying out liquid-solid separation to obtain aluminum-removed slag and a liquid after iron removal, wherein the liquid after iron removal mainly comprises the following components:
| element(s) | Al | Ca | Fe | Mn | Ni | Co | Mg |
| content/(g/L) | 0.04 | 0.42 | <0.001 | 6.36 | 93.9 | 10.83 | 1.80 |
Heating the solution 500m L to 60 deg.C, adding nickel fluoride 2.80g according to theoretical amount of calcium and magnesium, removing calcium and magnesium for 4 hr, separating liquid from solid to obtain calcium and magnesium residue and calcium and magnesium-removed liquid, wherein the calcium and magnesium-removed liquid contains calcium 0.05 g/L and magnesium 0.06 g/L.
The liquid after calcium and magnesium removal is sent to P204 for extraction and impurity removal, the organic phase composition is 25 percent of P204+75 percent of sulfonated kerosene, 32 percent of NaOH is adopted for sodium soap, the sodium soap rate is 40 percent, and the sodium soap is organically recycled by 15 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.5 mol/L H2SO4The back extraction solution is 2.0 mol/L HCl, the iron-back solution is 4.5 mol/L HCl, and the chlorine washing solution is 10 g/L H2SO4。
P204 raffinate is sent to P507 for extraction and separation of nickel and cobalt, a P507 extraction organic phase is 25% of P507+ 75% of kerosene, sodium soap is carried out by using 32% of NaOH, the sodium soap rate is 40%, and the sodium soap is organic and is recycled by 15 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.5 mol/L H2SO4The back extraction solution is 0.5 mol/L H2SO4The acid washing liquid is 10 g/L H2SO4。
Obtaining nickel sulfate and cobalt sulfate solution, and sending to evaporation crystallization, washing and drying to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate products.
Claims (10)
1. A method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt is characterized by comprising the following steps:
(1) acid dissolution: adding water into the mixed nickel cobalt hydroxide for slurrying, adding sulfuric acid for dissolving out, and performing liquid-solid separation to obtain manganese slag and a nickel cobalt sulfate solution;
(2) neutralizing and removing iron and aluminum: adding the nickel-cobalt sulfate solution obtained in the step (1) into a nickel/cobalt/manganese-based neutralizing agent for reaction, and performing liquid-solid separation to obtain nickel-cobalt-iron-aluminum slag and a liquid after iron and aluminum removal;
(3) secondary acid dissolution: adding water into the nickel-cobalt-iron-aluminum slag obtained in the step (2) for slurrying, adding sulfuric acid for dissolving out, and performing liquid-solid separation to obtain manganese slag and a nickel-cobalt sulfate solution;
(4) secondary neutralization for removing iron and aluminum: adding the nickel-cobalt sulfate solution obtained in the step (3) into calcium oxide slurry for reaction, and performing liquid-solid separation to obtain iron-aluminum slag and iron-aluminum-removed liquid;
(5) removing calcium and magnesium: combining the solutions obtained in the steps (2) and (4) after removing the aluminum, adding a precipitator for reaction, and performing liquid-solid separation to obtain calcium-magnesium slag and a solution after removing the calcium and the magnesium;
(6) p204 extraction and impurity removal: the calcium and magnesium removed liquid obtained in the step (5) is sent to P204 for extraction and impurity removal, copper, manganese, zinc and calcium impurities are removed, P204 raffinate is obtained, and the loaded organic phase is recycled through the steps of back extraction, iron stripping and chlorine washing;
(7) p507, nickel and cobalt extraction and separation: sending the P204 raffinate obtained in the step (6) to P507 for extracting and separating nickel and cobalt to obtain pure nickel sulfate and cobalt sulfate solution;
(8) evaporation and crystallization: evaporating and crystallizing pure nickel sulfate and cobalt sulfate solution to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate products.
2. The method of claim 1, wherein the nickel/cobalt/manganese-based neutralizing agent in step (2) is one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate, cobalt carbonate, basic nickel carbonate, basic cobalt carbonate, cobalt oxide, nickel oxide, manganese hydroxide, manganese carbonate, basic manganese carbonate, and manganese oxide.
3. The method according to claim 1 or 2, wherein the precipitating agent in step (5) is one or more of nickel fluoride, cobalt fluoride and manganese fluoride.
4. The method according to claim 3, wherein the amount of the precipitating agent added in the step (5) is 2:1 of the amount of the fluorine substance added in the precipitating agent to the amount of the calcium and magnesium ion-containing substance in the solution after removing the aluminum.
5. The method according to claim 1 or 2, wherein the step (1) of adding water slurry to control the liquid-solid ratio to be 2: 1-4: 1; the specific conditions for adding sulfuric acid for dissolution are as follows: adding sulfuric acid to control the pH value of the ore pulp to be 1.0-2.0, controlling the dissolution temperature to be 25-90 ℃, and controlling the dissolution time to be 1-3 h.
6. The method according to claim 1 or 2, wherein the specific conditions for the reaction of adding the neutralizing agent in the step (2) are as follows: controlling the end point pH value of the ore pulp to be 3.5-5.0, the reaction temperature to be 25-90 ℃, and the reaction time to be 2-5 h.
7. The method according to claim 1 or 2, wherein the water slurrying in the step (3) is performed to control the liquid-solid ratio to be 3: 1-4: 1; the specific conditions for adding sulfuric acid for dissolution are as follows: adding sulfuric acid to control the pH value of the ore pulp to be 1.0-2.0, controlling the dissolution temperature to be 25-90 ℃, and controlling the dissolution time to be 1-3 h.
8. The method according to claim 1 or 2, wherein the specific conditions for the reaction of adding the calcium oxide slurry in the step (4) are as follows: controlling the end point pH value of the ore pulp to be 3.5-5.0, the reaction temperature to be 25-90 ℃, and the reaction time to be 2-5 h.
9. The method as claimed in claim 1, wherein the organic phase composition in step (6) is 10-25% of P204+ sulfonated kerosene, sodium soap is carried out by using liquid alkali, the sodium soap rate is 30-60%, and sodium soap organic recycling is 10-30 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.1-0.5 mol/L H2SO4Stripping solution1.0-2.0 mol/L HCl, 4.5-6.0 mol/L HCl as iron-reflecting liquid, and 2-10 g/L H as chlorine-washing liquid2SO4。
10. The method as claimed in claim 1, wherein the organic phase in step (7) is 10-25% of P507+ sulfonated kerosene, sodium soap is carried out by using liquid alkali, the sodium soap rate is 30-60%, and sodium soap organic recycling is 10-30 g/L Ni2+The nickel sulfate solution is subjected to nickel soap, and the washing liquid is 0.1-0.5 mol/L H2SO4The stripping solution is 0.1-0.5 mol/L H2SO4The acid washing liquid is 2-10 g/L H2SO4。
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