CN116516152A - Method for comprehensively recovering valuable metals from copper-scandium-containing nickel-cobalt sulfate solution - Google Patents
Method for comprehensively recovering valuable metals from copper-scandium-containing nickel-cobalt sulfate solution Download PDFInfo
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- CN116516152A CN116516152A CN202310465536.XA CN202310465536A CN116516152A CN 116516152 A CN116516152 A CN 116516152A CN 202310465536 A CN202310465536 A CN 202310465536A CN 116516152 A CN116516152 A CN 116516152A
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- nickel
- cobalt
- copper
- scandium
- sulfate solution
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- 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 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 150000002739 metals Chemical class 0.000 title claims abstract description 21
- NZOBMQKUUTZNND-UHFFFAOYSA-N copper scandium Chemical compound [Sc].[Cu] NZOBMQKUUTZNND-UHFFFAOYSA-N 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 245
- 239000010949 copper Substances 0.000 claims abstract description 167
- 229910052802 copper Inorganic materials 0.000 claims abstract description 157
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 154
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 153
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 152
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 147
- 239000010941 cobalt Substances 0.000 claims abstract description 127
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 126
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 117
- 238000001556 precipitation Methods 0.000 claims abstract description 95
- 239000002893 slag Substances 0.000 claims abstract description 77
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 76
- 238000011084 recovery Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 173
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 72
- 238000002386 leaching Methods 0.000 claims description 48
- 238000000605 extraction Methods 0.000 claims description 27
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 25
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 239000004571 lime Substances 0.000 claims description 13
- 239000008267 milk Substances 0.000 claims description 13
- 235000013336 milk Nutrition 0.000 claims description 13
- 210000004080 milk Anatomy 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000009388 chemical precipitation Methods 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 22
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 22
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 22
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 20
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- -1 nickel salt Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- UGGGZZFHTCGPFY-UHFFFAOYSA-H S(=O)([O-])[O-].[Sc+3].S(=O)([O-])[O-].S(=O)([O-])[O-].[Sc+3] Chemical compound S(=O)([O-])[O-].[Sc+3].S(=O)([O-])[O-].S(=O)([O-])[O-].[Sc+3] UGGGZZFHTCGPFY-UHFFFAOYSA-H 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 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 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IEWUUVGDINEFTP-UHFFFAOYSA-J cobalt(2+) nickel(2+) dicarbonate Chemical compound [Co++].[Ni++].[O-]C([O-])=O.[O-]C([O-])=O IEWUUVGDINEFTP-UHFFFAOYSA-J 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical class [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- LQPWUWOODZHKKW-UHFFFAOYSA-K scandium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Sc+3] LQPWUWOODZHKKW-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of metallurgy, and particularly relates to a method for comprehensively recovering valuable metals from a copper-scandium-containing nickel-cobalt sulfate solution, which comprises the following steps: (1) scandium recovery: adding sodium sulfite into a nickel cobalt sulfate solution containing copper and scandium, controlling the pH of an end point to be 3.0-4.0, stirring and reacting at 15-40 ℃, and carrying out solid-liquid separation to obtain scandium slag and a first nickel cobalt sulfate solution; (2) copper recovery: heating the first nickel cobalt sulfate solution to 45-95 ℃, adding a copper removing agent, controlling the pH of the end point to 3.0-5.0, stirring for reaction, and carrying out solid-liquid separation to obtain copper slag and a second nickel cobalt sulfate solution; (3) recovery of nickel and cobalt: adding a neutralizing agent into the second nickel cobalt sulfate solution, controlling the pH of the end point to 8.5-9.5, and carrying out solid-liquid separation to obtain a solution after nickel and cobalt precipitation and nickel and cobalt slag, and recovering nickel and cobalt from the nickel and cobalt slag. The method can separate and obtain high-grade copper and scandium products, and simultaneously recover nickel and cobalt respectively.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for comprehensively recovering valuable metals from a copper-scandium-containing nickel-cobalt sulfate solution.
Background
Scandium extraction mainly extracts or recovers scandium in some intermediate products and byproducts, and up to now, scandium extraction methods have been classified into three types: scandium extraction from primary minerals, scandium recovery from industrial waste residues, scandium recovery from industrial waste liquid. When ore containing associated scandium is treated by hydrometallurgy, scandium and target elements are leached out, and scandium is discharged along with waste liquid after the target elements are recovered, so industrial waste liquid is also a raw material source for recovering scandium. Hydrometallurgy is a main method for extracting scandium, the current scandium extraction process is relatively single, and the improvement of the leaching rate and the reduction of scandium extraction cost are main directions of scandium extraction in the future, so that scandium resource recovery process is optimized, production cost is reduced, and the method has great significance for effective utilization of scandium resources.
Nickel cobalt ore is a scandium-containing resource with high value, scandium content in nickel cobalt hydroxide intermediate products is generally considered to be 20g/t, namely, the scandium is recovered, the existence form of scandium in the nickel cobalt hydroxide intermediate products is in an ionic state, nickel cobalt in the nickel cobalt hydroxide intermediate products is often converted into salts or electrolytic products by a wet smelting method, and valuable metals are recovered by the following method in the wet smelting: firstly, leaching nickel and cobalt by using inorganic acid, wherein the leaching solution contains a small amount of impurities (leaching together with nickel and cobalt) such as silicon, copper, calcium, manganese, zinc and the like, wherein silicon is usually removed by a chemical precipitation method, manganese, copper and zinc are usually removed by an extraction method, and in the silicon removal process, most of copper and scandium are also enriched into silicon removal slag along with silicon, and meanwhile, the loss of nickel and cobalt is small, so that the recovery rate of valuable metals is improved, and the nickel and cobalt in the silicon removal slag are often required to be recovered for the second time: the leaching agent is added to dissolve nickel and cobalt in the leaching agent, then the leaching agent is continuously removed, one or more of an extraction method, a resin adsorption method and a precipitation method are adopted as the common method for recovering or removing scandium from a nickel and cobalt sulfate solution in the prior art, scandium is enriched by resin or an extractant, then the scandium is desorbed or back extracted respectively, the precipitant is added into a desorption solution or back extracted liquid, the common scandium precipitant is hydroxide, fluoride, oxalate and carbonate, and the precipitation is calcined to prepare scandium oxide, however, the extraction method and the resin adsorption method are generally only aiming at the condition of low scandium concentration, and the washing, back extraction, regeneration of the extractant, adsorption, desorption and regeneration cycles of the resin are longer, and the treatment efficiency is low. The method for comprehensively recovering valuable metals from the nickel cobalt sulfate solution containing copper and scandium provided by the invention has the advantages of short flow, simplicity in operation and higher scandium and copper recovery rate, the obtained scandium slag has higher value, copper can be separated independently, and nickel and cobalt after copper scandium separation can be continuously and respectively produced into nickel salt/cobalt salt and electrolytic nickel/electrolytic cobalt, so that the full recovery of valuable metals is realized.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a method for comprehensively recovering valuable metals from a nickel cobalt sulfate solution containing copper and scandium.
The technical scheme of the invention is as follows:
a method for comprehensively recovering valuable metals from a copper-scandium-containing nickel-cobalt sulfate solution comprises the following steps:
(1) Scandium recovery: adding sodium sulfite into a nickel cobalt sulfate solution containing copper and scandium, controlling the pH of an end point to be 3.0-4.0, stirring and reacting at 15-40 ℃, and carrying out solid-liquid separation to obtain scandium slag and a first nickel cobalt sulfate solution;
(2) Recovery of copper: heating the first nickel cobalt sulfate solution to 45-95 ℃, adding a copper removing agent, controlling the pH of the end point to 3.0-5.0, stirring for reaction, and carrying out solid-liquid separation to obtain copper slag and a second nickel cobalt sulfate solution;
(3) Recovery of nickel and cobalt: and adding a neutralizing agent into the second nickel cobalt sulfate solution, controlling the pH of the end point to 8.5-9.5, and carrying out solid-liquid separation to obtain a nickel cobalt precipitated solution and nickel cobalt slag, and recovering nickel cobalt.
Preferably, in the step (1) of the present invention, sc is contained in the copper-scandium-containing nickel cobalt sulfate solution 3+ 0.1-20g/L，Cu 2+ 0.1-50g/L, pH2.5-3.5. In the step (1) of the invention, sodium sulfite and scandium ions undergo a double decomposition reaction:
3SO 3 2- +2Sc 3+ ＝Sc 2 (SO 3 ) 3 (s) A process for preparing (1-1)
Through multiple experimental demonstration, the reaction is found to occur in a nickel cobalt sulfate solution system when the temperature is lower than 40 ℃, scandium sulfite precipitate is generated, but the reaction is basically not generated when the temperature reaches more than 45 ℃, but copper ions in the solution are removed at the moment, and reddish brown cuprous oxide precipitate is generated.
In the process of recycling copper and scandium, when the end point pH is too low, sulfur dioxide is easy to generate after sodium sulfite is added, the utilization rate of sodium sulfite is reduced, and when the pH exceeds 4.0, the hydrolysis reaction of copper ions, the hydrolysis reaction of sodium sulfite and the reaction of scandium ions and sodium sulfite are all carried out, so that scandium and copper can not be separated thoroughly, and the purpose of respectively extracting scandium and copper can not be achieved. Therefore, in order to ensure the grade of scandium slag, the pH value should be controlled to be 3.0-4.0 when scandium is recovered, and the temperature is controlled to be 15-40 ℃, copper is not hydrolyzed basically, copper and other metal ions do not react with sodium sulfite, and only scandium sulfite precipitate is generated.
Preferably, in the step (2), the copper removing agent is one of sodium carbonate, sodium hydroxide, lime milk, calcium oxide, sodium sulfite and sodium bisulphite. When sodium carbonate, sodium hydroxide, lime milk and calcium oxide are used as copper removing agents, the copper hydrolysis reaction mainly occurs in the copper recovery process, and the pH value should be controlled to be 4.0-5.0 to ensure complete copper precipitation, when the pH value is lower than 4.0, copper hydrolysis is incomplete, when the pH value is higher than 5.0, copper removing agent consumption is increased, other impurities are hydrolyzed and precipitated together with copper, and along with the further increase of the pH value, part of nickel cobalt ions are precipitated together with the copper removal process, so that the recovery rate of nickel cobalt is reduced, and therefore, the pH value of copper removal is controlled to be 4.0-5.0. The pH of the copper removal agent is preferably controlled to be 3.0-5.0 under the preferable conditions of the two copper removal agents, wherein when the copper removal agent is sodium sulfite or sodium bisulphite, the pH is not lower than 3.0 and not higher than 4.3, and when sodium carbonate, sodium hydroxide, lime milk and calcium oxide are used as the copper removal agent, the pH is not lower than 4.0 and not higher than 5.0.
Preferably, when the copper scavenger is sodium sulfite or sodium bisulfite, the step (1) and the step (2) can be interchanged in the present invention, wherein the excess coefficient of sodium sulfite or sodium bisulfite is 1.5-4.0. The main reasons for sodium sulfite to remove scandium without copper at lower temperatures and copper without scandium at higher temperatures are: the copper ions are hydrolyzed to a lower degree at a lower temperature and are not hydrolyzed substantially, whereas the reaction of sodium sulfite with scandium ions is exothermic, so that the reaction is easier to carry out at a lower temperature, and the hydrolysis of both sodium sulfite and copper ions increases with increasing reaction temperature, while the reaction of sodium sulfite or sodium bisulfite with copper ions to cuprous oxide also occurs, which reaction is inhibited when the temperature is increased because the reaction of scandium with sodium sulfite is exothermic. Therefore, by controlling the reaction temperature, the reaction of scandium and sodium sulfite and the reaction of sodium sulfite or sodium bisulphite and copper can be completely separated, thereby achieving the purpose of respectively recovering copper and scandium. Because the pH change range caused by the reaction of sodium sulfite and scandium or copper is smaller, the pH of the nickel cobalt sulfate solution needs to be controlled to be 2.5-3.5 in advance, if the pH is lower than 2.5, the effect of respectively recovering copper scandium can be achieved by increasing the dosage of sodium sulfite, and if the pH is higher than 3.5, after the copper removing agent is added, hydrolysis of sodium sulfite and copper ions in the solution will take a dominant role in scandium recovery, so that scandium and copper are not thoroughly separated, namely copper is converted into copper hydroxide in scandium precipitation, and the scandium slag grade is reduced.
In the step (2) of the invention, when the reaction temperature is 45-95 ℃, sodium sulfite or sodium bisulphite is used as a copper removing agent, the following oxidation-reduction reactions respectively occur:
SO 3 2- +2H 2 O+2Cu 2+ ＝Cu 2 O(s)+4H + +SO 4 2- (1-2)
HSO 3 - +2H 2 O+2Cu 2+ ＝Cu 2 O(s)+5H + +SO 4 2- (1-3)
When sodium sulfite or sodium bisulphite is used as a copper removing agent, the pH value should be controlled to be 3.0-4.3, and meanwhile, the temperature is controlled to be 45-95 ℃, scandium is not contained in the nickel cobalt sulfate solution or does not react with sodium sulfite or sodium bisulphite mainly because of the control of the temperature, other metal ions are not hydrolyzed or precipitated under the condition, and the precipitation reaction of sodium sulfite or sodium bisulphite and copper takes the dominant role to generate cuprous oxide precipitation, so that the separation of copper and scandium is achieved.
In the scandium recovery process, under the condition of not adding a neutralizing agent, in the step (1), the pH value of the system is not obviously increased when the adding amount of sodium sulfite is 1.5-10 times of the theoretical using amount. When the sodium sulfite is less than 1.5 times of the theoretical amount, although sodium sulfite does not react with metal ions except copper and scandium in the solution, the scandium is not completely precipitated, the scandium recovery rate is less than 50 percent, when the sodium sulfite is more than 10 times of the theoretical amount, excessive sodium sulfite mainly undergoes hydrolysis reaction, the pH value of the system is gradually increased, and meanwhile, part of hydrogen ions generated by the hydrolysis of copper ions are consumed, so that the hydrolysis process of the copper ions is further promoted to be forward, the copper content in scandium slag is higher, and the separation of copper and scandium is not thorough:
SO 3 2- +2H 2 O＝HSO 3 - +OH - ，HSO 3 -- +2H 2 O＝H 2 SO 3 +OH - (1-4)
Cu 2+ +2H 2 O＝Cu(OH) 2 (s)+2H + (1-5)
Particularly, when sodium sulfite or sodium bisulphite is used as a copper removing agent to recover copper, the respective extraction of copper and scandium can be realized by controlling different temperatures, and the reactions of the sodium sulfite or the sodium bisulphite and the scandium are not interfered with each other, so that the recovery of copper and the recovery of scandium in the step (1) and the step (2) can be exchanged, but when sodium carbonate, sodium hydroxide, lime milk and calcium oxide are used as the copper removing agent, the higher pH value (4.0-5.0) is controlled, and if scandium ions are also contained in a nickel cobalt sulfate solution before copper removal, scandium ions are hydrolyzed to generate scandium hydroxide, so that the scandium precipitation rate is higher when copper is recovered, the grade of copper slag is reduced, and scandium and copper are not thoroughly separated.
In order to ensure that copper is completely precipitated, when sodium sulfite or sodium bisulphite is used as a copper removing agent, the proper copper removing agent dosage is controlled, when the excess coefficient of sodium sulfite or sodium bisulphite is lower than 1.5, the copper precipitation rate is lower than 30 percent, and when the excess coefficient is higher than 4.0, the copper precipitation is complete, and meanwhile, the hydrolysis degree of scandium is increased due to the addition of the excessive copper removing agent and the higher reaction temperature, copper and scandium are not thoroughly separated, so that the grade of copper slag is reduced. When the excess coefficient of sodium sulfite or sodium bisulphite is 1.5-4.0, copper is completely precipitated, scandium ions and nickel cobalt ions are not hydrolyzed, no precipitate is generated, and therefore, the excess coefficient of sodium sulfite or sodium bisulphite in the copper recovery process is controlled to be 1.5-4.0.
Preferably, in the steps (1) and (2) of the invention, the stirring reaction time is 1-4h.
In the step (3), the neutralizer is preferably one of sodium hydroxide, sodium carbonate, lime milk and calcium oxide, the step (3) is a nickel-cobalt precipitation process, and the pH is controlled to 8.5-9.5 to basically and completely convert nickel-cobalt in the solution into nickel-cobalt hydroxide or nickel-cobalt carbonate.
Preferably, in the step (3) of the present invention, nickel cobalt slag is treated: adding water into nickel-cobalt slag to prepare slurry, wherein the water adding amount is not strictly required, the slurry is stirred with water, the temperature is raised to 50-95 ℃, concentrated sulfuric acid is added, the pH of the final point is controlled to be 1.0-2.5, the nickel-cobalt can be completely leached, the acid dissolving time is 1-4h, the solid-liquid separation is carried out after the acid dissolving is finished, a first nickel-cobalt leaching solution is obtained, and the nickel-cobalt is recovered from the first nickel-cobalt leaching solution.
Preferably, in the step (3), the post-solution treatment of the nickel and cobalt deposition is carried out: and (3) performing aeration oxidation on the solution after nickel and cobalt precipitation, simultaneously controlling the pH of the end point to 9.5-10.0, performing secondary nickel and cobalt precipitation, performing solid-liquid separation to obtain a secondary nickel and cobalt precipitation solution and secondary nickel and cobalt precipitation slag, washing and acid-leaching the secondary nickel and cobalt precipitation slag to obtain a second nickel and cobalt leaching solution, and recycling nickel and cobalt from the second nickel and cobalt leaching solution. Specifically, the pH value of the nickel-cobalt precipitation solution is adjusted to 9.5-10.0, secondary nickel-cobalt precipitation is carried out, a small amount of residual nickel-cobalt ions can be converted into hydroxide or carbonate or sulfate precipitation, the reduction substances in the nickel-cobalt precipitation solution can be removed through aeration oxidation, the oxidation process of sulfite and hydrogen sulfite ions excessively introduced in the early stage is accelerated, the sulfite and hydrogen sulfite ions are converted into sulfate ions, and the secondary nickel-cobalt precipitation solution can be used for producing sodium sulfate byproducts and further treating wastewater. The main reactions occurring during aeration oxidation:
2SO 3 2- +O 2 ＝2SO 4 2- (1-6)
2HSO 3 - +2OH - +O 2 ＝2SO 4 2- +2H 2 O type (1-7)
Preferably, the nickel cobalt leaching solution recycling nickel cobalt step of the invention is: removing silicon by a chemical precipitation method, deeply removing impurities by P204 extraction, and extracting and separating nickel and cobalt by C272 or P507 to obtain refined nickel salt or cobalt salt solution. Specifically, the nickel cobalt contained in the obtained nickel cobalt leaching solution after washing and acid-dissolving the precipitated nickel cobalt slag can be extracted by P507 or C272, and separated, for example: the method comprises the steps of pre-removing impurities from the nickel-cobalt leaching solution by a chemical precipitation method, adjusting the pH value to 4.5-6.0, removing impurities from the solution by P204, extracting the impurities from the solution by P204, extracting cobalt from the P204 raffinate mainly containing nickel-cobalt by P507 or C272, and leaving nickel in the raffinate, wherein the raffinate is a refined nickel sulfate solution after oil removal, and can be used for producing nickel salt or electrolytic nickel, and the cobalt solution after the cobalt extraction is subjected to back extraction by inorganic acid (such as hydrochloric acid and sulfuric acid) by P507 or C272, and can be used for producing cobalt salt or electrolytic cobalt.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the method can separate high-grade copper and scandium products from the nickel cobalt sulfate solution containing copper and scandium, and simultaneously recover nickel and cobalt respectively.
2. In the method, scandium, nickel, cobalt and copper ions can be completely separated through the reaction of sodium sulfite and scandium, the purity of the obtained scandium sulfite precipitate reaches more than 94%, the scandium precipitation rate reaches more than 98%, and the full recovery of copper, nickel and cobalt is not influenced.
3. In the method, the reaction of sodium sulfite with copper and scandium is carried out separately by controlling the reaction temperature, the mutual interference is avoided, the purity of the recovered product and the recovery rate of scandium and copper are not influenced, wherein the recovery rate of copper is more than 97%, the purity of cuprous oxide is more than 94%, and the purity of other copper-containing copper carbonates and copper hydroxides is more than 91%.
4. In the method, the nickel cobalt is completely converted into carbonate or hydroxide to be precipitated by adding a neutralizer into the nickel cobalt sulfate solution after copper and scandium are recovered, and then nickel cobalt ions are acid-dissolved, washed and leached, wherein the recovery rate of nickel cobalt is over 99 percent.
5. In the method, the nickel and the cobalt are separated by removing impurities through a chemical precipitation method, extracting and removing impurities through P204 and extracting and separating nickel and cobalt through P507 or C272, so that the effect of respectively recovering the nickel and the cobalt is achieved.
Drawings
FIG. 1 is a flow chart of the comprehensive recovery of valuable metals from a copper and scandium containing nickel cobalt sulfate solution according to the present invention.
FIG. 2 is a flow chart of the recovery of nickel cobalt according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Scandium recovery: taking No. 1 nickel sulfate1L of cobalt solution, adding industrial sodium sulfite with purity of 82% into the cobalt solution at 15 ℃, adding sodium sulfite with the dosage of 4.96 times of the excess coefficient of the reaction of the sodium sulfite and scandium, stirring the mixture for 1h, filtering the mixture to obtain scandium slag and a first nickel cobalt sulfate solution (the components are shown in Table 3), drying the scandium slag at the constant temperature of 105 ℃ and the dry weight of 0.37g, and detecting that the scandium slag contains 26.65% of scandium and 71.78% of sulfite, and Sc 2 (SO 3 ) 3 The purity is 97.73%, the copper content is only 0.015%, the nickel and cobalt content is less than 0.001%, and the scandium precipitation rate is 98.61%;
(2) Recovery of copper: taking 0.8L of the first nickel cobalt sulfate solution obtained in the step (1), heating to 45 ℃, continuously adding industrial sodium sulfite with the purity of 82%, adding sodium sulfite with the dosage which is 4 times of the excess coefficient of the sodium sulfite in the reaction with copper, stirring and reacting for 2 hours, filtering to obtain 3.32g of copper slag and a second nickel cobalt sulfate solution (the components are shown in the table 5), and detecting that the copper slag contains copper 85.22% and the nickel cobalt content is less than 0.001%, and Cu 2 The O purity is 95.87%, and the copper precipitation rate is 98.51%;
(3) Recovery of nickel and cobalt: because the content of nickel and cobalt in the second nickel and cobalt sulfate solution is lower, the second nickel and cobalt sulfate solution and other nickel and cobalt sulfate solutions with higher nickel and cobalt ions in the existing production system enter a nickel and cobalt precipitation process (adding liquid alkali with the mass concentration of 10 percent) to carry out two-stage nickel and cobalt precipitation, wherein the pH value of a first stage control end point is 9.25, a first-stage nickel and cobalt precipitation rear solution and a first-stage nickel and cobalt precipitation slag are obtained, the liquid alkali with the mass concentration of 10 percent is continuously added into the first-stage nickel and cobalt precipitation rear solution, the pH value of the end point is 9.88, meanwhile, air is introduced to oxidize reducing substances therein, and the oxidizing process is carried out for 4 hours by aeration, so that a nickel and cobalt precipitation rear solution and a second-stage nickel and cobalt precipitation slag are obtained, the nickel concentration in the nickel and cobalt precipitation rear solution is lower than 1mg/L, the copper and scandium concentrations are both lower than 0.1mg/L, the concentration of cobalt is lower than 0.5mg/L, the sulfite ion concentration is lower than 50mg/L, and the water slurry is added into the second-stage nickel and the slag to prepare slurry with the solid mass ratio of 1:1, adding sulfuric acid for leaching to obtain nickel cobalt leaching solution (the acid leaching temperature is 50 ℃, the time is 1h, the pH is 2.50), the leaching rates of nickel and cobalt reach more than 99%, adding limestone powder into the nickel cobalt leaching solution to remove silicon (the control end point is 4.50), removing impurities by the depth of P204 extraction with the volume concentration of 25% (the P204 raffinate contains less than 0.005g/L and the manganese is less than 0.001 g/L), extracting cobalt by the P507 raffinate with the volume concentration of 15%, the P507 raffinate contains 90-120g/L and the cobalt is less than 0.001g/L, obtaining refined nickel sulfate solution, carrying out back extraction on the P507 after extracting cobalt by using sulfuric acid of 3N, controlling the pH of the back extraction solution to 2.50, obtaining refined cobalt sulfate solution, wherein the cobalt sulfate solution contains 80-100g/L and the nickel is less than 0.1g/L, the nickel sulfate and the cobalt sulfate solution can be respectively used for producing nickel sulfate crystals or electrolytic nickel, cobalt sulfate crystals or electrolytic cobalt, and specific nickel cobalt sulfate recovery conditions and results are shown in tables 6-7.
Example 2
(1) Scandium recovery: taking 5L of No. 2 nickel cobalt sulfate solution, adding industrial sodium sulfite with purity of 82% into the solution at 40 ℃, adding sodium sulfite with the dosage of 10 times of the excess coefficient of the reaction of the sodium sulfite and scandium, stirring and reacting for 2 hours, filtering to obtain scandium slag and a first nickel cobalt sulfate solution (the components are shown as 3), drying the scandium slag at the constant temperature of 105 ℃ and the dry weight of 6.0g, and detecting that the scandium slag contains 27% of scandium and 72.22% of sulfite, and Sc 2 (SO 3 ) 3 The post purity is 99.01%, the copper content is only 0.026%, the nickel and cobalt content is less than 0.001%, and the scandium precipitation rate is up to 98.18%;
(2) Recovery of copper: taking 4.85L of the first nickel cobalt sulfate solution obtained in the step (1), heating to 95 ℃, continuously adding industrial sodium sulfite with the purity of 82%, adding sodium sulfite with the dosage which is 1.5 times of the excess coefficient of the sodium sulfite in the reaction with copper, stirring and reacting for 4 hours, filtering to obtain 56.9g of copper slag and a second nickel cobalt sulfate solution (the components are shown in the table 5), and detecting that the copper slag contains 84.25 percent of copper and less than 0.001 percent of nickel cobalt, and Cu 2 The O purity is 94.78 percent, and the copper precipitation rate is 98.84 percent;
(3) Recovery of nickel and cobalt: adding a neutralizing agent into the second nickel cobalt sulfate solution to enter a nickel cobalt precipitation process: adding lime milk to perform two-stage nickel and cobalt precipitation, wherein the pH value of the end point of one stage is controlled to be 8.77, a first-stage nickel and cobalt precipitation post-liquid and a first-stage nickel and cobalt precipitation slag are obtained, continuously adding lime milk into the first-stage nickel and cobalt precipitation post-liquid, controlling the pH value of the end point of the second-stage nickel and cobalt precipitation post-liquid to be 9.55, simultaneously introducing air to oxidize reducing substances in the lime milk, performing aeration oxidation for 4 hours, obtaining a nickel and cobalt precipitation post-liquid and a second-stage nickel and cobalt precipitation slag, wherein the nickel concentration in the nickel and cobalt precipitation post-liquid is lower than 1mg/L, the copper and scandium concentration is lower than 0.1mg/L, the cobalt concentration is lower than 0.5mg/L, the sulfite ion concentration is lower than 50mg/L, adding water into the nickel and cobalt precipitation slag to prepare slurry, and the solid mass ratio of the slurry is 0.5:1, adding sulfuric acid for leaching to obtain nickel cobalt leaching solution (the acid leaching temperature is 95 ℃, the time is 1h, the pH value is 1.50), the leaching rates of nickel and cobalt reach more than 99%, adding limestone powder into the nickel cobalt leaching solution to remove silicon (the control end point is 4.89), the P204 extraction depth impurity with the volume concentration of 25% (the P204 raffinate contains less than 0.005g/L and the manganese is less than 0.001 g/L), the C272 with the volume concentration of 15% is used for extracting cobalt, the C272 raffinate contains 90-120g/L and the cobalt is less than 0.001g/L, a refined nickel sulfate solution is obtained, the C272 after cobalt extraction is back extracted by sulfuric acid of 4N, the pH value of the back extraction solution is controlled to 3.51, and a refined cobalt sulfate solution is obtained, the cobalt sulfate solution contains 80-100g/L and the nickel is less than 0.1g/L, and the nickel sulfate and the cobalt sulfate solution can be respectively used for producing nickel sulfate crystals or electrolytic nickel, cobalt sulfate crystals or electrolytic cobalt. Specific nickel cobalt recovery conditions and results are shown in tables 6 to 7.
Example 3
(1) Scandium recovery: 500L of No. 3 nickel cobalt sulfate solution is taken, industrial sodium sulfite with the purity of 82% is added into the solution at the temperature of 30 ℃, the sodium sulfite is added according to the excess coefficient of 1.51 times of the reaction of the sodium sulfite and scandium, scandium slag and a first nickel cobalt sulfate solution (the components are shown in table 3) are obtained by filtering after stirring and reacting for 2 hours, the scandium slag is dried at the constant temperature of 105 ℃ and has the dry weight of 37kg, and the scandium slag contains 26.60% of scandium and 71.65% of sulfate radical and Sc through detection 2 (SO 3 ) 3 The purity is 97.54%, the copper content is only 0.020%, the nickel and cobalt content is less than 0.001%, and the scandium precipitation rate is 98.42%;
(2) Recovery of copper: taking 499L of the first nickel cobalt sulfate solution obtained in the step (1), heating to 55 ℃, continuously adding industrial sodium sulfite with the purity of 82%, adding sodium sulfite with the dosage which is 2.51 times of the excess coefficient of the sodium sulfite in the reaction with copper, stirring and reacting for 1h, filtering to obtain 8.93kg of copper slag and a second nickel cobalt sulfate solution (the components are shown in the table 5), and detecting that the copper slag contains copper 84.59% and nickel cobalt content is less than 0.001%, and Cu 2 The O purity is 95.16%, and the copper precipitation rate is 99.07%;
(3) Recovery of nickel and cobalt: adding a neutralizing agent into the second nickel cobalt sulfate solution to enter a nickel cobalt precipitation process: adding lime milk to perform two-stage nickel and cobalt precipitation, wherein the pH value of the end point of one stage is controlled to be 9.49, a first-stage nickel and cobalt precipitation post-liquid and a first-stage nickel and cobalt precipitation slag are obtained, continuously adding lime milk into the first-stage nickel and cobalt precipitation post-liquid, controlling the pH value of the end point of the second-stage nickel and cobalt precipitation post-liquid to be 10.00, simultaneously introducing air to oxidize reducing substances in the lime milk, performing aeration oxidation for 8 hours, obtaining a nickel and cobalt precipitation post-liquid and a second-stage nickel and cobalt precipitation slag, wherein the nickel concentration in the nickel and cobalt precipitation post-liquid is lower than 1mg/L, the copper and scandium concentration is lower than 0.1mg/L, the cobalt concentration is lower than 0.5mg/L, the sulfite ion concentration is lower than 50mg/L, adding water into the nickel and cobalt precipitation slag to prepare slurry, and the solid mass ratio of the slurry is 0.8:1, adding sulfuric acid for leaching to obtain nickel cobalt leaching solution (the acid leaching temperature is 60 ℃, the time is 2h, the pH value is 1.00), the leaching rates of nickel and cobalt reach more than 99%, adding limestone powder into the nickel cobalt leaching solution to remove silicon (the control end point is 5.00), removing impurities in a P204 extraction depth with the volume concentration of 25% (the P204 raffinate contains less than 0.005g/L and the manganese is less than 0.001 g/L), extracting cobalt by a C272 with the volume concentration of 15%, the C272 raffinate contains 90-120g/L and the cobalt is less than 0.001g/L, obtaining refined nickel sulfate solution, carrying out back extraction on the C272 after extracting cobalt by sulfuric acid with the concentration of 3.5N, controlling the pH value of the back extraction solution to 2.63, and obtaining refined cobalt sulfate solution, wherein the cobalt sulfate solution contains 80-100g/L and the nickel is less than 0.1g/L, and the nickel sulfate and the cobalt sulfate solution can be respectively used for producing nickel sulfate crystals or electrolytic nickel, cobalt sulfate crystals or electrolytic cobalt. Specific nickel cobalt recovery conditions and results are shown in tables 6 to 7.
Example 4
(1) Scandium recovery: taking 100L of No. 4 nickel sulfate solution, adding industrial sodium sulfite with purity of 82% into the solution at 30 ℃, adding sodium sulfite with the dosage which is 6.22 times of the excess coefficient of the reaction of the sodium sulfite and scandium, stirring and reacting for 4 hours, filtering to obtain scandium slag and a first nickel cobalt sulfate solution (the components are shown in table 3), drying the scandium slag at a constant temperature of 105 ℃ and with a dry weight of 462g, and detecting that the scandium slag contains 25.68% of scandium and 69.17% of sulfite, and Sc 2 (SO 3 ) 3 The purity is 94.17%, the copper content is only 0.034%, the cobalt content is less than 0.001%, and the scandium precipitation rate is up to 98.87%;
(2) Copper (Cu)Is recovered: taking 99.5L of the first nickel sulfate solution obtained in the step (1), heating to 60 ℃, continuously adding sodium bisulphite with the purity of 99.5%, adding sodium bisulphite with the dosage of 1.5 times of the excess coefficient of the sodium bisulphite in the reaction with copper, stirring and reacting for 2 hours, filtering to obtain 2.65kg of copper slag and a second nickel cobalt sulfate solution (the components are shown in table 5), and detecting that the copper slag contains 85.02% of copper and less than 0.001% of nickel, and Cu 2 The O purity is 95.65 percent, and the copper precipitation rate is 98.06 percent;
(3) Recovery of nickel: adding a neutralizing agent into the second nickel sulfate solution to enter a nickel precipitation process: adding a sodium carbonate solution with the mass concentration of 15% for two-stage nickel precipitation, wherein the pH value of the end point of the first stage is controlled to be 8.50, a first-stage nickel precipitation solution and a first-stage nickel precipitation slag are obtained, continuously adding the sodium carbonate solution with the mass concentration of 15% into the first-stage nickel precipitation solution, controlling the pH value of the end point of the second-stage nickel precipitation to be 9.62, introducing air to oxidize reducing substances in the solution, and carrying out aeration oxidation for 12 hours, so as to obtain a nickel precipitation oxidized solution and a second-stage nickel precipitation slag, wherein the copper and scandium concentrations in the nickel precipitation oxidized solution are both lower than 0.1mg/L, the nickel concentration is lower than 0.5mg/L, the sulfite ion concentration is lower than 50mg/L, and adding water into the nickel precipitation slag for pulping, wherein the solid mass ratio of the prepared slurry is 1.5:1, adding sulfuric acid to leach to obtain nickel leaching solution (the acid leaching temperature is 55 ℃, the time is 4h, the pH value is 2.22), the leaching rate of nickel reaches more than 99 percent, adding limestone powder to the nickel leaching solution to remove silicon (the control end point is 5.50), and removing impurities deeply by P204 extraction with the volume concentration of 25 percent (the calcium content of P204 raffinate is lower than 0.005g/L and the manganese content of the P204 raffinate is lower than 0.001 g/L), so as to obtain refined nickel sulfate solution, wherein the nickel sulfate solution contains 80-100g/L of nickel, and can be used for producing nickel sulfate crystals or electrolytic nickel. Specific nickel recovery conditions and results are shown in tables 6 to 7.
Example 5
(1) Scandium recovery: the conditions were the same as in example 1 except that the scandium precipitation time was 4 h; scandium slag and the first nickel cobalt sulfate solution components are shown in table 3;
(2) Recovery of copper: taking 0.8L of the first nickel cobalt sulfate solution obtained in the step (1), heating to 45 ℃, adding 10% liquid alkali, regulating pH to 4.98, carrying out total reaction for 1h, filtering to obtain 4.55g of copper slag and a second nickel cobalt sulfate solution (the components are shown in Table 5), and detecting to obtain copper slagCopper 62.18%, cu (OH) 2 Purity 95.2%, copper precipitation rate 98.51%;
(3) Recovery of nickel and cobalt: the same as in example 1.
Example 6
(1) Scandium recovery: the scandium slag and the first nickel cobalt sulfate solution compositions are as shown in table 3, as in example 1;
(2) Recovery of copper: taking 0.8L of the first nickel cobalt sulfate solution obtained in the step (1), heating to 95 ℃, adding a sodium carbonate solution with the mass concentration of 15%, regulating the pH value to 4.02, filtering after the total reaction is 2 hours to obtain 6.04g of copper slag and a second nickel cobalt sulfate solution (the components are shown in the table 5), and detecting to obtain copper slag copper 47.43% and CuCO 3 Purity 91.9%, copper precipitation 99.75%.
(3) Recovery of nickel and cobalt: the same as in example 1.
Example 7
(1) Recovery of copper: 15L of No. 5 cobalt sulfate solution is taken, the temperature is raised to 45 ℃, industrial sodium sulfite with the purity of 82% is added into the solution, the sodium sulfite is added according to the excess coefficient of the reaction of the sodium sulfite and copper, the sodium sulfite is added according to the excess coefficient of the reaction of the sodium sulfite, the stirring reaction is carried out for 4 hours, and the filtration is carried out to obtain 7.6g of copper slag and a first nickel cobalt sulfate solution (the composition is shown in the table 3), wherein the copper slag contains copper 84.29%, the cobalt content is less than 0.001%, the scandium content is only 0.022%, and Cu 2 The O purity is 94.83%, and the copper precipitation rate is up to 97.06%;
(2) Scandium recovery: taking 14.85L of the first cobalt sulfate solution obtained in the step (1), continuously adding industrial sodium sulfite with the purity of 82 percent at 15 ℃, adding sodium sulfite with the dosage of 1.51 times of the excess coefficient of the sodium sulfite and scandium reaction, stirring and reacting for 1h, filtering to obtain scandium slag and a second nickel cobalt sulfate solution (the components are shown in table 5), drying the scandium slag at the constant temperature of 105 ℃ and the dry weight of 5.5g, and detecting that the scandium slag contains 26.60 percent of scandium, the cobalt content is less than 0.001 percent and the Sc 2 (SO 3 ) 3 Purity 97.54%, scandium precipitation rate 98.52%;
(3) Recovery of cobalt: adding a neutralizing agent into the second cobalt sulfate solution to enter a cobalt precipitation process, adding calcium oxide to perform one-stage cobalt precipitation, controlling the end point pH to be 9.51, introducing air to oxidize the reducing substance substances therein, performing aeration oxidation for 10 hours to obtain a cobalt precipitation oxidized solution and cobalt precipitation slag, wherein the concentrations of copper and scandium in the cobalt precipitation oxidized solution are lower than 0.1mg/L, the concentration of cobalt is lower than 0.5mg/L, the concentration of sulfite ions is lower than 50mg/L, adding water into the cobalt precipitation slag to prepare slurry, and the solid mass ratio of the slurry is 2:1, adding sulfuric acid for leaching to obtain cobalt leaching solution (the acid leaching temperature is 75 ℃, the time is 2h, the pH value is 1.55), the leaching rate of cobalt reaches more than 99 percent, adding limestone powder into the cobalt leaching solution to remove silicon (the control end point is 4.72), extracting cobalt by using C272 with the volume concentration of 15 percent (the cobalt of C272 raffinate is lower than 0.001 g/L), back-extracting the C272 after extracting cobalt by using sulfuric acid with the concentration of 3.5N, and controlling the pH value of the back-extracting solution to 3.09 to obtain refined cobalt sulfate solution, wherein the cobalt sulfate solution contains cobalt of 80-100g/L, and can be used for producing cobalt sulfate crystals or electrolytic cobalt. Specific cobalt recovery conditions and results are shown in tables 6 to 7.
Example 8
(1) Recovery of copper: 50L of No. 6 nickel cobalt sulfate solution is taken, after the temperature is raised to 95 ℃, sodium bisulphite with the purity of 99.5 percent is added into the solution, the sodium bisulphite is added according to the excessive coefficient of the sodium bisulphite and copper reaction of 1.5 times, the copper slag obtained by filtering after stirring and reacting for 1 hour is 2.86kg and the first nickel cobalt sulfate solution (the components are shown in the table 3), and the copper content 85.37 percent and the nickel cobalt content are detected to be less than 0.001 percent, meanwhile, the scandium content is only 0.013 percent and the copper content is Cu 2 The O purity is 96.04%, and the copper precipitation rate is up to 97.66%;
(2) Scandium recovery: taking 49.8L of the first nickel cobalt sulfate solution obtained in the step (1), continuously adding industrial sodium sulfite with the purity of 82% at 40 ℃, adding sodium sulfite with the dosage of 6.18 times of the excess coefficient of the sodium sulfite in the reaction with scandium, stirring and reacting for 4 hours, filtering to obtain scandium slag and a second nickel cobalt sulfate solution (the components are shown in table 5), drying the scandium slag at the constant temperature of 105 ℃ and the dry weight of 1.87kg, and detecting that the scandium slag contains 26.67% of scandium and less than 0.001% of nickel cobalt and Sc 2 (SO 3 ) 3 Purity 97.80%, scandium precipitation rate 98.67%.
(3) Recovery of nickel and cobalt: the same as in example 1.
TABLE 1 principal Components (unit: g/L) of copper-scandium-containing Nickel cobalt sulfate solution
| Numbering device | Application examples | Ni | Co | Cu | Sc | pH |
| 1# | 1、5、6 | 5.26 | 0.40 | 3.60 | 0.10 | 3.45 |
| 2# | 2 | 80 | 6.62 | 10.00 | 0.33 | 3.50 |
| 3# | 3 | 40.15 | 5.00 | 15.28 | 20.00 | 3.00 |
| 4# | 4 | 65.64 | 0 | 23.11 | 1.20 | 2.50 |
| 5# | 7 | 0 | 80.00 | 0.44 | 0.10 | 3.07 |
| 6# | 8 | 12.32 | 0.066 | 50.00 | 0.10 | 3.50 |
TABLE 2 conditions for recovering scandium (examples 1-6) and copper (examples 7-8) in step (1)
TABLE 3 first Nickel cobalt sulfate solution Main component, slag Dry basis Main component
From tables 1 to 3, it is clear that the scandium recovery process does not cause nickel cobalt loss and copper does not form precipitation together with scandium from the change of the original components of the first nickel cobalt sulfate solution and the nickel cobalt sulfate solution containing copper and scandium in examples 1 to 6, so that the separation effect of scandium and copper, nickel and cobalt is better; from the changes of the components of the first nickel cobalt sulfate solution and the original components of the nickel cobalt sulfate solution containing copper and scandium in examples 7-8, it is evident that the copper recovery process does not cause cobalt loss, scandium does not form precipitation together with copper, and therefore the separation effect of copper, scandium, nickel and cobalt is better.
TABLE 4 conditions for recovering copper (examples 1-6) and scandium (examples 7-8) in step (2)
TABLE 5 Nickel-cobalt solution and copper slag after scandium and copper recovery
As is clear from tables 3 to 5, the composition changes of the second nickel cobalt sulfate solution composition and the first nickel cobalt sulfate solution composition in examples 1 to 6 show that the copper recovery process does not cause nickel cobalt loss, and therefore the separation effect of copper from nickel and cobalt is good; as is clear from the composition changes of the second nickel cobalt sulfate solution composition and the first nickel cobalt sulfate solution composition in examples 7 to 8, the scandium recovery process did not cause the loss of nickel cobalt, and therefore the separation effect of scandium and nickel cobalt was good. In conclusion, by adopting the technical scheme of the invention, the separation of copper and scandium can be realized, and meanwhile, the recovery rate of nickel and cobalt is kept high.
TABLE 6 Nickel-cobalt recovery conditions (Nickel-cobalt sulfate ion-containing mixed solution is used as the precursor solution for precipitating nickel-cobalt)
TABLE 7 refining of Nickel cobalt sulfate leach solutions
As can be seen from tables 6 and 7, the mixed solution containing nickel cobalt sulfate ions is taken as a nickel cobalt precipitation precursor solution, a neutralizer is added to precipitate nickel cobalt, then aeration oxidation is carried out on the nickel cobalt precipitation precursor solution, the end point pH is controlled to 9.5-10.0, secondary nickel cobalt precipitation is carried out, solid-liquid separation is carried out to obtain secondary nickel cobalt precipitation precursor solution and secondary nickel cobalt precipitation residue, washing and pulping are carried out on the secondary nickel cobalt precipitation residue, sulfuric acid dissolution leaching is carried out to obtain a second nickel cobalt leaching solution, silicon is removed from the nickel cobalt leaching solution through a chemical precipitation method, P204 extraction depth is carried out, and C272 or P507 extraction separation is carried out to obtain refined nickel salt or cobalt salt solution, thus nickel and cobalt can be separated, and the effect of respectively recovering nickel and cobalt is achieved.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (10)
1. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel-cobalt sulfate solution is characterized by comprising the following steps of:
(1) Scandium recovery: adding sodium sulfite into a nickel cobalt sulfate solution containing copper and scandium, controlling the pH of an end point to be 3.0-4.0, stirring and reacting at 15-40 ℃, and carrying out solid-liquid separation to obtain scandium slag and a first nickel cobalt sulfate solution;
(2) Recovery of copper: heating the first nickel cobalt sulfate solution to 45-95 ℃, adding a copper removing agent, controlling the pH of the end point to 3.0-5.0, stirring for reaction, and carrying out solid-liquid separation to obtain copper slag and a second nickel cobalt sulfate solution;
(3) Recovery of nickel and cobalt: and adding a neutralizing agent into the second nickel cobalt sulfate solution, controlling the pH of the end point to 8.5-9.5, and carrying out solid-liquid separation to obtain a nickel cobalt precipitated solution and nickel cobalt slag, and recovering nickel cobalt.
2. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the step (1), sc is contained in the copper-scandium-containing nickel cobalt sulfate solution 3+ 0.1-20g/L，Cu 2+ 0.1-50g/L，pH2.5-3.5。
3. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the step (1), the excess coefficient of sodium sulfite is 1.5-10.
4. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the step (2), the copper removing agent is one of sodium carbonate, sodium hydroxide, lime milk, calcium oxide, sodium sulfite and sodium bisulphite.
5. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 4, wherein the method comprises the following steps: when the copper scavenger is sodium sulfite or sodium bisulfite, the sequence of step (1) and step (2) can be interchanged, wherein the excess coefficient of sodium sulfite or sodium bisulfite is 1.5-4.0.
6. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the steps (1) and (2), the stirring reaction time is 1-4h.
7. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the step (3), the neutralizing agent is one of sodium hydroxide, sodium carbonate, lime milk and calcium oxide.
8. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 1, wherein the method comprises the following steps: in the step (3), nickel-cobalt slag is treated: adding water into nickel-cobalt slag to prepare slurry, heating to 50-95 ℃, adding concentrated sulfuric acid, controlling the pH of the end point to 1.0-2.5, carrying out acid dissolution for 1-4h, carrying out solid-liquid separation after the acid dissolution is finished to obtain a first nickel-cobalt leaching solution, and recycling nickel-cobalt from the first nickel-cobalt leaching solution.
9. The method for comprehensively recovering valuable metals from the copper-scandium-containing nickel cobalt sulfate solution according to claim 8, wherein the method comprises the following steps: in the step (3), treating the post-nickel-cobalt precipitation solution: and (3) performing aeration oxidation on the solution after nickel and cobalt precipitation, simultaneously controlling the pH of the end point to 9.5-10.0, performing secondary nickel and cobalt precipitation, performing solid-liquid separation to obtain a secondary nickel and cobalt precipitation solution and secondary nickel and cobalt precipitation slag, washing and acid-leaching the secondary nickel and cobalt precipitation slag to obtain a second nickel and cobalt leaching solution, and recycling nickel and cobalt from the second nickel and cobalt leaching solution.
10. The method for comprehensively recovering valuable metals from the copper-containing scandium-containing nickel cobalt sulfate solution according to claim 8 or 9, which is characterized in that: the nickel cobalt leaching solution recovery method comprises the following steps: removing silicon by a chemical precipitation method, deeply removing impurities by P204 extraction, and extracting and separating nickel and cobalt by C272 or P507 to obtain refined nickel salt or cobalt salt solution.
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