CN115109943B - Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step - Google Patents
Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step Download PDFInfo
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- CN115109943B CN115109943B CN202210762711.7A CN202210762711A CN115109943B CN 115109943 B CN115109943 B CN 115109943B CN 202210762711 A CN202210762711 A CN 202210762711A CN 115109943 B CN115109943 B CN 115109943B
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- zinc
- copper
- manganese
- cobalt
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- 239000011701 zinc Substances 0.000 title claims abstract description 88
- 239000010949 copper Substances 0.000 title claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 68
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 60
- 239000010941 cobalt Substances 0.000 title claims abstract description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011572 manganese Substances 0.000 title claims abstract description 48
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 40
- -1 manganese metals Chemical class 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000605 extraction Methods 0.000 claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001556 precipitation Methods 0.000 claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011575 calcium Substances 0.000 claims abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 16
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 6
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 230000001376 precipitating effect Effects 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- 229960001763 zinc sulfate Drugs 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 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 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 3
- 238000011084 recovery Methods 0.000 abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000084 colloidal system Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- VHGVAYOJTGPXFA-UHFFFAOYSA-K copper sodium sulfanide Chemical compound [Cu+2].[SH-].[Na+].[SH-].[SH-] VHGVAYOJTGPXFA-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 84
- 229940099596 manganese sulfate Drugs 0.000 description 11
- 239000011702 manganese sulphate Substances 0.000 description 11
- 235000007079 manganese sulphate Nutrition 0.000 description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- HLSUFBULQFEQIX-UHFFFAOYSA-L [Zn].[Ca].[Co].[Mn].[Cu](Cl)Cl Chemical compound [Zn].[Ca].[Co].[Mn].[Cu](Cl)Cl HLSUFBULQFEQIX-UHFFFAOYSA-L 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 235000006748 manganese carbonate Nutrition 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NIUDBNWLJDCPOK-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Mn+2].[Cu+2] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Mn+2].[Cu+2] NIUDBNWLJDCPOK-UHFFFAOYSA-J 0.000 description 2
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- HFVKDUSMUFKQNU-UHFFFAOYSA-D [Cl-].[Ca+2].[Co+2].[Zn+2].[Cu+2].[Mn+2].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[Ca+2].[Co+2].[Zn+2].[Cu+2].[Mn+2].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] HFVKDUSMUFKQNU-UHFFFAOYSA-D 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- QCMLJYVKYRRZQH-UHFFFAOYSA-N [Mn].[Ca].[Zn] Chemical compound [Mn].[Ca].[Zn] QCMLJYVKYRRZQH-UHFFFAOYSA-N 0.000 description 1
- BYLUTIAAKVHIQC-UHFFFAOYSA-N [Mn].[Co].[Zn].[Ca] Chemical compound [Mn].[Co].[Zn].[Ca] BYLUTIAAKVHIQC-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
-
- 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
- C22B47/00—Obtaining manganese
-
- 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)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting and recovering copper, zinc, cobalt and manganese metals from a copper chloride manganese zinc cobalt solution step by step, which comprises the procedures of sodium hydrosulfide copper precipitation, p204 zinc extraction, sulfuric acid back extraction, neutralization precipitation, calcium aluminum removal and manganese powder replacement cobalt precipitation. According to the method, the sodium hydrosulfide solution is adopted to rapidly deposit copper at a low pH value, the separation of copper and zinc and manganese is realized by controlling the pH value of an end point by utilizing the difference of solubility products of different sulfide deposits, and synchronous precipitation of zinc and manganese during copper sulfide deposition is avoided, and the copper recovery rate is more than 99%; the selective extraction of p204 at low pH value is adopted, so that the extraction and separation of zinc and other metals are realized, and the extraction recovery rate of zinc is more than 99%; the calcium, iron and aluminum in the solution are removed by adopting the combined precipitation of sodium sulfate and a neutralizer, so that the problem that the obtained colloid is difficult to filter in the process of removing iron and aluminum by adopting a neutralization hydrolysis method independently can be solved; the recovery rate of cobalt by adopting a manganese powder substitution method is more than 99 percent. The method of the invention realizes the fractional extraction and recycling of copper, zinc, cobalt and manganese metals economically and conveniently.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for extracting and recovering copper, zinc, cobalt and manganese metals from a copper chloride manganese zinc cobalt calcium solution step by step.
Background
The hydrometallurgical process of cobalt-containing material is that cobalt in cobalt carbonate, cobalt hydroxide, cobalt oxide, etc. are leached with sulfuric acid to extract cobalt into solution, and manganese, copper, zinc, calcium, etc. in the material are also leached into leaching solution. The cobalt solution is subjected to iron removal, p204 is adopted for extraction and impurity removal, hydrochloric acid back extraction is adopted, separation of manganese, copper, zinc, calcium, aluminum and the like from cobalt is realized, and a copper-containing manganese zinc calcium-based solution is obtained after back extraction of an extraction load organic phase by hydrochloric acid, and is called copper-manganese-zinc-cobalt-calcium chloride solution for short, wherein the content of valuable metals such as copper, manganese, zinc and the like is extremely high, and the cobalt content is low, but the cobalt content is extremely high, so that the solution has extremely high resource utilization value.
At present, the treatment methods of the copper chloride manganese zinc cobalt calcium solution comprise a lime precipitation method, an alkali neutralization method, an oxidation neutralization method and the like, and aims at solidification of heavy metal ions in the solution and innocuous treatment and discharge of the solution in principle, and recovery of valuable metals in the solution is not considered. Among them, the most commonly used method is sodium carbonate precipitation, and the produced carbonate precipitate is sent to a fire system for recovering copper and cobalt. However, the method has large alkali consumption and high cost, so that the recovery rate of cobalt and copper is extremely low, and manganese and zinc are slag-formed and lost.
Chinese patent (publication No. CN 104445424A) proposes a method for preparing battery-grade manganese sulfate crystals by regulating pH value to 3.0-5.5 with lime, hydrolyzing and precipitating to remove aluminum iron, adding sodium sulfide (or ammonium sulfide) and precipitating to remove heavy metals (cobalt, zinc, copper and the like) at pH value of 4.0-6.0, extracting manganese by Cyanex272, back extracting with sulfuric acid to obtain manganese sulfate solution, and crystallizing. The method has the defects that on one hand, in the process of precipitating iron and aluminum by adjusting the pH value with lime, the obtained slag is colloid, the solid-liquid separation is extremely difficult, meanwhile, the calcium content in the solution is increased, and a larger burden is brought to the subsequent calcium removal.
Chinese patent (issued publication No. CN 105296754B) proposes a method for removing calcium by sodium sulfate precipitation, regulating pH value by sodium carbonate solution, precipitating and separating copper and manganese powder, replacing and recovering cobalt, and finally recovering manganese by sodium carbonate precipitation to obtain crude manganese carbonate precipitation. The method has the defects that on one hand, slag obtained during precipitation by sodium carbonate is colloid, solid-liquid separation is difficult, on the other hand, zinc recovery is not considered, and meanwhile, the purity of various separated slag is low.
Chinese patent (publication No. CN 105967217B) proposes a method for obtaining coarse manganese carbonate by sequentially carbonating and precipitating copper with a copper chloride solution through non-copper salt type indissolvable carbonate, replacing cobalt with a metal reducing agent, precipitating zinc with a sulfide precipitating agent, precipitating calcium with a soluble sulfate precipitating agent, evaporating and concentrating the calcium-precipitated solution to produce manganese chloride crystals, or carbonating and precipitating manganese through soluble carbonate. The method effectively realizes the full separation and recovery of copper, cobalt, manganese, zinc and calcium in the copper-manganese chloride solution.
In China patent (publication No. CN 108585051A), copper and manganese chloride solution is reacted with concentrated sulfuric acid to synthesize coarse manganese sulfate crystals after copper ions are neutralized and precipitated by manganese carbonate, heavy metal ions are precipitated by manganese sulfide, calcium ions are preliminarily precipitated by manganese sulfate, and calcium ions are deeply precipitated by active manganese fluoride; and recrystallizing the crude manganese sulfate crystal to obtain the battery-grade manganese sulfate crystal. The method adopts the manganese-containing material to remove and recycle Cu, zn, ca and other components in the copper-manganese chloride solution in the whole flow, combines five-stage countercurrent serial recrystallization purification process, greatly improves the quality of manganese sulfate, ensures the high-efficiency utilization of manganese resources and no wastewater discharge in the whole flow, simultaneously realizes the precipitation conversion of manganese chloride to synthesize crude manganese sulfate by directly adopting concentrated sulfuric acid, and avoids the complex process of firstly extracting manganese ions and then back extracting sulfuric acid or firstly precipitating manganese ions by carbonate and then dissolving and synthesizing manganese sulfate by sulfuric acid.
Yang Jingjun in the paper "full separation and analysis of copper, manganese, zinc, cobalt and calcium chloride solution", sulfate precipitation is first added to remove calcium, carbonate or sulfide precipitation is then added to obtain mixed precipitate of copper, cobalt and zinc, and then manganese chloride crystal is prepared by crystallization, and the mixed precipitate of copper, cobalt and zinc is passed throughDissolving in inorganic acid, adding reducer to reduce copper and form copper sulfide precipitate, adding sodium hypochlorite to cobalt-zinc solution to oxidize Co 2+ Oxidized to Co (0H) 3 And the sediment is extracted, and finally, the separation of valuable metals is realized.
In Chinese patent CN112575200A, the pH value is regulated to 0-4 by adopting an alkali solution or an acid solution, then crude copper sulfide slag, crude zinc sulfide, manganese sulfide precipitate and the like are added for size mixing, the potential is controlled to be 220mV, copper sulfide deposition is carried out by replacing the copper sulfide, and the liquid after copper deposition is subjected to size mixing by adopting manganese sulfide to replace to produce zinc sulfide slag.
According to the above analysis, for Cu 2+ The treatment method adopted is mainly divided into three types: the first carbonate precipitation method is to adjust the pH value of the system and produce copper carbonate precipitation, and in the copper precipitation process, iron aluminum and the like are precipitated, and the obtained copper carbonate is colloid, so that the solid-liquid separation is difficult, and the industrial application of the method is limited. The second metal replacement method mainly adopts iron powder replacement, and has the defect of introducing a large amount of iron ions and increasing the subsequent iron removal workload. Meanwhile, in the replacement process, the copper removal end point is difficult to grasp, and excessive iron powder is added, so that excessive iron powder also enters the sponge copper. The third sulfide precipitation method has the defect that the obtained copper sulfide precipitate is leached by adding a reducing agent when being treated again and dissolved, and the treatment is difficult. For Zn 2+ The method is mainly sulfide precipitation method at present, and the zinc sulfide slag obtained by the method is difficult to comprehensively utilize. For Co 2+ The treatment methods adopted are divided into two types: one is sulfide precipitation; the other is a metal substitution method. The two methods have advantages and disadvantages and can be selected according to the process characteristics. For Mn of 2+ The treatment methods adopted at present are mainly divided into three types: purifying and impurity-removing the first stock solution, and crystallizing to produce battery-grade manganese sulfate crystals; purifying the second stock solution, removing impurities, and precipitating sodium carbonate to produce industrial manganese carbonate; the third kind of preliminary impurity removal is carried out by using Cyanex272 extractionExtracting manganese by the extracting agent, and crystallizing after back extraction by sulfuric acid to produce battery-grade manganese sulfate. The process flow has the defects, and the recycling of the copper chloride, manganese zinc cobalt calcium solution is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for extracting and recycling copper, zinc, cobalt and manganese metals from a copper chloride manganese zinc cobalt calcium solution step by step, which has good treatment effect, high recovery rate and environmental friendliness.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step comprises the following steps:
(1) Copper deposition by sodium hydrosulfide solution: adding sodium hydrosulfide solution into copper chloride manganese zinc cobalt solution with pH value of 1.5-2.5 at normal temperature, controlling pH value of reaction end point to be less than 0.2, carrying out copper sulfide precipitation, and filtering to obtain copper sulfide concentrate and copper precipitation post-solution;
(2) p204 extraction of zinc: mixing p204 with sulfonated kerosene according to a volume ratio of 1:4-5 to obtain an extracted organic phase, and saponifying the extracted organic phase with 30% sodium hydroxide or 25% ammonia water by mass fraction to obtain a post-soap organic phase with a saponification rate of 30-40%; adding the post-copper precipitation organic phase into the post-copper precipitation liquid, and selectively extracting zinc under the condition that the pH value of the extraction balance is controlled to be 2.5-3 to obtain a zinc-containing loaded organic phase and zinc extraction residual liquid;
(3) Sulfuric acid back extraction: after the zinc-containing loaded organic phase is pickled, sulfuric acid is used for back extraction to prepare a crude zinc sulfate solution;
(4) Neutralizing and precipitating calcium aluminum removal: adding sodium sulfate and a neutralizer into the zinc extraction raffinate to adjust the pH value to 4.5-5.0, continuously reacting for 2 hours to precipitate and remove calcium and aluminum, and filtering to obtain waste residues containing calcium sulfate and aluminum hydroxide and calcium and aluminum removing liquid, and discarding the waste residues;
(5) Replacing and precipitating cobalt by manganese powder: adding manganese powder into the solution after removing calcium and aluminum to replace and precipitate cobalt, filtering to obtain cobalt slag and high-manganese solution, returning the cobalt slag to a cobalt raw material treatment system for leaching and dissolving treatment, wherein the high-manganese solution has extremely low impurity content and can be recycled according to the prior art.
As the optimization of the technical scheme of the invention, the copper-manganese-zinc-cobalt chloride solution contains 40-120 g/L, ca 0.3.3-10 g/L, co < 1g/L, cu-20 g/L, zn-20 g/L, al 0.1.1-10 g/L, fe 0.001.001-0.02 g/L of Mn.
In the step (1), the mass concentration of the sodium hydrosulfide solution is 10-15%, the obtained copper sulfide concentrate contains more than or equal to 50% of Cu, less than 0.3% of Zn, less than 0.3% of Mn and less than 0.05% of Co, and the obtained copper-precipitating solution contains less than 0.05g/L of Cu as a raw material in the downstream copper-smelting industry.
Further, in the step (2), the liquid volume ratio of the organic phase after soap to the liquid volume ratio after copper precipitation is 3-5:1, and the extraction stage number is 7; the zinc extraction raffinate contains less than 0.05g/L of Zn and has pH of 2.5-3.
In the step (3), the acid liquor used for pickling the zinc-containing loaded organic phase is sulfuric acid or hydrochloric acid solution with the concentration of 0.2mol/L, the washing volume ratio is 3-5:1, the washing stage number is 4, and the washing liquor is returned for reuse.
Further, the zinc-containing loaded organic phase after pickling is subjected to back extraction by adopting a 2mol/L sulfuric acid solution, and the pH value of the back extraction end point is controlled to be 2.5-4, so that a crude zinc sulfate solution is obtained, wherein the crude zinc sulfate solution contains 110-130 g/L, mn < 3g/L, co < 0.05g/L, cu < 0.03g/L, ca < 0.5g/L, al < 0.5g/L of Zn and can be used as a raw material in the downstream zinc smelting industry.
Further, in the step (4), the added amount of sodium sulfate is 2 times of the theoretical amount required for precipitating all calcium ions in the solution into calcium sulfate, and the neutralizer is NaoH and NaCO 3 、NaHCO 3 ，NH 4 One or more of OH, ca < 0.5g/L, al < 0.003g/L, fe < 0.0005g/L.
Further, in the manganese powder replacement cobalt precipitation reaction in the step (5), the manganese powder consumption is 6-8 times of the theoretical consumption, and the reaction time is 2 hours at 60-80 ℃; the obtained high manganese solution contains Mn of 40-130 g/L, co which is less than 0.0003g/L, cu which is less than 0.0003g/L, zn which is less than 0.0003g/L, ca which is less than 0.5g/L, al which is less than 0.005g/L, fe which is less than 0.0005g/L.
Compared with the existing treatment method of the copper chloride manganese zinc cobalt calcium solution, the method has the following beneficial effects:
(1) The invention adopts sodium hydrosulfide solution to rapidly precipitate copper under the condition of low pH value (pH value is 1.5-2.5), utilizes the difference of solubility products of different sulfide precipitates, controls the pH value of a reaction end point (pH value is less than 0.2), realizes the separation of copper and zinc and manganese, avoids synchronous precipitation of zinc and manganese during sulfide copper precipitation, and ensures that the copper recovery rate is more than 99 percent.
(2) According to the extraction characteristic curve of the p204 extractant, the p204 extractant is adopted to selectively extract zinc under the condition of low pH value (pH 2.5-3), so that the extraction separation of zinc and other metals is realized, and the extraction recovery rate of zinc is more than 99%.
(3) The method can solve the problem that the obtained colloid is difficult to filter in the process of removing aluminum by a single neutralization hydrolysis method by adopting sodium sulfide and a neutralizer to jointly precipitate and remove iron and aluminum in the solution.
(4) The cobalt in the solution is recovered by utilizing a metal replacement method, so that the recovery of the cobalt is realized, the recovery rate of the cobalt is more than 98%, and meanwhile, the zinc, copper and the like in the solution are deeply purified.
In conclusion, the method can economically and conveniently realize the fractional extraction and recycling of copper, zinc, cobalt and manganese metals, has high recovery rate of each metal and is environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step in the invention.
Detailed Description
The process of the present invention and its effects will be described in detail below with reference to the accompanying drawings and specific examples.
Example 1
Referring to fig. 1, the method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step provided in this embodiment includes the following steps:
(1) Copper deposition by sodium hydrosulfide solution: 3000mL of copper chloride manganese zinc cobalt solution is taken, and the main components of the solution are as follows: cu 13.81g/L, mn 98.7.7 g/L, zn 15.6.15.6 g/L, ca 4.81.81 g/L, al 4.78.78 g/L, co 0.69g/L, fe 0.001g/L, pH value = 2.5. And (3) mechanically stirring at normal temperature, slowly dropwise adding 10% sodium hydrosulfide solution, controlling the pH value in the reaction process, stopping adding the sodium hydrosulfide solution when the pH value at the end point is less than 0.2, continuing the reaction for 1h, performing vacuum filtration after the reaction is finished, performing liquid-solid separation to obtain 3325mL of copper-precipitated solution, and drying and weighing 71.88g of filter residues (copper sulfide concentrate). The obtained copper-precipitating solution contains Cu 0.0048g/L, pH value less than 0.1, copper sulfide concentrate contains Cu 57.6%, zn 0.21%, mn 0.28%, co 0.03%, and is used as raw material in downstream copper smelting industry. The recovery rate of copper precipitation is 99.60%.
(2) p204 zinc extraction and sulfuric acid back extraction to prepare a crude zinc sulfate solution:
A. mixing 20L of p204 extractant and 80L of sulfonated kerosene according to a volume ratio of 1:4 to obtain an extracted organic phase; and saponifying the extracted organic phase by using 30% sodium hydroxide solution with a saponification rate of 40% to obtain a soap organic phase for later use.
B. Sufficient sulfuric acid washing liquid of 0.2mol/L and sulfuric acid solution of 2mol/L are prepared for standby.
C. The extraction experiment is carried out by adopting an experimental continuous countercurrent mixing clarifying tank, wherein the volume of a single-stage stirring chamber of the mixing clarifying tank is 1L, the volume of a mixing chamber is 3L, and the mixing chamber is set to be 7 stages of zinc extraction sections, 4 stages of washing sections and 4 stages of back extraction sections. And (3) carrying out a continuous zinc extraction experiment to examine the stability of the extraction process, wherein the liquid volume ratio of the organic phase after the soap to the copper deposition is 4:1. And respectively sampling and analyzing the metal content of the solutions at the inlet end and the outlet end according to a certain time interval. The experimental results are shown in tables 1-2. Experimental results show that the zinc extraction recovery rate is more than 99%.
TABLE 1 example 1 copper precipitation post-liquid, extraction stage aqueous phase exit raffinate Metal content (g/L)
。
TABLE 2 Metal content (g/L) of crude Zinc sulfate solution at the aqueous phase outlet of the stripping section of example 1
。
(3) Neutralizing and precipitating calcium aluminum removal: 3000mL of zinc extraction raffinate is taken, 63.8g of sodium sulfate is added under mechanical stirring, the pH value of the system is continuously regulated to 5.0 by adopting sodium hydroxide, the reaction is continued for 2 hours, 2875mL of calcium and aluminum removal liquid is obtained after the reaction is completed, the filter residue is dried and heavy to obtain 48.5g of zinc sulfide slag, and 0.44g/L, al 0.0027.0027 g/L, fe 0.0004.0004 g/L of Ca is contained in the calcium and aluminum removal liquid.
(4) Replacing and precipitating cobalt by manganese powder: 2000mL of calcium and aluminum removing solution is taken, the temperature is raised to 60 ℃ under mechanical stirring, 7.92g of electrolytic manganese metal powder is added for reaction for 2 hours, the reaction is completed, vacuum filtration is carried out, the weight of filter residues is 9.78g after drying, 1945mL of high manganese solution is adopted, and the main components of the high manganese solution are 98.80g/L, co 0.0002g/L, cu 0.0002.0002 g/L, zn 0.0002g/L, ca 0.43g/L, al 0.0027g/L, fe 0.0004.0004 g/L. Cobalt displacement recovery was 98.44%.
Example 2
Referring to fig. 1, the method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step provided in this embodiment includes the following steps:
(1) Copper deposition by sodium hydrosulfide solution: 3000mL of copper chloride manganese zinc cobalt solution is taken, and the main components of the solution are as follows: cu 8.81g/L, mn 70.27g/L, zn 14.36.36 g/L, ca 3.27g/L, al 3.99g/L, co 0.59g/L, fe 0.001g/L, pH value=1.5. Mechanically stirring at normal temperature, slowly dripping 15% sodium hydrosulfide solution, controlling the pH value in the reaction process, stopping adding the sodium hydrosulfide solution when the end-point pH value is less than 0.2, continuing the reaction for 1h, performing vacuum suction filtration after the reaction is finished, performing liquid-solid separation to obtain 3218mL of copper-precipitated solution, and drying and weighing 50.48g of filter residues (copper sulfide concentrate). The copper-precipitating solution contains Cu 0.0042g/L, pH less than 0.1, cu 53.46%, zn 0.25%, mn 0.27% and Co 0.025%. The recovery rate of copper precipitation is 99.48%.
(2) Extracting zinc under the condition of low pH value of the P204 extractant and carrying out sulfuric acid back extraction to prepare a crude zinc sulfate solution:
A. mixing 20L of P204 extractant and 100L of sulfonated kerosene according to a volume ratio of 1:5 to obtain an extracted organic phase; and the mixed organic phase is saponified by ammonia water with the mass fraction of 25 percent, the saponification rate is 35 percent, and the organic phase after soap is obtained for standby.
B. Sufficient sulfuric acid washing liquid of 0.2mol/L and sulfuric acid solution of 2.5mol/L are prepared for standby.
C. The extraction experiment is carried out by adopting an experimental continuous countercurrent mixing clarifying tank, wherein the volume of a single-stage stirring chamber of the mixing clarifying tank is 1L, the volume of a mixing chamber is 3L, and the mixing chamber is set to be 7 stages of zinc extraction sections, 4 stages of washing sections and 4 stages of back extraction sections. And (3) carrying out a continuous zinc extraction experiment to examine the stability of the extraction process, wherein the volume ratio of the liquid flow of the organic phase after the soap to the liquid flow after copper precipitation is 5:1. And respectively sampling and analyzing the metal content of the solutions at the inlet end and the outlet end according to a certain time interval. The results are shown in tables 3 to 4. The zinc extraction recovery rate was shown to be greater than 99%.
TABLE 3 example 2 copper precipitation post-liquid, extraction stage aqueous phase exit raffinate Metal content (g/L)
。
TABLE 4 Metal content (g/L) of crude Zinc sulfate solution at the aqueous phase outlet of the stripping section of example 2
。
(3) Neutralizing and precipitating calcium aluminum removal: 3000mL of zinc-extracted liquid is taken, 56g of sodium sulfate is added under mechanical stirring, the pH value of the system is continuously regulated to 4.8 by adopting sodium hydroxide, the reaction is continued for 2 hours, 2895mL of calcium-aluminum-removed liquid is obtained after the reaction is completed, filter residues are discarded, and 0.44g/L, al g/L, fe 0.0004.0004 g/L of Ca is contained in the calcium-aluminum-removed liquid.
(4) Replacing and precipitating cobalt by manganese powder: 2000mL of calcium and aluminum removing solution is taken, the temperature is raised to 60 ℃ under mechanical stirring, 7.92g of electrolytic manganese metal powder is added for continuous reaction for 2 hours, vacuum suction filtration is carried out after the reaction is finished, the weight of filter residue is 9.78g, 1945mL of high manganese solution is dried, and the main components of the solution are 71.60g/L Mn, 0.0002g/L, cu g/L Co, 0.0002g/L Zn, 0.44g/L Ca, 0.0028g/L Al and 0.0003g/L Fe. Cobalt displacement recovery was 98.87%.
The method adopts the sodium hydrosulfide solution to rapidly precipitate copper under the condition of low pH value, realizes the separation of copper and zinc and manganese, and avoids synchronous precipitation of zinc and manganese during copper sulfide precipitation. Copper recovery is greater than 99%; the selective extraction of the p204 extractant under the condition of low pH value is adopted, so that the extraction separation of zinc and other metals is realized, and the extraction recovery rate of zinc is more than 99 percent; the calcium, iron and aluminum in the solution are removed by adopting the combined precipitation of sodium sulfate and a neutralizer, so that the problem that the obtained colloid is difficult to filter in the process of removing iron and aluminum by adopting a neutralization hydrolysis method independently can be solved; the cobalt in the solution is recovered by adopting a manganese powder replacement method, so that the recovery of cobalt is realized, the recovery rate of cobalt is more than 98%, and meanwhile, the zinc and copper in the solution are deeply purified; the method of the invention can economically and conveniently realize the fractional extraction and recycling of copper, zinc, cobalt and manganese metals.
In the foregoing, the invention is directed to a preferred embodiment, and any form of simple modification, equivalent variation and variation of the above embodiments according to the technical matter of the invention fall within the scope of the invention.
Claims (8)
1. A method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step is characterized by comprising the following steps:
(1) Copper deposition by sodium hydrosulfide solution: adding sodium hydrosulfide solution into copper chloride manganese zinc cobalt solution with pH value of 1.5-2.5 at normal temperature, controlling pH value of reaction end point to be less than 0.2, carrying out copper sulfide precipitation, and filtering to obtain copper sulfide concentrate and copper precipitation post-solution;
(2) p204 extraction of zinc: mixing p204 with sulfonated kerosene according to a volume ratio of 1:4-5 to obtain an extracted organic phase, and saponifying the extracted organic phase with a 30% sodium hydroxide solution or 25% ammonia water to obtain a saponification rate of 30-40% to obtain a post-soap organic phase; adding the post-soap organic phase into the post-copper precipitation solution, and controlling the extraction balance pH value to be 2.5-3, and selectively extracting zinc to obtain a zinc-containing loaded organic phase and zinc extraction residual liquid;
(3) Sulfuric acid back extraction: after the zinc-containing loaded organic phase is pickled, sulfuric acid is used for back extraction to prepare a crude zinc sulfate solution;
(4) Neutralizing and precipitating calcium aluminum removal: adding sodium sulfate and a neutralizer into the zinc extraction raffinate to adjust the pH value to 4.5-5.0, continuously reacting for 2 hours to precipitate and remove calcium and aluminum, and filtering to obtain waste residues containing calcium sulfate and aluminum hydroxide and calcium and aluminum removing liquid, and discarding the waste residues;
(5) Replacing and precipitating cobalt by manganese powder: adding manganese powder into the solution after removing calcium and aluminum to replace and precipitate cobalt, filtering to obtain cobalt slag and high-manganese solution, returning the cobalt slag to a cobalt raw material treatment system for leaching and dissolving treatment, and recycling the high-manganese solution.
2. The method for stepwise extracting and recovering copper, zinc, cobalt and manganese metals from copper, manganese, zinc and cobalt chloride solution according to claim 1, wherein the copper, manganese, zinc and cobalt chloride solution contains Mn 40-120 g/L, ca 0.3-10 g/L, co <
1g/L、Cu 5~20 g/L、Zn 5~20g/L、Al 0.1~10g/L、Fe 0.001~0.02g/L。
3. The method for stepwise extracting and recovering copper, zinc, cobalt and manganese metals from a copper-manganese-zinc-cobalt chloride solution according to claim 1, wherein in the step (1), the mass concentration of the sodium hydrosulfide solution is 10-15%, the obtained copper sulfide concentrate contains more than or equal to 50% of Cu, less than 0.3% of Zn, less than 0.3% of Mn and less than 0.05% of Co, and the obtained copper-precipitating post-solution contains less than 0.05g/L of Cu.
4. The method for stepwise extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution according to claim 1, wherein in the step (2), the liquid volume ratio of the organic phase after soap to the liquid after copper precipitation is 3-5:1, and the extraction stage number is 7; the zinc extraction raffinate contains less than 0.05g/L of Zn and has pH of 2.5-3.
5. The method for extracting and recovering copper, zinc, cobalt and manganese metals from a copper-manganese-zinc-cobalt chloride solution step by step according to claim 1, wherein in the step (3), the acid liquor used for pickling the zinc-containing loaded organic phase is sulfuric acid or hydrochloric acid solution with the concentration of 0.2mol/L, the washing volume ratio is 3-5:1, the washing stage number is 4, and the washing liquor is returned for reuse.
6. The method for stepwise extracting and recovering copper, zinc, cobalt and manganese metals from a copper-manganese-zinc-cobalt chloride solution according to claim 5, wherein the zinc-bearing organic phase after pickling is back extracted by adopting a 2mol/L sulfuric acid solution and the pH value of the back extraction end point is controlled to be 2.5-4, so that a crude zinc sulfate solution is obtained, wherein 110-130 g/L, mn < 3g/L, co < 0.05g/L, cu < 0.03g/L, ca < 0.5g/L, al < 0.5g/L of Zn is contained in the crude zinc sulfate solution, and the crude zinc sulfate solution can be used as a raw material in the downstream zinc smelting industry.
7. The method for stepwise extracting and recovering copper, zinc, cobalt and manganese metals from copper, manganese, zinc and cobalt chloride solution according to claim 1, wherein in the step (4), sodium sulfate is added in an amount which is 2 times of the theoretical amount required for precipitating all calcium ions in the solution into calcium sulfate, and the neutralizing agent is NaoH or NaCO 3 、NaHCO 3 ，NH 4 One or more of OH, and Ca < 0.5g/L, al < 0.003g/L, fe < 0.0005g/L in the calcium-iron-aluminum-removing post-liquid.
8. The method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step according to claim 1, wherein in the manganese powder displacement cobalt precipitation reaction in the step (5), the manganese powder consumption is 6-8 times of the theoretical consumption, and the reaction time is 2 hours at 60-80 ℃; the obtained high manganese solution contains Mn of 40-130 g/L, co which is less than 0.0003g/L, cu which is less than 0.0003g/L, zn which is less than 0.0003g/L, ca which is less than 0.5g/L, al which is less than 0.005g/L, fe which is less than 0.0005g/L.
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