CN114134323A - Process method for separating copper and manganese and application thereof - Google Patents
Process method for separating copper and manganese and application thereof Download PDFInfo
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- CN114134323A CN114134323A CN202111440439.2A CN202111440439A CN114134323A CN 114134323 A CN114134323 A CN 114134323A CN 202111440439 A CN202111440439 A CN 202111440439A CN 114134323 A CN114134323 A CN 114134323A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 239000011572 manganese Substances 0.000 title claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000012074 organic phase Substances 0.000 claims abstract description 115
- 238000000605 extraction Methods 0.000 claims abstract description 86
- 238000005406 washing Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007127 saponification reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 11
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 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
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000015096 spirit Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 17
- -1 sulfur ions Chemical class 0.000 description 16
- 239000008346 aqueous phase Substances 0.000 description 14
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910001437 manganese ion Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 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
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process method for separating copper and manganese and application thereof. The process method comprises the following steps: performing saponification reaction on the extracted organic phase to obtain a saponified organic phase; mixing, extracting and standing the saponified organic phase and the copper-manganese feed liquid to obtain a loaded organic phase and an extraction water phase; washing the loaded organic phase to obtain a washed loaded organic phase; and carrying out back extraction on the washed loaded organic phase to obtain a back extraction solution containing copper ions and a regenerated organic phase. The whole separation process is simple and convenient to operate, the phase separation is quick, the environment is protected, and the used extraction reagent is low in water solubility, stable and recyclable after regeneration.
Description
Technical Field
The invention relates to the field of new energy, and relates to a process method for separating copper and manganese and application thereof.
Background
The new energy battery is more and more widely applied to industries such as vehicles, energy storage, electronic equipment and the like, the usage amount is increased year by year, and the waste battery generated therewith becomes a problem to be solved urgently. There are many studies on extraction methods.
CN 102242266A discloses a method for recovering cobalt, copper, zinc and manganese in manganese chloride residual liquid. The main contents are as follows: the method comprises the steps of adjusting the chloride ion concentration of manganese chloride residual liquid to 250-350 g/L, extracting cobalt, copper and zinc in the manganese chloride residual liquid by using N235, keeping manganese in raffinate, then performing back extraction on the cobalt, copper and zinc in an organic phase by using a back extractant to obtain pure cobalt chloride, copper chloride solution and zinc precipitate, washing, drying and calcining the zinc precipitate to obtain a zinc oxide product, wherein the manganese in the raffinate is extracted by using P204 in the same series, performing back extraction by using acid to obtain a manganese salt solution, and evaporating, crystallizing and drying the manganese salt solution to obtain a manganese salt product, wherein the copper extraction capacity is poor and needs to be further improved.
CN108517425A discloses a method for reducing calcium and magnesium ions in electrolytic manganese qualified liquid. Preparing an extraction organic phase by adjusting the pH value of the qualified electrolytic manganese solution; saponifying the extracted organic phase with alkali liquor to obtain a sodium soap organic phase, and carrying out manganese soap treatment on the sodium soap organic phase with a manganese sulfate solution to obtain a manganese soap organic phase; extracting by taking the obtained manganese soap organic phase as an extracting agent and taking the electrolytic manganese qualified liquid with the adjusted pH as an extraction liquid to obtain a calcium-magnesium metal ion loaded organic phase and a deeply purified electrolytic manganese qualified liquid; the obtained organic phase loaded with calcium and magnesium metal ions is washed with manganese by dilute manganese sulfate solution, and then sulfuric acid is adopted for back extraction to obtain a regenerated extraction organic phase and a water phase loaded with calcium and magnesium metal ions, and the regenerated extraction organic phase can be recycled. The extraction method can remove calcium and magnesium ions in manganese, but cannot play a role in prompting the extraction of copper ions.
Korean smile, Marshmania. Cyanex272 process for separating copper and manganese in wastewater to prepare battery-grade manganese sulfate explores [ J ] colored equipment, 2020(02):41-43 discloses that Mn is extracted by Cyanex272, Mn is separated from Ca and Mg simultaneously, and Mn is refined and enriched after sulfuric acid back extraction. And evaporating, concentrating, centrifugally separating and drying to obtain a manganese sulfate crystal. The copper ion treatment mode adopts ammonium sulfide to precipitate copper, the ammonium sulfide is a toxic reagent, and excessive sulfur ions cause the waste water to generate stink and generate secondary pollution to the environment.
How to separate copper and manganese elements quickly, environmentally and stably is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a method for separating copper and manganese, which is rapid and environment-friendly and has low process cost, and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a process for separating copper and manganese, comprising the steps of:
and (4) carrying out saponification reaction on the extracted organic phase to obtain a saponified organic phase.
And mixing, extracting and standing the saponified organic phase and the copper-manganese feed liquid to obtain a loaded organic phase and an extraction water phase.
And washing the loaded organic phase to obtain a washed loaded organic phase.
And carrying out back extraction on the washed loaded organic phase to obtain a back extraction solution containing manganese ions and a regenerated organic phase.
The extraction process of the invention mainly comprises four steps: (1) preparing a high-purity extracting agent and a diluting agent into an extracted organic phase with a certain volume fraction, and then performing saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase; (2) mixing, extracting and layering the saponified organic phase-to-liquid material obtained in the step (1) to obtain a loaded organic phase and an extraction aqueous phase, and carefully controlling the pH of the extraction aqueous phase to be 1.5-3; (3) washing the loaded organic phase by using a detergent to wash out the extracted or carried metal ions to obtain a washed loaded organic phase and a washed residual liquid; (4) and (4) carrying out back extraction on the washed loaded organic phase obtained in the step (3) by using a back extractant, and controlling the pH of a back extracted solution to obtain a back extracted solution enriched in metal ions and a regenerated organic phase. The whole separation process is simple and convenient to operate, the phase separation is quick, the environment is protected, and the used extraction reagent is low in water solubility, stable and recyclable after regeneration.
As a preferable technical scheme of the invention, the extraction organic phase is prepared by an extracting agent and a diluting agent.
Preferably, the extractant is a carboxylic acid extractant.
Preferably, the extractant is CPH 88.
Preferably, the structural formula of CPH88 is shown as formula 1.
Preferably, the extractant comprises 5 to 30% by volume fraction of the organic phase, wherein the volume fraction of the extractant can be 5%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the diluent comprises escai id110, mineral spirits, toluene, hexane, heptane or dodecane, or any one or combination of at least two thereof, wherein typical but non-limiting examples are: combinations of escoid 110 and mineral spirits, solvent spirits and toluene, toluene and hexane, hexane and heptane, or heptane and dodecane, and the like.
The invention selects an extractant CPH88, the main component of which is a carboxylic acid compound. The preparation method comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
As a preferred embodiment of the present invention, the alkaline compound in the saponification reaction includes any one or a combination of at least two of sodium hydroxide, magnesium oxide, potassium hydroxide or ammonia, wherein the combination is exemplified by, typically but not limited to: a combination of sodium hydroxide and magnesium oxide, a combination of magnesium oxide and potassium hydroxide, a combination of potassium hydroxide and ammonia water, or the like.
Preferably, the saponification degree of the saponified organic phase is 20-55%, wherein the saponification degree may be 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, or 55%, etc., but is not limited to the recited values, and other values not recited in this numerical range are also applicable.
As a preferable technical scheme of the invention, the solvent of the copper-manganese feed liquid comprises chloride salt or sulfate.
In a preferred embodiment of the present invention, the mixing speed is 500 to 800rmp, and the mixing speed may be 500rmp, 550rmp, 600rmp, 650rmp, 700rmp, 750rmp, or 800rmp, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the mixing time is 5-30 min, wherein the time can be 5min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, etc., but is not limited to the recited values, and other non-recited values in the range of the values are also applicable.
Preferably, the volume ratio of the saponified organic phase to the copper-manganese feed liquid is 1: (0.1 to 10), wherein the volume ratio may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the extraction is a multistage countercurrent fractional extraction.
Preferably, the multistage countercurrent fractional extraction has 2 to 18 stages, wherein the stages can be 2 stages, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages, 10 stages, 11 stages, 12 stages, 13 stages, 14 stages, 15 stages, 16 stages, 17 stages or 18 stages, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the temperature of the extraction is 22 to 30 ℃, wherein the temperature can be 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the standing time is 2-30 min, wherein the standing time can be 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
As a preferable technical scheme of the invention, the pH value of the raffinate water phase is 1.5-3.0. The pH may be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred technical scheme of the invention, the detergent in the washing comprises inorganic acid.
Preferably, the number of washing stages is 1 to 15, wherein the number of washing stages may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, but is not limited to the enumerated values, and other non-enumerated values in the range of the enumerated values are also applicable.
Preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid, or a combination of at least two thereof.
Preferably, the concentration of the inorganic acid is 0.5 to 4mol/L, wherein the concentration may be 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, or 4mol/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the stripping agent in the stripping comprises inorganic acid.
Preferably, the number of the back extraction is 1 to 15, wherein the number of the back extraction can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, but is not limited to the enumerated values, and other non-enumerated values in the range of the enumerated values are also applicable.
Preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof;
preferably, the concentration of the inorganic acid is 0.5 to 4mol/L, wherein the concentration may be 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, or 4mol/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the volume ratio of the stripping agent to the washed loaded organic phase is 1: (0.1 to 10), wherein the volume ratio may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred technical scheme of the invention, the regenerated organic phase is recycled.
Preferably, the total flow number of the process method is 3-45, wherein the reaction number may be 3, 5, 10, 15, 20, 25, 30, 35, 40 or 45, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
The second purpose of the invention is to provide the application of the process for separating copper and manganese according to the first purpose, and the process is applied to the technical field of chemical extraction.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the extractant CPH88 is used for extraction, so that copper can be separated from the high-manganese feed liquid, and the loss of manganese can not be caused; the acidity required by copper extraction is high, alkali is not required to be consumed to adjust the pH value, the copper-manganese separation effect is good, and the separation effect can be achieved by washing with a small amount of acid.
Drawings
FIG. 1 is a flow chart of the separation of copper and manganese ions in examples 1 to 8 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound CPH88 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 25%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (containing 0.49g/L of nickel, 0.74g/L of cobalt, 39.80g/L of manganese, 2.17g/L of copper and 0.17g/L of magnesium, having a pH value of 1.0-1.5, specifically originating from an intermediate material obtained after P204 impurity removal of a leachate of a positive electrode material of a waste lithium ion battery), extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) from the extraction tank respectively with the saponified organic phase in the step (1), mixing at a stirring speed of 850rpm/min and a mixing time of 15min and a temperature of 25 ℃, performing multistage countercurrent extraction, wherein the extraction stages are 6 stages, standing and layering to obtain a loaded organic phase and an extracted residual aqueous phase with a pH value of 2.0;
(3) the washing system is a hydrochloric acid system, a sulfuric acid system is used for back extraction, 9-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 1mol/L hydrochloric acid, back extraction is carried out by adopting 4mol/L sulfuric acid, and the number of the back extraction stages is 5; the flow ratio of the washing acid to the loaded organic phase is 1:6.94, and the flow ratio of the 4mol/L sulfuric acid to the loaded organic phase is 1:12.60, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 2
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound CPH88 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 30%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (0.0078 g/L of nickel, 0.088g/L of cobalt, 91.67g/L of manganese, 0.291g/L of copper and 0.002g/L of zinc, wherein the pH value is 1.18, the feed liquid is specifically derived from P204 impurity-removing back extraction liquid), respectively extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) of the saponified organic phase from the extraction tank in the step (1), mixing at the stirring speed of 800rpm/min, the mixing time of 15min and the temperature of 25 ℃, performing multistage countercurrent extraction, wherein the number of extraction stages is 5, standing and layering to obtain a loaded organic phase and an extraction residual aqueous phase with the pH value of 2.6;
(3) the washing system is a hydrochloric acid system, a sulfuric acid system is used for back extraction, 7-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 1mol/L hydrochloric acid, back extraction is carried out by adopting 4mol/L sulfuric acid, and the number of the back extraction stages is 5; the flow ratio of the washing acid to the loaded organic phase is 1:4.64, and the flow ratio of the 4mol/L sulfuric acid to the loaded organic phase is 1:10.6, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 3
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound CPH88 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 20%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 20%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (containing 0.00177g/L nickel, 0.1367g/L cobalt, 91.08g/L manganese, 0.35g/L copper and 0.095g/L zinc, having a pH value of 1.74, specifically originating from the feed liquid from P204 impurity removal back extraction liquid), respectively extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) from the extraction tank with the saponified organic phase in the step (1), mixing at a stirring speed of 800rpm/min, a mixing time of 15min and a temperature of 25 ℃, performing multistage countercurrent extraction, wherein the number of extraction stages is 5 stages, standing for 30min for layering to obtain a loaded organic phase and a raffinate aqueous phase with a pH value of 2.8;
(3) the washing system is a hydrochloric acid system, a sulfuric acid system is used for back extraction, 7-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 1mol/L hydrochloric acid, back extraction is carried out by adopting 4mol/L sulfuric acid, and the number of the back extraction stages is 5; the flow ratio of the washing acid to the loaded organic phase is 1:5.52, and the flow ratio of the 4mol/L sulfuric acid to the loaded organic phase is 1:10, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 4
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound CPH88 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 35%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (0.0057 g/L of nickel, 0.15g/L of cobalt, 98.78g/L of manganese, 0.42g/L of copper, 0.086g/L of iron, 0.0024g/L of zinc, pH value of 1.43, specifically from the feed liquid derived from C272 impurity removal back extraction liquid), extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) from the extraction tank respectively with the saponified organic phase in the step (1), mixing at the stirring speed of 800rpm/min, mixing time of 15min and temperature of 25 ℃, carrying out multistage countercurrent extraction, extracting stage number of 5, standing for 30min for layering to obtain a loaded organic phase and an extracted residual aqueous phase with pH value of 1.8;
(3) the washing system is a hydrochloric acid system, a sulfuric acid system is used for back extraction, 7-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 1mol/L hydrochloric acid, back extraction is carried out by adopting 4mol/L sulfuric acid, and the number of the back extraction stages is 5; the flow ratio of the washing acid to the loaded organic phase is 1:3.7, and the flow ratio of the 4mol/L sulfuric acid to the loaded organic phase is 1:11, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 5
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound CPH88 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 25%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (containing 0.43g/L of nickel, 1.61g/L of cobalt, 48.96g/L of manganese, 1.78g/L of copper and 0.0029g/L of magnesium, having a pH value of 2.15, specifically originating from the feed liquid from P507 impurity removal back extraction liquid), respectively extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) from the extraction tank with the saponified organic phase in the step (1), mixing at a stirring speed of 850rpm/min, a mixing time of 15min and a temperature of 25 ℃, performing multistage countercurrent extraction, having extraction stages of 6 stages, standing for 30min for layering to obtain a loaded organic phase and an extraction residual aqueous phase with a pH value of 2.7;
(3) the washing system is a hydrochloric acid system, a sulfuric acid system is used for back extraction, 11-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 1mol/L hydrochloric acid, back extraction is carried out by adopting 4mol/L sulfuric acid, and the number of the back extraction stages is 7; the flow ratio of the washing acid to the loaded organic phase is 1:7, and the flow ratio of the 4mol/L sulfuric acid to the loaded organic phase is 1:13, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 6
The embodiment provides a method for separating copper and manganese and an application thereof, and the specific steps are as follows, wherein the copper and manganese ion separation process is shown in figure 1:
(1) dissolving the prepared carboxylic acid compound BC211 in Escaid110, wherein the volume percentage of the BC211 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 30%, wherein the saponified organic phase is used as an organic phase system;
(2) taking the feed liquid as an aqueous phase system (2.93 g/L of nickel, 2.95g/L of cobalt, 2.74g/L of manganese, 2g/L of copper, 1.22g/L of iron and 2.04 of pH value, specifically, the feed liquid is derived from C272 impurity removal back extraction liquid), respectively extracting 1-stage inflow (the volume ratio of the saponified organic phase to the feed liquid is 1:1) from the extraction tank with the saponified organic phase in the step (1), mixing at a stirring speed of 650rpm/min, a mixing time of 15min and a temperature of 25 ℃, performing multistage countercurrent extraction, wherein the number of extraction stages is 6 stages, standing for 30min for layering to obtain a loaded organic phase and a raffinate aqueous phase with a pH value of 1.7;
(3) a sulfuric acid system is used for both the washing system and the back extraction system, 11-stage countercurrent washing is carried out on the loaded organic phase obtained in the step (2) by adopting 3.5mol/L sulfuric acid, back extraction is carried out by adopting 7mol/L sulfuric acid, and the number of the back extraction stages is 7; the flow ratio of the washing acid to the loaded organic phase is 1:5, and the flow ratio of the 7mol/L sulfuric acid to the loaded organic phase is 1:9, so that a metal ion enriched solution and a regenerated organic phase are obtained.
The preparation method of the carboxylic acid compound CPH88 comprises the following steps: 20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate, and spin-drying the solvent, 35.4g of the objective product was obtained.
Example 7
In this example, the conditions were the same as in example 1 except that the carboxylate CPH88 was replaced with the carboxylate BC 196. The preparation method of the carboxylic acid compound BC196 comprises the following steps: adding 28.6g of isooctanol, 200mL of Tetrahydrofuran (THF) and 8.8g of 60% sodium hydride (dispersed in mineral oil) into a three-neck flask, and reacting at 60-70 ℃ for 6 hours to generate a large amount of white solid and a small amount of sodium particles; dripping 20mL of 10mol/L THF solution of 2-bromohexanoic acid at 60 ℃ and continuing to react for 4h at 60 ℃; cooling, performing rotary evaporation to remove THF, adding 200mL of water and 200mL of Ethyl Acetate (EA) into the concentrated solution, shaking for layering, and taking a water layer; the aqueous layer is acidified by hydrochloric acid until the pH value is approximately equal to 1, extracted by ethyl acetate, and the organic phase is washed by water for 2 times and spin-dried to obtain 38g of light yellow product.
Example 8
In this example, the conditions were the same as in example 1 except that the carboxylate CPH88 was replaced with the carboxylate BC 197. The preparation method of the carboxylic acid compound BC197 comprises the following steps: a250 mL round-bottom flask was charged with 25g (0.15mol) of methyl tetrahydrophthalic anhydride, 100mL of toluene, 25mL (0.19mol) of isooctanol, a few drops of concentrated sulfuric acid, heated to 80 ℃ and stirred for 1.5h, the reaction was stopped, and the remaining isooctanol was distilled off to obtain 25.7g of a product.
The copper content of the raffinate was tested for examples 1-8, where the same homogeneous copper manganese feed was used for examples 1-8, and the results are shown in Table 1.
TABLE 1
| Copper content (mg/L) | |
| Example 1 | 0.5 |
| Example 2 | 0.178 |
| Example 3 | 0.193 |
| Example 4 | 0.213 |
| Example 5 | 0.437 |
| Example 6 | 0.486 |
| Example 7 | 4.63 |
| Example 8 | 4.61 |
The results show that the extractant series CPH88, BC196 and BC197 can effectively separate copper and manganese and avoid the loss of manganese caused by copper precipitation, and the comparison between examples 1-6 and examples 7-8 shows that the extraction rate of copper of BC196 and BC197 is inferior to that of CPH88 under the same pH condition.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A process for separating copper and manganese, comprising the steps of:
performing saponification reaction on the extracted organic phase to obtain a saponified organic phase;
mixing, extracting and standing the saponified organic phase and the copper-manganese feed liquid to obtain a loaded organic phase and an extraction water phase;
washing the loaded organic phase to obtain a washed loaded organic phase;
and carrying out back extraction on the washed loaded organic phase to obtain a back extraction solution containing copper ions and a regenerated organic phase.
2. The process of claim 1, wherein the organic extraction phase is formulated with an extractant and a diluent;
preferably, the extractant is a carboxylic acid extractant;
preferably, the extractant is CPH 88;
preferably, the structural formula of CPH88 is shown as formula 1,
preferably, the extractant accounts for 5-30% of the extracted organic phase in terms of volume fraction;
preferably, the diluent comprises any one of Escaid110, mineral spirits, toluene, hexane, heptane or dodecane or a combination of at least two thereof.
3. A process as claimed in claim 1 or 2, wherein the alkaline compound in the saponification reaction comprises any one or a combination of at least two of sodium hydroxide, magnesium oxide, potassium hydroxide or ammonia water;
preferably, the saponification degree of the saponified organic phase is 20-55%.
4. A process according to any one of claims 1 to 3, wherein the solvent for the copper manganese liquor comprises a chloride or sulphate salt.
5. A process according to any one of claims 1 to 4, wherein the mixing is at a rate of from 500 to 800 rmp;
preferably, the mixing time is 5-30 min;
preferably, the volume ratio of the saponified organic phase to the copper-manganese feed liquid is 1: (0.1 to 10);
preferably, the extraction is a multi-stage countercurrent fractional extraction;
preferably, the number of stages of the multistage countercurrent fractional extraction is 2-18;
preferably, the temperature of the extraction is 22-30 ℃;
preferably, the standing time is 2-30 min.
6. A process according to any one of claims 1 to 5, wherein the pH of the aqueous raffinate phase is from 1.5 to 3.0.
7. A process according to any one of claims 1 to 6, wherein the washing agent comprises a mineral acid;
preferably, the washing stages are 1-15 stages;
preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof;
preferably, the concentration of the inorganic acid is 0.5-4 mol/L.
8. The process according to any one of claims 1 to 7, wherein the stripping agent comprises an inorganic acid;
preferably, the number of the back extraction stages is 1-15;
preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof;
preferably, the concentration of the inorganic acid is 0.5-4 mol/L;
preferably, the volume ratio of the stripping agent to the washed loaded organic phase is 1: (0.1-10).
9. The process according to any one of claims 1 to 8, wherein the regenerated organic phase is recycled;
preferably, the total flow stages of the process method are 3-45 stages.
10. Use of a process for the separation of copper and manganese according to any one of claims 1 to 9 in the field of new energy.
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| CN114836631B (en) * | 2022-06-15 | 2023-12-01 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese liquid generated by extraction and recovery of battery materials |
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