CN112499686A - Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid - Google Patents
Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011572 manganese Substances 0.000 title claims abstract description 93
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 48
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 239000012535 impurity Substances 0.000 claims abstract description 39
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 19
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 19
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 19
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001556 precipitation Methods 0.000 claims description 19
- -1 aluminum ions Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910001437 manganese ion Inorganic materials 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 8
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006115 defluorination reaction Methods 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000002222 fluorine compounds Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 23
- 239000011737 fluorine Substances 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000010949 copper Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910020630 Co Ni Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- PVIFNYFAXIMOKR-UHFFFAOYSA-M manganese(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Mn+3] PVIFNYFAXIMOKR-UHFFFAOYSA-M 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Abstract
The invention discloses a method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid, which comprises the following steps: adding a precipitator into the waste manganese solution, and removing solid-phase impurities to obtain a crude manganese solution; adding manganese powder into the crude manganese solution to obtain a refined manganese solution; adding sulfide into the crude manganese solution to obtain a purified manganese solution; adding aluminum salt and a settling agent A into the purified manganese solution to obtain a manganese sulfate solution; adding aluminum, a complexing agent B and an alkaline substance into a manganese sulfate solution, and oxidizing to obtain the manganese oxyhydroxide. The invention skillfully utilizes the combination of the impurity removal reagent and product doping, solves the problem of residual excessive impurity removal reagent in the impurity removal process, and improves the performance of the product.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid.
Background
The waste manganese liquid is from a P204 extraction purification impurity removal process section in a nickel-cobalt production enterprise, impurities extracted into an organic phase are subjected to back extraction in the process section to obtain waste liquid, the main component of the waste manganese liquid is manganese element, and a small amount of copper, zinc, cobalt, calcium and the like are also contained. Meanwhile, along with the retirement of the ternary battery, waste manganese liquid can be formed in the process of disassembling and utilizing the waste ternary cathode material and recovering nickel, cobalt, manganese and lithium through wet processing; the recycling of the waste manganese liquid is in need of solution.
At present, the waste manganese liquid in China is mainly used for producing battery-grade manganese sulfate; or the manganese slag is formed by precipitating the manganese solution, and then the manganese slag is transferred to other manganese production enterprises for reprocessing. The production process flow of battery-grade manganese sulfate in the related technology is shown in figure 1, and a large amount of sulfuric acid and liquid alkali are consumed for extraction in the production process; the process has long operation time, high production cost and poor production efficiency, and is only used as an environment-friendly supporting project.
In the related technology, the treatment flow of the manganese waste liquid precipitation method is shown in figure 2, about 2 tons of sodium carbonate are needed for precipitating 1 ton of manganese, the subsequent wastewater treatment cost, labor, energy and the like are also needed, and the price of the waste manganese metal for treating 1 ton is preliminarily estimated to be about 5000 yuan; meanwhile, the manganese waste residue still needs to be post-treated, so that the consumption is increased, and the production benefit is low.
The overall utilization rate of the manganese waste is low in the related technology, the consumption of auxiliary materials is high, and the production benefit is low. Therefore, a method for utilizing waste manganese liquid with high manganese utilization rate and good production efficiency is needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for recycling the manganese waste liquid has high overall utilization rate of manganese elements and good production benefit.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid comprises the following steps:
s1, calcium removal: adjusting the pH value of the waste manganese liquid to 5.0-5.5 under a heating condition, adding a precipitator, and removing solid phase impurities to obtain a crude manganese solution;
s2, reduction: adding manganese powder into the crude manganese solution, adjusting the pH to 1.5-3.0 under a heating condition, and removing solid phase impurities to obtain a refined manganese solution;
s3, precipitation: adding sulfide into the crude manganese solution, adjusting the pH to 4.0-5.0 under a heating condition, and removing solid phase impurities to obtain a purified manganese solution;
s4, defluorination: adding an aluminum salt I and a settling agent A into the purified manganese solution, adjusting the pH to 5.0-5.5 under a heating condition, and performing solid-liquid separation to obtain a manganese sulfate solution;
s5, preparation: adding aluminum salt II, complexing agent B and alkaline substance into manganese sulfate solution to obtain finished product solution, introducing oxidant into the finished product solution, and controlling reaction conditions to obtain the manganese oxyhydroxide.
According to some embodiments of the present invention, in the calcium removing step, the heating temperature is 80 to 90 ℃ and the reaction time is 2 to 5 hours.
According to some embodiments of the invention, the calcium removal step further comprises sampling and analyzing the liquid phase.
According to some embodiments of the invention, the precipitating agent is fluoride; preferably, the fluoride is at least one of sodium fluoride, ammonia fluoride, potassium fluoride, and manganese fluoride.
According to some embodiments of the invention, the fluoride is manganese fluoride.
The manganese fluoride reduces the introduction of impurity ions (such as sodium ions, potassium ions, ammonium ions and the like).
According to some embodiments of the invention, in the reduction step, the heating temperature is 55-75 ℃ and the reaction time is 3-6 h.
According to some embodiments of the invention, in the reducing step, the solid phase impurities are mainly copper.
Manganese powder is used as a reducing agent, and under the condition of strong stirring, metal manganese is fully contacted with ions such as copper, zinc, cobalt and nickel in the solution to generate a displacement reaction, so that most metal ions in the solution are removed. Copper in the solid-phase impurities is used as a raw material for copper smelting enterprises.
According to some embodiments of the invention, the sulfide comprises at least one of sodium sulfide, potassium sulfide, ammonium sulfide, hydrogen sulfide, and manganese sulfide.
According to some embodiments of the invention, the sulfide is at least one of manganese sulfide and hydrogen sulfide.
The manganese powder is adopted to primarily remove heavy metals, and then the sulfide is adopted to deeply remove the heavy metals, so that the content of the heavy metals in the filtrate is greatly reduced, and the national standard is met.
According to some embodiments of the invention, the aluminum salt is at least one of aluminum sulfate and polyaluminum sulfate.
The excessive aluminum ions realize the doping of the manganese oxyhydroxide.
According to some embodiments of the invention, the settling agent a is polyacrylamide.
The precipitator A has flocculation effect on the aluminum fluoride and accelerates the precipitation of fluorine ions; the settling agent A has complexation with manganese ions to form a complex, so that the oxidation potential of the synthesized hydroxyl manganese oxide is reduced.
According to some embodiments of the present invention, in the precipitation step, the heating temperature is 60 to 70 ℃ and the reaction time is 2 to 5 hours.
According to some embodiments of the invention, in the step of removing fluorine, the heating temperature is 70-80 ℃ and the reaction time is 2-5 h.
According to some embodiments of the invention, the mass ratio of the complexing agent B to the manganese element in the manganese sulfate solution is 0.005-0.025: 1.
According to some embodiments of the invention, the aluminium salt ii is at least one of aluminium sulphate and polyaluminium sulphate. According to some embodiments of the invention, the alkaline substance is sodium hydroxide.
According to some embodiments of the invention, the complexing agent B is at least one of citric acid and EDTA.
According to some embodiments of the invention, the concentration of the alkaline substance is 4 to 10 mol/L.
According to some embodiments of the invention, the concentration of manganese ions in the finished liquid is 1-2.5 mol/L.
According to some embodiments of the invention, the mass ratio of the aluminum ions in the finished product liquid to the manganese ions in the finished product liquid is 0.01-0.05: 1.
according to some embodiments of the invention, the oxidant is oxygen or air; preferably, the oxidant is air.
According to some embodiments of the invention, the reaction conditions in the preparing step are: the reaction temperature is 50-70 ℃, the reaction pH is 8-10, the stirring speed is 200-300 rpm, and the air flow is 35-55 Nm3/h。
According to some embodiments of the invention, the preparing step comprises stirring at a speed of 150 to 360 rpm.
The method for preparing the aluminum-doped manganese oxyhydroxide by using the waste manganese solution according to the embodiment of the invention has at least the following beneficial effects: the invention adopts the precipitator (such as manganese fluoride) to remove calcium, does not introduce new heavy metal ion impurities, and does not influence the quality of the manganese solution; firstly, removing calcium ions by a precipitator, and further reducing the concentration of the calcium ions in the solution in the process of treating other impurity ions in the subsequent process; in the heavy metal impurity removal process, manganese powder is selected to replace heavy metal ions in the solution, the heavy metal ions are converted into metal simple substances, and meanwhile, the manganese ions are generated in the manganese powder replacement process, so that the concentration of the manganese ions in the solution is improved under the condition that impurity ions are not introduced; sulfides are selected for further precipitation of the heavy metal ions, further impurity removal of the heavy metal ions is realized by the sulfides, heavy metal impurity ions in the solution are greatly reduced, and meanwhile, the consumption of the sulfides is low and the production cost is low; the impurity removal of fluorine ions is realized by selecting aluminum salt and the settling agent A, the aluminum ions are elements for subsequent doping, and the settling agent A realizes the precipitation fluorine removal and reduces the potential for producing the manganese oxyhydroxide; the combination of the reagent for impurity removal and product doping is skillfully utilized, the problem that the reagent is excessive and remains in the impurity removal process is solved, and the performance of the product is improved.
Drawings
FIG. 1 is a flow chart of a process for producing manganese sulfate for a battery in the related art;
FIG. 2 is a process flow diagram of a manganese waste liquid precipitation method in the related art;
FIG. 3 is a process flow diagram of an embodiment of the invention;
FIG. 4 SEM image (1000X) of aluminum-doped manganese oxyhydroxide prepared according to example one;
FIG. 5 SEM image (3000 ×) of aluminum doped manganese oxyhydroxide prepared by example one;
FIG. 6 SEM image (10000 ×) of aluminum-doped manganese oxyhydroxide prepared by example one;
FIG. 7 SEM image (1000X) of aluminum-doped manganese oxyhydroxide prepared in example two;
FIG. 8 SEM image (3000 ×) of aluminum doped manganese oxyhydroxide prepared for example two;
FIG. 9 SEM image (10000X) of aluminum doped manganese oxyhydroxide prepared by example two.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
The main components of the manganese waste liquid in the first embodiment of the present invention are shown in table 1.
Table 1 main components of waste manganese liquor selected in the first embodiment of the present invention
| Element(s) | Mn | Zn | Cu | Ca | Co | Ni | Mg | Fe |
| Content (g/L) | 100 | 2 | 5 | 3 | 0.05 | 0.015 | 0.01 | 0.0035 |
The first embodiment of the invention is as follows: a method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid, as shown in fig. 3, comprising the following steps:
s1, precipitation and calcium removal (purification A):
adding the waste manganese solution into a reaction kettle, starting stirring, controlling the temperature at 85 ℃, adjusting the pH value of the solution to 5.3, adding a manganese fluoride settling agent to enable the concentration of Ca element in the solution to reach a specified value (0.005g/L), continuing to react for not less than 2 hours, filtering and separating, aging the filtrate for 24 hours, and finely filtering the aging solution to obtain a rough manganese solution;
s2, manganese displacement precipitation (purification B):
adding the crude manganese solution into a reaction kettle, starting stirring, heating to 60 ℃, adjusting the pH value of the solution to 1.8, gradually adding manganese powder to enable the Cu element in the solution to reach a specified value (0.1g/L), continuing to react for 2 hours, and filtering and separating to obtain a refined manganese solution;
s3, sulfiding precipitation (clean C):
adding the refined manganese solution into a reaction kettle, starting stirring, controlling the temperature at 65 ℃, adjusting the pH value of the solution to 4.5, adding a hydrogen sulfide settling agent to enable the Cu element in the solution to reach a specified value (0.001g/L), continuing to react for 1h, and filtering and separating to obtain a purified manganese solution;
s4, defluorination (purification D):
adding the purified manganese solution into a reaction kettle, starting stirring, controlling the temperature at 78 ℃, adjusting the pH value of the solution to 5.3, adding polyaluminium sulfate (the mass ratio of fluorine to aluminum is 1:2) and polyacrylamide (the mass ratio of Al to polyacrylamide is 1000:1), allowing F ions to reach a specified value (0.005g/L), continuing to react for 2 hours, and filtering and separating to obtain a manganese sulfate solution, wherein the components of the manganese sulfate solution after the fluorine removal is finished in the embodiment are shown in Table 2;
TABLE 2 composition of manganese sulfate solution after completion of defluorination in this example
| Element(s) | Mn | Zn | Cu | Ca | Co | Ni | Mg | Fe | F | Al |
| Content (g/L) | 100 | 0.001 | 0.001 | 0.008 | 0.001 | 0.001 | 0.005 | 0.001 | 0.01 | 1.46 |
S5, preparation: according to the reaction conditions, the aluminum sulfate and EDTA (the mass concentration ratio of Mn element to Al element is 58.3: 1; the mass concentration ratio of Mn element to EDTA is 70.2:1) are mixed in proportion, the manganese sulfate solution and the sodium hydroxide solution (the mass concentration is 32%) are added into a reaction container, and air (the flow rate is 25Nm3And/h), controlling the stirring speed of the reaction vessel to be 230rpm, controlling the pH value to be 9.5 and the reaction temperature to be 56 ℃, continuously reacting, continuously feeding the solution into an ageing tank after the particle size of particles in the solution reaches a specified value (D50 is 10.5 mu m), carrying out solid-liquid separation, drying, metering and packaging, and producing to obtain the aluminum-doped manganese oxyhydroxide.
The quality indexes of the aluminum-doped manganese oxyhydroxide prepared by the embodiment are shown in Table 3.
TABLE 3 quality index of aluminum-doped manganese oxyhydroxide prepared in this example
As can be seen from Table 3, the aluminum-doped manganese oxyhydroxide prepared in example one had a low impurity content.
The main components of the waste manganese solution used in the second embodiment of the present invention are shown in table 4.
Table 4 main components of waste manganese liquid selected in example two of the present invention
| Element(s) | Mn | Zn | Cu | Ca | Co | Ni | Mg | Fe |
| Content (g/L) | 150 | 2.5 | 6.3 | 3.2 | 0.06 | 0.03 | 0.013 | 0.005 |
The second embodiment of the invention is as follows: a method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid, as shown in fig. 3, comprising the following steps:
s1, precipitation and calcium removal (purification A):
adding the waste manganese solution into a reaction kettle, starting stirring, controlling the temperature at 83 ℃, adjusting the pH value of the solution to 5.3, adding a manganese fluoride settling agent to ensure that the Ca element in the solution reaches a specified value (0.005g/L), continuously reacting for 2h, filtering and separating, aging the filtrate for 24h, and finely filtering the aged solution to obtain a crude manganese solution;
s2, manganese displacement precipitation (purification B):
adding the crude manganese solution into a reaction kettle, starting stirring, heating to 60 ℃, adjusting the pH value of the solution to 1.8, gradually adding manganese powder to enable the Cu element in the solution to reach a specified value (0.1g/L), continuing to react for 2 hours, and filtering and separating to obtain a refined manganese solution;
s3, sulfiding precipitation (clean C):
adding the crude manganese solution into a reaction kettle, starting stirring, controlling the temperature at 65 ℃, adjusting the pH value of the solution to 4.5, adding a manganese sulfide settling agent to enable the Cu element in the solution to reach a specified value (0.001g/L), continuing to react for 2 hours, filtering and separating to obtain a purified manganese solution;
s4, defluorination (purification D):
adding the purified manganese solution into a reaction kettle, starting stirring, controlling the temperature to be 79 ℃, adjusting the pH value of the solution to 5.2, adding polyaluminium sulfate (the mass ratio of fluorine to aluminum is 1:2) and polyacrylamide (the mass ratio of Al to polyacrylamide is 1000:1) to enable the F element in the solution to reach a specified value (0.005g/L), continuing to react for 2 hours, and filtering and separating to obtain a manganese sulfate solution, wherein the components of the manganese sulfate solution after the fluorine removal in the embodiment are shown in Table 5;
TABLE 5 composition of manganese sulfate solution after completion of defluorination in this example
| Element(s) | Mn | Zn | Cu | Ca | Co | Ni | Mg | Fe | F | Al |
| Content (g/L) | 151 | 0.001 | 0.001 | 0.007 | 0.0013 | 0.0012 | 0.006 | 0.0012 | 0.012 | 1.57 |
S5, preparation: according to the reaction conditions, aluminum sulfate and complexing agent EDTA (the mass concentration ratio of Mn element to Al element is 58.3: 1; the mass concentration ratio of Mn element to EDTA is 70.2:1) are mixed in proportion, manganese sulfate solution and sodium hydroxide solution (the mass concentration is 32%) are added into a reaction kettle, and air (the flow is 25 Nm/Nm)3And/h), continuously reacting at the reaction temperature of 60 ℃ under the condition that the stirring speed of the reaction kettle is controlled to be 220rpm, the pH value is 9.6, and the particle size of particles in the solution reaches a specified value (15.3 mu m of D50), continuously feeding the particles into an ageing tank, carrying out solid-liquid separation, drying, metering and packaging to produce the aluminum-doped manganese oxyhydroxide.
The quality index of the aluminum-doped manganese oxyhydroxide prepared by the embodiment is shown in Table 6.
TABLE 6 quality index of aluminum-doped manganese oxyhydroxide prepared in this example
As can be seen from Table 6, the aluminum-doped manganese oxyhydroxide prepared in example two had a low impurity content.
The pH adjustment processes not specifically described in the first and second embodiments of the present invention may be performed by conventional methods and parameters.
SEM images of the manganese oxyhydroxide prepared in the first embodiment of the invention under different magnifications are shown in FIGS. 4-6, and it is known from FIGS. 4-6 that the manganese oxyhydroxide prepared in the first embodiment of the invention is spherical particles.
SEM images of the manganese oxyhydroxide prepared in the second embodiment of the invention under different magnifications are shown in FIGS. 7-9, and it is known from FIGS. 7-9 that the manganese oxyhydroxide prepared in the second embodiment of the invention is spherical particles.
According to the method for recycling the waste manganese liquid, calcium ions in the waste manganese liquid are precipitated in a fluoride combination mode, and the calcium ions are removed from the liquid phase in a calcium fluoride mode; manganese powder is used for replacing and removing copper, zinc, nickel, cobalt and other ions, so that primary impurity removal of metal ions and recovery of other metal ions are realized, and the cost is reduced; after the primary impurity removal is finished, a small amount of residual copper, zinc, nickel and cobalt ions in the solution are removed from the liquid phase in the form of sulfide by selecting sulfide, so that the concentration of heavy metal ions in the solution is greatly reduced, and the solution is purified. If the manganese powder or the sulfide is used independently to remove heavy metal ions in the solution, the consumption of the manganese powder and the sulfide is extremely high; when the manganese powder is used alone to remove heavy metal ions in the solution, the heavy metal ions in the solution reach the standard, the using amount of the manganese powder is 5-10 times of the amount of heavy metal substances in the solution, and excessive manganese powder can be accumulated in a solid phase, so that resource waste is caused; when the hydrogen sulfide is used alone to remove the heavy metal ions in the solution, the manganese ions in the solution are coprecipitated with other heavy metal ions due to the high concentration of the manganese ions in the solution, so that the consumption of sulfides is increased. The method adopts a mode of combining manganese powder and sulfide, the manganese powder is only used for primarily removing most heavy metal ions, the consumption is low, the using amount of the manganese powder is 1-1.5 times of the amount of heavy metal substances in the solution, the sulfide is adopted for deeply purifying the heavy metals, the total amount of the sulfide is low, the caused pH value change is small, the chance of forming precipitates with manganese is low, and the consumption is low; meanwhile, sodium ions enter the solution to have little influence on the manganese oxyhydroxide coated by the subsequent precipitation. The method for removing impurities by combining manganese powder and sulfide has the advantages that the use amount of the manganese powder and the sulfide can be greatly reduced, and the production cost is greatly reduced; the mode is an economical combination and environment-friendly mode.
After the impurities of calcium ions and heavy metal ions in the solution are removed, a small amount of fluorine ion impurities exist in the solution, and the fluorine ions have a large negative effect on the electrochemical performance of the manganese oxyhydroxide, so that the fluorine ions in the solution need to be removed before the manganese oxyhydroxide is prepared; according to the invention, the impurity removal of fluorine ions is realized by combining the aluminum salt and the settling agent A, the settling agent A improves the impurity removal effect of the fluorine ions, reduces the impurity removal time and has no influence on the subsequent procedures; the settling agent A has flocculation effect on aluminum fluoride, and the precipitation of fluorine ions is accelerated; the settling agent A has complexation with manganese ions to form a complex, so that the oxidation potential of the synthesized hydroxyl manganese oxide is reduced. Adding a complexing agent B into the manganese solution after the fluorine ions are subjected to impurity removal, and oxidizing and precipitating to produce hydroxyl manganese oxide; the complexing agent B has complexing effect with manganese ions, and the oxidation potential of the hydroxyl manganese oxide is reduced. The aluminum-doped product has good quality, and when the product is used for preparing lithium manganate, the capacity and the cycle performance of the lithium manganate can be improved.
In conclusion, the production method is characterized in that the solution is purified and enriched by an extraction method, impurities in the solution are directly purified by a chemical combination method, and cation impurity removal is realized by removing calcium ions and heavy metal ion impurities; in the related technology, the fluoride and calcium form precipitate, and the aging time is at least 12h, but the precipitation of the method does not need to be subjected to an aging process, the calcium ion precipitation is directly subjected to solid-liquid separation, the liquid phase directly enters a reduction and precipitation process, and in the process of precipitating heavy metal ions by using sulfide, the process conditions are favorable for forming precipitate with calcium and fluorine ions, so that the effects of aging and further removing calcium ions are achieved. The purification mode of removing calcium firstly and then removing heavy metal ions by combining manganese powder and sulfide achieves the purposes of impurity removal and purification of waste manganese liquid and formation of organic combination of product production technology and planning; the flow of the manganese combination liquid, the flow of the alkaline liquid and the flow of air are controlled in an accurate metering mode, the reaction process is controlled by automatically adjusting the alkaline flow according to the change of the pH value, the temperature of a reaction system is automatically controlled according to reaction conditions, and the quality of the manganese oxyhydroxide is controllable. The method combines the characteristics of the raw material liquid to design the characteristics of the product, thereby not only reducing the process difficulty, but also reducing the production cost, and simultaneously fully embodying the characteristics of the product.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid is characterized by comprising the following steps: the method comprises the following steps:
s1, calcium removal: adjusting the pH value of the waste manganese liquid to 5.0-5.5 under a heating condition, adding a precipitator, and removing solid phase impurities to obtain a crude manganese solution;
s2, reduction: adding manganese powder into the crude manganese solution, adjusting the pH to 1.5-3.0 under a heating condition, and removing solid phase impurities to obtain a refined manganese solution;
s3, precipitation: adding sulfide into the refined manganese solution, adjusting the pH to 4.0-5.0 under a heating condition, and removing solid phase impurities to obtain a purified manganese solution;
s4, defluorination: adding an aluminum salt I and a settling agent A into the purified manganese solution, adjusting the pH to 5.0-5.5 under a heating condition, and performing solid-liquid separation to obtain a manganese sulfate solution;
s5, preparation: adding aluminum salt II, complexing agent B and alkaline substance into manganese sulfate solution to obtain finished product solution, introducing oxidant into the finished product solution, and controlling reaction conditions to obtain the manganese oxyhydroxide.
2. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the precipitating agent is fluoride; preferably, the fluoride is at least one of sodium fluoride, ammonia fluoride, potassium fluoride and manganese fluoride; more preferably, the fluoride is manganese fluoride.
3. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the sulfide comprises at least one of sodium sulfide, potassium sulfide, ammonium sulfide, manganese sulfide and hydrogen sulfide; more preferably, the sulfide is at least one of manganese sulfide and hydrogen sulfide.
4. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the aluminum salt I is at least one of aluminum sulfate and polyaluminium sulfate; the settling agent A is polyacrylamide.
5. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the mass ratio of the complexing agent B to the manganese element in the manganese sulfate solution is 0.005-0.025: 1.
6. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the aluminum salt II is at least one of aluminum sulfate and polyaluminium sulfate; the alkaline substance is sodium hydroxide; the complexing agent B is at least one of citric acid and EDTA.
7. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the concentration of manganese ions in the finished product liquid is 1-2.5 mol/L.
8. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the mass ratio of the aluminum ions in the finished product liquid to the manganese ions in the finished product liquid is 0.01-0.05: 1.
9. the method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the oxidant is oxygen or air; preferably, the oxidant is air.
10. The method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using the waste manganese solution according to claim 1, characterized in that: the reaction conditions are as follows: the reaction temperature is 50-70 ℃, the reaction pH is 8-10, the stirring speed is 200-300 rpm, and the oxidant flow is 35-55 Nm3/h。
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