CN115216629B - Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste - Google Patents
Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste Download PDFInfo
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- CN115216629B CN115216629B CN202210753105.9A CN202210753105A CN115216629B CN 115216629 B CN115216629 B CN 115216629B CN 202210753105 A CN202210753105 A CN 202210753105A CN 115216629 B CN115216629 B CN 115216629B
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002243 precursor Substances 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000002386 leaching Methods 0.000 claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 72
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 69
- 239000010937 tungsten Substances 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 48
- 239000010941 cobalt Substances 0.000 claims abstract description 48
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 235000021110 pickles Nutrition 0.000 claims abstract description 45
- 238000011084 recovery Methods 0.000 claims abstract description 39
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 20
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003456 ion exchange resin Substances 0.000 claims description 22
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 6
- 230000029087 digestion Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 1
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000001396 Malus hupehensis Species 0.000 description 1
- 235000005057 Malus hupehensis Nutrition 0.000 description 1
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 1
- 229940074393 chlorogenic acid Drugs 0.000 description 1
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 1
- 235000001368 chlorogenic acid Nutrition 0.000 description 1
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 firstly Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of battery waste recovery, and discloses a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste. The method mainly comprises the following steps: carrying out primary acid leaching on the tungsten-doped ternary precursor waste and an acid solution to obtain primary acid leaching solution and primary acid leaching slag containing nickel, cobalt and manganese elements; in the presence of a reducing agent, carrying out secondary reducing acid leaching on the primary acid leaching slag and the acid solution to obtain secondary acid leaching liquid and secondary acid leaching slag; and regulating the pH value of the second-stage pickle liquor, filtering, and absorbing and recovering tungsten element in the filtrate by using weak-alkaline anion exchange resin to obtain sodium tungstate products and absorbed liquor containing nickel, cobalt and manganese elements. The method has the advantages of simple process, convenient operation and low cost, and ensures that the recovery rates of nickel, cobalt, manganese and tungsten in the tungsten-doped ternary precursor waste are all over 99 percent.
Description
Technical Field
The invention relates to the technical field of battery waste recovery, in particular to a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste.
Background
At present, a nickel-cobalt-manganese ternary material is one of main positive electrode materials of lithium ion batteries, and is widely applied to electric vehicles, electric bicycles, high-power batteries, middle-low grade mobile phones and notebook computers.
The ternary composite positive electrode material precursor product takes nickel salt, cobalt salt and manganese salt as raw materials, wherein the content ratio (x: y: z) of nickel, cobalt and manganese elements can be adjusted according to actual needs.
In order to improve the electrochemical performance of the positive electrode material, elements such as magnesium, aluminum, zirconium, tungsten and the like are mostly adopted to dope and modify the precursor at present. Unqualified tungsten-doped centrifugal materials, tungsten-doped slurrying groove materials, tungsten-doped sintering materials, tungsten-doped drying materials, ground reclaimed materials and other tungsten-doped ternary waste materials can be generated in the process of producing the tungsten-doped ternary precursor. The content of nickel element, cobalt element and manganese element in the tungsten-doped nickel-cobalt-manganese ternary precursor waste is high, and the tungsten-doped ternary precursor waste is directly treated by adopting a reduction acid leaching method, so that the later-stage tungsten element is difficult to separate from the nickel element, cobalt element and manganese element, the recovery rate of the nickel element, cobalt element, manganese element and tungsten element is low, and the effective recovery of the nickel element, cobalt element, manganese element and tungsten element is not realized.
However, the method of directly adopting alkaline leaching to obtain tungsten element with high recovery rate consumes a large amount of alkali, so that the treatment cost is high, and the separation and purification of tungsten and other metal elements cannot be thoroughly realized, therefore, the added value of the nickel, cobalt, manganese and tungsten metal element products is low.
CN108199106a discloses a process for recovering waste materials in the production process of nickel-cobalt-manganese ternary precursor, firstly, sulfuric acid solution is used for carrying out acid dissolution reaction on the nickel-cobalt-manganese ternary precursor waste materials, and then, the reducibility of valuable metal active sulfides recovered in the precipitation mother liquor of the nickel-cobalt-manganese ternary precursor is used for carrying out oxidation reduction reaction with partial oxides insoluble in acid in the nickel-cobalt-manganese ternary precursor waste materials, so that the purpose of recovery is achieved. However, the scheme only relates to recycling of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese ternary precursor waste, and the recycling rate of the nickel element, cobalt element and manganese element is low, and comprehensive recycling of metal element in the tungsten-doped ternary precursor waste cannot be achieved through the scheme.
CN110607439a discloses a method for treating spherical nickel protoxide by sectional oxidation acid leaching, which comprises carrying out two-stage countercurrent oxidation acid leaching on mechanically activated nickel protoxide to obtain nickel leaching solution, taking nickel cobalt manganese ternary precursor waste as raw material for consuming residual acid, and using the leaching solution after acid consumption for synthesizing ternary precursor, preparing high-purity nickel plate, nickel sulfate, nickel chloride crystal and the like. However, the technical scheme disclosed in the prior art does not relate to recovery rates of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese ternary precursor waste, and comprehensive recovery and utilization of metal elements in the tungsten-doped ternary precursor waste cannot be realized through the scheme.
Therefore, the method for treating the tungsten-doped ternary precursor waste has important practical significance, and is simple in process, low in cost and high in metal element recovery rate.
Disclosure of Invention
The invention aims to overcome the defects that the comprehensive recovery of nickel, cobalt, manganese and tungsten elements in tungsten-doped ternary precursor waste cannot be realized or the recovery rate is low and the separation of tungsten elements from nickel, cobalt and manganese elements is difficult in the prior art.
In order to achieve the above purpose, the invention provides a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste, which comprises the following steps:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching slag;
(2) In the presence of a reducing agent, carrying out secondary acid leaching on the primary acid leaching slag and a second sulfuric acid solution to obtain a secondary acid leaching liquid I and a secondary acid leaching slag;
(3) Adjusting the pH value of the second-stage pickle liquor I to 2-6 by using an alkaline substance I to obtain a second-stage pickle liquor II, and then filtering the second-stage pickle liquor II to obtain a second-stage pickle liquor III;
(4) Adopting ion exchange resin to carry out selective adsorption recovery on tungsten element in the two-stage pickle liquor III, and obtaining liquid I after adsorption and ion exchange resin loaded with tungsten element;
(5) Contacting the ion exchange resin loaded with tungsten element with an analysis solution to obtain a sodium tungstate solution through analysis;
the method further comprises the steps of: and recycling the residual elements contained in the first-stage pickle liquor I and the absorbed liquid I, wherein the residual elements contained in the first-stage pickle liquor I and the absorbed liquid I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element.
The invention has at least the following advantages:
(1) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste can realize effective separation of nickel, cobalt and manganese elements and tungsten elements;
(2) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste can ensure that the recovery rates of the nickel, cobalt, manganese and tungsten are all over 99 percent;
(3) The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste has the advantages of simple process, convenient operation and low cost, and has strong practicability and high economic value.
Drawings
FIG. 1 is a process flow diagram of the treatment of tungsten doped ternary precursor waste.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the invention provides a method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste, which comprises the following steps:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching slag;
(2) In the presence of a reducing agent, carrying out secondary acid leaching on the primary acid leaching slag and a second sulfuric acid solution to obtain a secondary acid leaching liquid I and a secondary acid leaching slag;
(3) Adjusting the pH value of the second-stage pickle liquor I to 2-6 by using an alkaline substance I to obtain a second-stage pickle liquor II, and then filtering the second-stage pickle liquor II to obtain a second-stage pickle liquor III;
(4) Adopting ion exchange resin to carry out selective adsorption recovery on tungsten element in the two-stage pickle liquor III, and obtaining liquid I after adsorption and ion exchange resin loaded with tungsten element;
(5) Contacting the ion exchange resin loaded with tungsten element with an analysis solution to obtain a sodium tungstate solution through analysis;
the method further comprises the steps of: and recycling the residual elements contained in the first-stage pickle liquor I and the absorbed liquid I, wherein the residual elements contained in the first-stage pickle liquor I and the absorbed liquid I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element.
Specifically, in the step (3), the second-stage pickling solution II is a solid-liquid mixture containing a small amount of solid particles or colloids.
Preferably, the method further comprises: regulating the pH value of the first-stage pickle liquor I to 2-6 by using an alkaline substance II to obtain a first-stage pickle liquor II, and filtering the first-stage pickle liquor II to obtain a feed liquid I containing nickel element, cobalt element and manganese element; and (3) using the feed liquid I as a raw material for producing a nickel, cobalt and manganese ternary precursor so as to recycle the nickel, cobalt and manganese ternary precursor.
Preferably, the method further comprises: and regulating the pH value of the adsorbed liquid I to 2-6 by using an alkaline substance III to obtain an adsorbed liquid II, concentrating the adsorbed liquid II to obtain a liquid II, and using the liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor so as to recycle.
Preferably, the concentration conditions are controlled so that the sum of the mass concentrations of nickel element, cobalt element and manganese element in the feed liquid II is more than or equal to 110g/L.
Preferably, the alkaline substance I, the alkaline substance II and the alkaline substance III according to the present invention are the same or different, and are each independently selected from at least one of NaOH solution, ammonia water and KOH solution.
The present invention is not particularly limited in the use concentration of the alkaline substance I, as long as the secondary pickle liquor I can be adjusted to reach a specified pH value, and the alkaline substance I is exemplified by a NaOH solution having a concentration of 30 wt%.
The present invention is not particularly limited in the concentration of the alkaline substance II to be used, as long as the first-stage pickle liquor I can be adjusted to achieve a prescribed pH value, and the alkaline substance II is exemplified by aqueous ammonia having a concentration of 25 to 28% by weight.
The present invention is not particularly limited in the concentration of the alkaline substance III to be used, as long as the post-adsorption liquid I can be adjusted to a specified pH, and the alkaline substance III is exemplified by a KOH solution having a concentration of 30% by weight.
Preferably, in step (1), the moisture content of the tungsten doped ternary precursor waste is 0.2-25wt%.
Preferably, in the step (1), the content of nickel element in the tungsten-doped ternary precursor waste is 20-75wt% based on metal element, the content of cobalt element is 0.3-15wt%, the content of manganese element is 0.1-22wt%, and the content of tungsten element is 0.05-0.5wt%.
Preferably, in step (1), the concentration of the first sulfuric acid solution is 20-35wt%.
Preferably, in step (1), the conditions of the one-stage acid leaching are controlled so that the pH value of the one-stage pickle liquor I obtained is 0 to 3.
Preferably, in step (1), the conditions of the one-stage acid leaching are such that: the leaching temperature is 40-94 ℃ and the leaching time is 0.5-4h. More preferably, in step (1), the conditions of the one-stage acid leaching satisfy: the leaching temperature is 70-90 ℃ and the leaching time is 1-2h.
Preferably, in the step (1), the concentration of the first sulfuric acid solution is controlled to be 20-35wt%, and the amount of the first sulfuric acid solution is 3-6mL for each 1g of the tungsten doped ternary precursor waste.
Preferably, in step (2), the concentration of the second sulfuric acid solution is 5-15wt%.
Preferably, in step (2), the conditions of the secondary acid leaching are controlled so that the pH value of the obtained secondary pickling solution I is 0-3.
Preferably, in step (2), the conditions of the second stage acid leaching include: the leaching temperature is 40-94 ℃ and the leaching time is 0.5-3h. More preferably, in step (2), the conditions of the second-stage acid leaching are such that: the leaching temperature is 70-90 ℃ and the leaching time is 1-2h.
Preferably, in step (2), the concentration of the second sulfuric acid solution is controlled to be 5-15wt%, and the amount of the second sulfuric acid solution is 4-9mL for each 1g of the first stage acid leaching residue.
Preferably, in step (2), the reducing agent is selected from at least one of hydrogen peroxide, sodium sulfite, ammonium sulfite, sodium thiosulfate and sodium metabisulfite.
Preferably, in step (2), the reducing agent is used in an amount of 3-9g per 100g of the tungsten doped ternary precursor waste. More preferably, in step (2), the reducing agent is used in an amount of 3.6 to 6.5g per 100g of the tungsten doped ternary precursor waste.
Preferably, in step (4), the ion exchange resin is a weakly basic anion exchange resin. More preferably, the weakly basic anion exchange resin is selected from at least one of D363, D354 and LSC-486.
The invention discloses a method for preparing a weak-alkaline anion exchange resin, which comprises the steps of (1) representing the model of the weak-alkaline anion exchange resin, wherein D363, D354 and LSC-486 represent the weak-alkaline anion exchange resin of macroporous acrylic series, D354 represents the weak-alkaline anion exchange resin of macroporous polystyrene, and LSC-486 represents the weak-alkaline anion exchange resin of macroporous acrylic series.
Particularly preferably, in step (4), the weakly basic anion exchange resin is a LSC-486 resin. The inventors have found that in this preferred case, the method of the present invention enables further improvements in the recovery of nickel, cobalt, manganese and tungsten elements from the tungsten doped ternary precursor waste.
Preferably, in the step (4), the conditions of the selective adsorption recovery are controlled so that the mass concentration of tungsten element in the adsorbed liquid I is less than 1mg/L.
Preferably, in step (5), the resolving liquid is a NaOH solution of 1-3 mol/L.
The method for selectively adsorbing and recovering the catalyst in the step (4) and the method for analyzing the catalyst in the step (5) preferably using 1 to 3mol/L NaOH solution as the analysis solution are not particularly limited, and those skilled in the art can perform the method according to conventional technical means known in the art, and those skilled in the art should not understand the limitation of the present invention.
In order to make the recovery rate of tungsten element higher, the invention provides a preferred specific method for selective adsorption recovery and analysis, which comprises the following steps:
s1: introducing the two-stage leaching solution III into a single-stage ion exchange resin column filled with LSC-486 weak-base anion exchange resin at the speed of 120-360mL/h to perform adsorption reaction to obtain a liquid I after adsorption and LSC-486 weak-base anion exchange resin I loaded with tungsten element;
s2: introducing water into the single-stage ion exchange resin column of the LSC-486 weak-base anion exchange resin I loaded with tungsten element obtained in the step S1 at a speed of 120-240mL/h to obtain a washing liquid and the LSC-486 weak-base anion exchange resin II loaded with tungsten element;
s3: introducing 1-3mol/L NaOH solution into the single-stage ion exchange resin column of the LSC-486 weak-alkali anion exchange resin II loaded with tungsten element obtained in the step S2 at a speed of 120-180mL/h to obtain the sodium tungstate solution.
Preferably, the single-stage ion exchange resin column has a height of 15-30cm and a diameter of 2-3cm.
Preferably, in step S1, the conditions of the adsorption reaction satisfy: the adsorption time is 0.5-7h, and the adsorption temperature is 20-40 ℃.
Preferably, in step S2, for every 100cm 3 The amount of water used is 120-300mL.
Preferably, in step S3, for every 100cm 3 The dosage of the NaOH solution of 1-3mol/L is 230-450mL.
Preferably, in step (5), the method further comprises: and concentrating, crystallizing, centrifuging and drying the sodium tungstate solution in sequence to obtain a sodium tungstate product.
It should be noted that the filtering, concentrating, crystallizing, centrifuging and drying methods described in the foregoing are not particularly limited, and those skilled in the art can select according to the techniques known in the art, and the present invention is not described herein in detail, and those skilled in the art should not understand the limitation of the present invention.
The present invention will be described in detail by examples.
Concentrated sulfuric acid of 95 wt.%: purchased from colone chemicals limited, adult city.
Hydrogen peroxide: purchased from national pharmaceutical group chemical company, inc.
LSC-486 weakly basic anion exchange resin: purchased from western amp, blue dawn technology materials, inc.
D354 weak basic anion exchange resin: purchased from Jining Malus hupehensis chemical Co.
D363 weakly basic anion exchange resin: purchased from Anhui tree chemical sales Co., ltd.
Precision filter: the model is LFD-1-1P, and the manufacturer is Li Feier Ten filter Co., ltd.
Tungsten doped ternary precursor waste I (source: hunan Zhongwei New energy technology Co., ltd.) is composed of: the water content is 15.81wt%, calculated as metal element, the nickel content in the tungsten-doped ternary precursor waste I is 44.77wt%, the cobalt content is 4.49wt%, the manganese content is 3.25wt%, and the tungsten content is 0.079wt% on a dry basis.
Tungsten doped ternary precursor waste II (source: hunan Zhongwei New energy technology Co., ltd.) is composed of: the water content is 0.48wt%, calculated as metal element, the nickel element content in the tungsten-doped ternary precursor waste I is 54.63wt%, the cobalt element content is 2.45wt%, the manganese element content is 3.18wt%, and the tungsten element content is 0.146wt% on a dry basis.
The calculation formula of the recovery rate of the metal element referred to in the following examples is:
nickel element recovery (%) = nickel element content in 1-two-stage acid leaching residue/nickel element content in tungsten doped ternary precursor waste x 100%;
cobalt element recovery (%) = cobalt element content in 1-two-stage acid leaching slag/cobalt element content in tungsten doped ternary precursor waste material x 100%;
manganese element recovery (%) = manganese element content in 1-two-stage acid leaching slag/manganese element content in tungsten doped ternary precursor waste material x 100%;
tungsten recovery (%) =1- (tungsten content in adsorbed liquid i+tungsten content in second-stage acid leaching residue)/tungsten content in tungsten-doped ternary precursor waste×100%;
the unit of the content of nickel, cobalt, manganese and tungsten elements in the calculation formula is g.
The content of nickel element in the second-stage acid leaching slag is measured by adopting an ICP method after digestion;
the cobalt element content in the second-stage acid leaching slag is measured by adopting an ICP method after digestion;
the manganese element content in the second-stage acid leaching slag is measured by adopting an ICP method after digestion;
measuring the tungsten element content in the second-stage acid leaching slag by adopting an ICP method after digestion;
the nickel element content in the tungsten-doped ternary precursor waste is measured by a dimethylglyoxime-EDTA complexometric titration method;
the cobalt element content in the tungsten-doped ternary precursor waste is measured by adopting a post-digestion ICP method;
determining the content of manganese element in the tungsten-doped ternary precursor waste by adopting a digestion ICP method;
measuring the content of tungsten element in the tungsten-doped ternary precursor waste by adopting a digestion ICP method;
the tungsten element content in the liquid I after adsorption is measured by adopting an ICP method.
Example 1
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste I and the first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching slag;
(2) Carrying out secondary acid leaching on all the obtained primary acid leaching residues, a reducing agent and a second sulfuric acid solution to obtain secondary acid leaching liquid I and secondary acid leaching residues;
(3) Regulating the pH value of the second-stage pickle liquor I by using a NaOH solution with the concentration of 30 weight percent to obtain a second-stage pickle liquor II, and filtering by using a precise filter to obtain a second-stage pickle liquor III with solid particles smaller than 15 mu m;
(4) Selectively adsorbing and recovering tungsten element in the second-stage pickle liquor III by adopting weak-alkali anion exchange resin to obtain a liquid I after adsorption and a weak-alkali anion exchange resin II loaded with tungsten element;
the method for selective adsorption recovery comprises the following steps:
s1: introducing the two-stage leaching solution III into a single-stage ion exchange resin column filled with weak-base anion exchange resin to perform adsorption reaction to obtain a liquid I after adsorption and a weak-base anion exchange resin I loaded with tungsten element;
s2: introducing water into the single-stage ion exchange resin column of the weak-alkaline anion exchange resin I loaded with tungsten element obtained in the step S1 to obtain washing liquid and weak-alkaline anion exchange resin II loaded with tungsten element;
(5) Introducing NaOH solution into the single-stage ion exchange resin column of the weak alkaline anion exchange resin II loaded with tungsten element obtained in the step S2 to obtain sodium tungstate solution;
(6) Concentrating, crystallizing, centrifuging and drying the sodium tungstate solution in sequence to obtain a sodium tungstate product;
(7) Regulating the pH value of the first-stage pickle liquor I by using a NaOH solution with the concentration of 30wt% to obtain a first-stage pickle liquor II, filtering the first-stage pickle liquor II by adopting a precise filter to obtain a feed liquid I with the solid particles containing nickel element, cobalt element and manganese element smaller than 15 mu m, and taking the feed liquid I as a raw material for producing ternary precursors of nickel, cobalt and manganese for recycling; the method comprises the steps of,
regulating the pH value of the adsorbed liquid I by using a NaOH solution with the concentration of 30wt% to obtain an adsorbed liquid II, concentrating the adsorbed liquid II to obtain a liquid II containing nickel element, cobalt element and manganese element, and taking the liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor for recycling;
the sum of the mass concentration of nickel element, cobalt element and manganese element in the feed liquid II is 110g/L.
The remaining specific parameters involved in this example are shown in table 1;
the recovery rate of the metal element in this example is shown in Table 2.
Example 2
This example was carried out using a procedure similar to example 1, except that in this example: the types of materials and process parameters used are different and are shown in Table 1.
The recovery rate of the metal element in this example is shown in Table 2.
Example 3
This example was carried out using a procedure similar to example 1, except that in this example: the types of materials and process parameters used are different and are shown in Table 1.
The recovery rate of the metal element in this example is shown in Table 2.
Example 4
This example was carried out using a procedure similar to example 1, except that in this example:
the amount of the reducing agent used was 3.5g per 100g of the tungsten doped ternary precursor waste I.
The remainder was the same as in example 1.
The remaining specific parameters involved in this example are shown in table 1;
the recovery rate of the metal element in this example is shown in Table 2.
Example 5
This example was carried out using a procedure similar to example 1, except that in this example:
the resin used in the selective adsorption recovery process is D363 weak base anion exchange resin.
The remainder was the same as in example 1.
The remaining specific parameters involved in this example are shown in table 1;
the recovery rate of the metal element in this example is shown in Table 2.
Comparative example 1
The comparative example adopts a one-stage acid leaching method to recover the metal elements in the tungsten-doped ternary precursor waste.
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste I and the first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching slag;
(2) And regulating the pH value of the first-stage pickle liquor I by using a NaOH solution with the concentration of 30wt% to obtain a first-stage pickle liquor II, filtering the first-stage pickle liquor II by adopting a precision filter to obtain a feed liquid with the solid particles containing nickel element, cobalt element and manganese element smaller than 15 mu m, and taking the feed liquid as a raw material for producing a nickel, cobalt and manganese ternary precursor for recycling.
See table 1 for the remaining specific parameters involved in this comparative example;
the recovery rates of the metal elements in this comparative example are shown in Table 2.
Comparative example 2
The comparative example adopts a method combining one-stage chlorogenic acid leaching and ion exchange resin adsorption to recover tungsten element so as to recover metal element in tungsten-doped ternary precursor waste.
(1) Performing primary acid leaching on the tungsten-doped ternary precursor waste I, hydrogen peroxide and a first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching residues;
(2) Regulating the pH value of the first-stage pickle liquor I by using a NaOH solution with the concentration of 30 weight percent to obtain a first-stage pickle liquor II, and filtering by using a precise filter to obtain a first-stage pickle liquor III with solid particles smaller than 15 mu m;
(3) Selectively adsorbing and recovering tungsten element in the first section of pickle liquor III by adopting weak-alkali anion exchange resin to obtain a liquid I after adsorption and weak-alkali anion exchange resin II loaded with tungsten element;
the method for selective adsorption recovery comprises the following steps:
s1: introducing the first-stage leaching solution III into a single-stage ion exchange resin column filled with weak-base anion exchange resin to perform adsorption reaction to obtain a liquid I after adsorption and a weak-base anion exchange resin I loaded with tungsten element;
s2: introducing water into the single-stage ion exchange resin column of the weak-alkaline anion exchange resin I loaded with tungsten element obtained in the step S1 to obtain washing liquid and weak-alkaline anion exchange resin II loaded with tungsten element;
(4) Introducing NaOH solution into the single-stage ion exchange resin column of the weak alkaline anion exchange resin II loaded with tungsten element obtained in the step S2 to obtain sodium tungstate solution;
(5) Concentrating, crystallizing, centrifuging and drying the sodium tungstate solution in sequence to obtain a sodium tungstate product;
(6) With H at a concentration of 5wt% 2 SO 4 And regulating the pH value of the adsorbed liquid I by using the solution to obtain adsorbed liquid II, concentrating the adsorbed liquid II to obtain a liquid containing nickel element, cobalt element and manganese element, and taking the liquid as a raw material for producing a ternary precursor of nickel, cobalt and manganese for recycling.
See table 1 for the remaining specific parameters involved in this comparative example;
the recovery rates of the metal elements in this comparative example are shown in Table 2.
Comparative example 3
This comparative example was conducted using a procedure similar to example 1, except that in this comparative example: the pH of the second-stage pickling solution II was adjusted to 1, and the rest was the same as in example 1.
The recovery rates of the metal elements in this comparative example are shown in Table 2.
TABLE 1
The recovery rate of the metal element in the tungsten doped ternary precursor waste is shown in table 2.
TABLE 2
In summary, the method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste provided by the invention can ensure that the recovery rates of nickel element, manganese element, cobalt element and tungsten element are all over 99 percent, and the method provided by the invention can also greatly reduce the consumption of reducing agent, reduce the adsorption time, and has important significance in reducing the production cost, saving the resources and improving the production efficiency.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The method for comprehensively recovering the metal elements in the tungsten-doped ternary precursor waste is characterized by comprising the following steps of:
(1) Carrying out primary acid leaching on the tungsten-doped ternary precursor waste and a first sulfuric acid solution to obtain primary acid leaching liquid I and primary acid leaching slag;
(2) In the presence of a reducing agent, carrying out secondary acid leaching on the primary acid leaching slag and a second sulfuric acid solution to obtain a secondary acid leaching liquid I and a secondary acid leaching slag;
(3) Adjusting the pH value of the second-stage pickle liquor I to 2-6 by using an alkaline substance I to obtain a second-stage pickle liquor II, and then filtering the second-stage pickle liquor II to obtain a second-stage pickle liquor III;
(4) Adopting ion exchange resin to carry out selective adsorption recovery on tungsten element in the two-stage pickle liquor III, and obtaining liquid I after adsorption and ion exchange resin loaded with tungsten element;
(5) Contacting the ion exchange resin loaded with tungsten element with an analysis solution to obtain a sodium tungstate solution through analysis;
the method further comprises the steps of: recycling residual elements contained in the first-stage pickle liquor I and the absorbed liquid I, wherein the residual elements contained in the first-stage pickle liquor I and the absorbed liquid I are respectively and independently selected from at least one of nickel element, cobalt element and manganese element;
wherein in the step (1), the condition of the primary acid leaching is controlled so that the pH value of the primary acid leaching solution I is 0-3; the conditions of the primary acid leaching are as follows: the leaching temperature is 40-94 ℃ and the leaching time is 0.5-4h;
in the step (2), controlling the condition of the secondary acid leaching so that the pH value of the obtained secondary acid leaching solution I is 0-3; the conditions of the two-stage acid leaching include: the leaching temperature is 40-94 ℃ and the leaching time is 0.5-3h; the amount of the reducing agent is 3-9g per 100g of the tungsten doped ternary precursor waste.
2. The method according to claim 1, wherein in step (2), the reducing agent is selected from at least one of hydrogen peroxide, sodium sulfite, ammonium sulfite, sodium thiosulfate, and sodium metabisulfite.
3. The process according to claim 1 or 2, wherein in step (4) the ion exchange resin is a weakly basic anion exchange resin.
4. A process according to claim 3, wherein the weakly basic anion exchange resin is selected from at least one of D363, D354 and LSC-486.
5. The method according to claim 1 or 2, wherein in step (4), the conditions of the selective adsorption recovery are controlled so that the mass concentration of tungsten element in the post-adsorption liquid I is < 1mg/L.
6. The method according to claim 1 or 2, wherein in step (5), the resolving liquid is a NaOH solution of 1-3 mol/L.
7. The method according to claim 1 or 2, wherein the method further comprises: and (3) concentrating, crystallizing, centrifuging and drying the sodium tungstate solution obtained in the step (5) in sequence to obtain a sodium tungstate product.
8. The method according to claim 1 or 2, wherein the method further comprises: regulating the pH value of the first-stage pickle liquor I to 2-6 by using an alkaline substance II to obtain a first-stage pickle liquor II, and filtering the first-stage pickle liquor II to obtain a feed liquid I containing nickel element, cobalt element and manganese element; and then the feed liquid I is used as a raw material for producing the nickel, cobalt and manganese ternary precursors so as to realize the recycling.
9. The method according to claim 1 or 2, wherein the method further comprises: and regulating the pH value of the adsorbed liquid I to 2-6 by using an alkaline substance III to obtain an adsorbed liquid II, concentrating the adsorbed liquid II to obtain a liquid II, and then using the liquid II as a raw material for producing a nickel, cobalt and manganese ternary precursor to realize recycling.
10. The method according to claim 9, wherein the concentration conditions are controlled so that the sum of the mass concentrations of nickel element, cobalt element and manganese element in the feed liquid II is not less than 110g/L.
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