CN117383557A - Purification and impurity removal method for acid leaching graphite waste residues of waste lithium battery materials - Google Patents
Purification and impurity removal method for acid leaching graphite waste residues of waste lithium battery materials Download PDFInfo
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- CN117383557A CN117383557A CN202311336084.1A CN202311336084A CN117383557A CN 117383557 A CN117383557 A CN 117383557A CN 202311336084 A CN202311336084 A CN 202311336084A CN 117383557 A CN117383557 A CN 117383557A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000010439 graphite Substances 0.000 title claims abstract description 138
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 138
- 239000002699 waste material Substances 0.000 title claims abstract description 116
- 238000002386 leaching Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002253 acid Substances 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 40
- 239000012535 impurity Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000746 purification Methods 0.000 title description 7
- 239000002893 slag Substances 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000009831 deintercalation Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 10
- 238000010494 dissociation reaction Methods 0.000 description 7
- 230000005593 dissociations Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
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- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials, and belongs to the technical field of recycling of waste lithium ion batteries. The method comprises the following steps: crushing and screening the blocky acid leaching graphite waste residues to obtain fine-grained graphite residues; stirring the mixture in water, and separating to obtain primary treated graphite waste residue and sulfate solution; heating the primary treated graphite waste residue in alkaline solution, and separating to obtain secondary treated graphite waste residue and solution containing aluminum, lithium and phosphorus; roasting the secondary treated graphite waste residue to obtain graphite waste residue with fluorine-containing organic matters removed; adding the graphite slag into an electrolytic tank, removing lithium, nickel, cobalt and manganese which are embedded in the graphite slag from the solution, obtaining pure graphite and leaching solution, concentrating, regulating the pH value of the leaching solution, recovering the nickel, cobalt and manganese, and then recovering the lithium through carbonate precipitation. The invention realizes the high-efficiency removal of metal ions and metallurgical residues in the graphite waste residues by combining multi-stage leaching and electrochemical deintercalation.
Description
Technical Field
The invention relates to the technical field of recycling of waste lithium ion batteries, in particular to a method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium ion batteries.
Background
In recent years, with the strong popularization and use of new energy automobiles and the aggravation of the updating of electronic products, the yield of waste lithium ion batteries presents a rapid increase trend, and the waste lithium ion batteries belong to high-grade metal mines and have high recovery values. And mechanically crushing the waste lithium ion battery to obtain anode and cathode mixed powder, and then adopting acid leaching to recycle valuable metals in the electrode material. However, the waste residue generated by the acid leaching process of the waste lithium battery material still remains a certain amount of valuable metals and metallurgical residues, is difficult to remove, belongs to dangerous wastes, cannot be freely transported and treated, and additionally increases the treatment cost. Meanwhile, graphite is used as a resource with wide application and has high recycling value. Therefore, developing a high-efficiency purification and impurity removal method for graphite waste residues has important practical significance for realizing the recycling of waste graphite. However, graphite waste residue obtained after acid leaching of the waste lithium battery material still contains a large amount of metal ions and metallurgical residues, and the metal ions embedded in the graphite waste residue are difficult to remove by traditional strong acid leaching.
Disclosure of Invention
Aiming at the problems, the invention provides a method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste, which realizes the efficient removal of metal ion impurities in the graphite waste by combining multi-stage leaching and electrochemical deintercalation.
The invention aims to provide a method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials, which comprises the following steps of:
s1, crushing massive acid leaching graphite waste residues, and screening to obtain fine-grained graphite residues;
s2, placing the fine-fraction graphite slag obtained in the step S1 into water for stirring, and after the stirring is completed, carrying out solid-liquid separation to obtain primary treatment graphite slag and sulfate solution;
s3, placing the primary treated graphite waste residue obtained in the step S2 into an alkaline solution for heating, and after the heating is completed, carrying out solid-liquid separation to obtain secondary treated graphite waste residue and a solution containing aluminum, lithium and phosphorus;
s4, performing anaerobic roasting on the secondary treatment graphite waste residue obtained in the step S3 to obtain graphite waste residue with fluorine-containing organic matters removed;
adding graphite waste residue with fluorine-containing organic matters removed into an electrolytic tank, adopting an electrochemical deintercalation method to deintercalate lithium, nickel, cobalt and manganese which are embedded in the graphite waste residue into a solution, carrying out solid-liquid separation to obtain pure graphite and leaching solution, concentrating, regulating the pH value of the leaching solution to 7.2-8.5, recovering nickel, cobalt and manganese, and then recovering lithium through carbonate precipitation.
Preferably, in S1, the mesh size used for sieving is less than 125. Mu.m.
Preferably, in S2, the ratio of fine fraction graphite slag to water is 1g:3-20ml.
Preferably, the stirring time is 30-90min.
Preferably, in S3, the ratio of the waste residue of the primary treatment graphite to the alkaline solution is 1g:15-30ml, and the concentration of the alkaline solution is 2mol/L.
Preferably, the heating temperature is 30-80 ℃, and the stirring time is 30-90min.
Preferably, in S3, the alkaline solution used includes, but is not limited to, sodium hydroxide, potassium hydroxide.
Preferably, in S4, the roasting temperature is 500-800 ℃, and the anaerobic roasting time is 30-60min.
Preferably, in S4, the electrochemical deintercalation method is to remove the anode end of the graphite waste residue electrolyzer containing fluorine organic matters, and the electrode material is platinum; the electrolyte is dilute sulfuric acid solution of 0.3-0.5 mol/L.
Preferably, the electrochemical deintercalation process has voltage of 10-15V, current of 0.2-0.4A and electrolysis time of 60-120min.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention realizes the high-efficiency removal of metal ions and metallurgical residues in the graphite waste residues by combining multi-stage leaching and electrochemical deintercalation, and lays a foundation for the recycling of waste graphite.
2) The invention eliminates the technical means of high-concentration strong acid treatment in the impurity removal process of the graphite slag, and realizes the high-efficiency removal of metal ion impurities in the graphite slag under the conditions of water washing, weak acid and weak base.
The waste residue generated after the valuable components are recovered by the waste lithium ion battery mainly comprises residual aluminum foil, negative electrode material graphite, metal elements remained on the surface of the graphite and embedded in the graphite, and various added reagent byproducts in the recovery process, belongs to dangerous wastes, cannot be freely transported and treated, additionally increases the treatment cost, and has higher separation, purification and recovery values. According to the technical scheme, the efficient impurity removal and purification of the graphite waste residue and the secondary recovery of valuable metal ions are synchronously realized under mild conditions, and the key problem in the recycling process of the graphite waste residue is solved.
The invention realizes the separation and purification of waste residue, waste diaphragm and other large particle diameters by a crushing and screening method; high-efficiency dissociation of graphite waste residues and removal of water-soluble impurities and a small amount of metal elements in the graphite waste residues are realized through hydraulic stirring; alkali leaching is carried out by sodium hydroxide and other alkalis to remove aluminum element, a small amount of lithium element and phosphorus; removing organic matters and fluorine impurities through anaerobic roasting; and leaching out residual nickel, cobalt, manganese, lithium and other metal elements in the waste residue by using an electrochemical deintercalation method.
Drawings
FIG. 1 is a schematic diagram of the technical process of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The technical flow diagram of the method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials is shown in figure 1, and the method comprises the following steps:
s1, putting massive acid leaching graphite waste into a ball mill for full crushing, breaking large particle aggregates formed in the acid leaching slag filter pressing process, screening the ground materials by using a 125 mu m screen, and removing coarse-grain copper aluminum foil, diaphragms and other large-grain impurities in the graphite slag to obtain fine-grain graphite slag;
s2, according to the solid-to-liquid ratio of 1g:3ml of fine-fraction graphite slag obtained in the step S1 is put into water, stirred for 60min, further dissociation of graphite slag particles is realized through hydraulic impact, meanwhile, water-soluble sulfate in the graphite slag is removed, and once-treated graphite slag and sulfate solution are obtained after solid-liquid separation; the hydraulic stirring can fully avoid excessive crushing of graphite particles while realizing dissociation of large particle agglomerates, thereby protecting a graphite structure;
and S element content in the waste graphite slag after the water leaching treatment in S2 is reduced from 3.48% to 0.33%.
S3, according to the solid-to-liquid ratio of 1g:15ml of the waste graphite slag subjected to primary treatment obtained in the step S2 is put into 2mol/L NaOH solution, water bath heating is carried out for 90min at 60 ℃, the 2mol/L NaOH solution is adopted to carry out alkaline leaching treatment on the graphite slag subjected to water washing, aluminum element, a small amount of lithium element and phosphate added in the process of leaching impurity removal of valuable metal in the graphite slag are removed, and solid-liquid separation is carried out to obtain secondary treated graphite slag and aluminum, lithium and phosphorus-containing solution;
specifically, in S3, aluminum foil with micro-particles remained in graphite slag is mainly removed, and LiAlO formed by Li is formed 2 The aluminum removal efficiency of the graphite slag is up to more than 98.5%, and meanwhile, the P element in the graphite slag after alkaline leaching is reduced from 2.66% to 0.02%.
S4, carrying out anaerobic roasting on the secondarily treated graphite waste residue obtained in the step S3 for 60min at 600 ℃, further removing fluorine-containing organic matters, putting the roasted graphite waste residue into an electrolytic tank, adopting a dilute sulfuric acid solution with the concentration of 0.3mol/L as electrolyte, taking platinum as an electrode material, carrying out electrochemical deintercalation process at the voltage of 15V and the current of 0.3A for 120min, deintercalating lithium, nickel, cobalt and manganese which are embedded in the graphite residue into a solution under the action of an electric field, carrying out solid-liquid separation to obtain pure graphite and a leaching solution, concentrating the leaching solution until lithium elements can form lithium carbonate precipitates, then adjusting the pH value of the leaching solution to 8.5 to enable nickel, cobalt and manganese to form precipitates to recover nickel, cobalt and manganese, adjusting the solution to be neutral, adding sodium carbonate into the solution according to the lithium ion content in the solution to precipitate lithium ions, and obtaining lithium carbonate through vacuum filtration and drying.
Example 2
The technical flow diagram of the method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials is shown in figure 1, and the method comprises the following steps:
s1, putting massive acid leaching graphite waste into a ball mill for full crushing, breaking large particle aggregates formed in the acid leaching slag filter pressing process, screening the ground materials by using a 125 mu m screen, and removing coarse-grain copper aluminum foil, diaphragms and other large-grain impurities in the graphite slag to obtain fine-grain graphite slag;
s2, according to the solid-to-liquid ratio of 1g:20ml of fine-fraction graphite slag obtained in the step S1 is put into water, stirred for 30min, further dissociation of graphite slag particles is realized through hydraulic impact, meanwhile, water-soluble sulfate in the graphite slag is removed, and once-treated graphite slag and sulfate solution are obtained after solid-liquid separation; the hydraulic stirring can fully avoid excessive crushing of graphite particles while realizing dissociation of large particle agglomerates, thereby protecting a graphite structure;
s3, according to the solid-to-liquid ratio of 1g:30ml of the waste graphite slag subjected to primary treatment obtained in the step S2 is put into 2mol/L NaOH solution, water bath heating is carried out for 80min at the temperature of 30 ℃, the 2mol/L NaOH solution is adopted to carry out alkaline leaching treatment on the graphite slag subjected to water washing, aluminum element, a small amount of lithium element and phosphate added in the process of leaching and impurity removal of valuable metal in the graphite slag are removed, and solid-liquid separation is carried out to obtain secondary treated graphite slag and aluminum, lithium and phosphorus-containing solution;
s4, carrying out anaerobic roasting at 800 ℃ for 30min on the secondarily treated graphite waste residue obtained in the step S3, further removing fluorine-containing organic matters, putting the graphite waste residue into an electrolytic tank, adopting a dilute sulfuric acid solution with the concentration of 0.5mol/L as an electrolyte, adopting platinum as an electrode material, carrying out electrochemical deintercalation process with the voltage of 10V and the current of 0.2A for 120min, deintercalating lithium, nickel, cobalt and manganese which are embedded in the graphite residue into a solution under the action of an electric field, carrying out solid-liquid separation to obtain pure graphite and a leaching solution, concentrating the leaching solution until lithium elements can form lithium carbonate precipitation, then adjusting the pH value of the leaching solution to 8.5 to enable nickel cobalt and manganese to form precipitates, recovering nickel, cobalt and manganese, adjusting the solution to be neutral, adding sodium carbonate according to the content of lithium ions in the solution to precipitate lithium ions in the solution, and obtaining lithium carbonate through vacuum filtration and drying.
Example 3
The technical flow diagram of the method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials is shown in figure 1, and the method comprises the following steps:
s1, putting massive acid leaching graphite waste into a ball mill for full crushing, breaking large particle aggregates formed in the acid leaching slag filter pressing process, screening the ground materials by using a 125 mu m screen, and removing coarse-grain copper aluminum foil, diaphragms and other large-grain impurities in the graphite slag to obtain fine-grain graphite slag;
s2, according to the solid-to-liquid ratio of 1g:10ml of fine-fraction graphite slag obtained in the step S1 is put into water, stirred for 90min, further dissociation of graphite slag particles is realized through hydraulic impact, meanwhile, water-soluble sulfate in the graphite slag is removed, and once-treated graphite slag and sulfate solution are obtained after solid-liquid separation; the hydraulic stirring can fully avoid excessive crushing of graphite particles while realizing dissociation of large particle agglomerates, thereby protecting a graphite structure;
s3, according to the solid-to-liquid ratio of 1g:20ml of the waste graphite slag subjected to primary treatment obtained in the step S2 is put into 2mol/L NaOH solution, water bath heating is carried out for 30min at 80 ℃, the 2mol/L NaOH solution is adopted to carry out alkaline leaching treatment on the graphite slag subjected to water washing, aluminum element, a small amount of lithium element and phosphate added in the process of leaching impurity removal of valuable metal in the graphite slag are removed, and solid-liquid separation is carried out to obtain secondary treated graphite slag and aluminum, lithium and phosphorus-containing solution;
s4, carrying out anaerobic roasting for 40min at 500 ℃, further removing fluorine-containing organic matters, placing the graphite waste residue into an electrolytic tank, adopting a dilute sulfuric acid solution with the concentration of 0.4mol/L as electrolyte, adopting platinum as an electrode material, carrying out electrochemical deintercalation process with the voltage of 12V and the current of 0.4A for 100min, deintercalating lithium, nickel, cobalt and manganese which are embedded in the graphite residue into a solution under the action of an electric field, carrying out solid-liquid separation to obtain pure graphite and a leaching solution, concentrating the leaching solution until lithium elements can form lithium carbonate precipitates, then adjusting the pH value of the leaching solution to 7-8.5 to enable nickel cobalt and manganese to form precipitates to recover nickel, cobalt and manganese, specifically, adjusting the pH value to 7.2, recovering nickel cobalt, continuously adjusting the pH value to 8.3, recovering manganese, adjusting the solution to be neutral, adding sodium carbonate into the solution according to the lithium ion content in the solution to precipitate, and carrying out vacuum filtration and drying to obtain lithium carbonate.
Comparative example 1
The conventional acid leaching method and the conventional impurity removal process are as follows:
crushing the massive acid leaching graphite waste, and screening by adopting a screen with the screen aperture of 74 mu m to obtain graphite slag;
graphite slag and 1mol/L sulfuric acid are mixed according to a solid-to-liquid ratio of 1g: after 10ml of the graphite slag is mixed, stirred at 60 ℃ for 90min for leaching, washed to be neutral after the stirring is finished, and dried to obtain primary acid leaching treated graphite slag;
anaerobic roasting the primary acid leaching treated graphite slag at 600 ℃ for 3 hours to obtain secondary treated graphite slag;
mixing the secondary treatment graphite slag with 1mol/L sulfuric acid according to a solid-to-liquid ratio of 1g: mixing 10mL, adding 1mL of 10% hydrogen peroxide for secondary acid leaching, stirring for 90min at 60 ℃, washing to be neutral after stirring, and drying to obtain acid leaching waste residues.
The content of each metal element in the acid leaching waste residue of the waste lithium battery material after treatment is shown in table 1, and compared with the invention, the metal ion residue in the acid leaching waste residue of comparative example 1 is far higher than the metal residue in the acid leaching waste residue after treatment according to the technical scheme of the invention. After the treatment by the method provided by the invention is adopted, the metal ion residual quantity in the acid leaching waste residue meets the requirement of low-temperature graphitization regeneration, and the regeneration and utilization value of the acid leaching graphite waste residue is greatly improved.
TABLE 1 comparison of residual amounts of conventional acid leaching and electrochemical deintercalation of metal ions
| Impurity element | Li | Al | Mn | Co | Ni | Cu | |
| Comparative example 1 | Traditional acid leaching (ppm) | 19.7 | 7.95 | 37.5 | 35 | 70 | 20 |
| Example 1 | Electrochemical de-intercalation (ppm) | 4.3 | 0 | 7.5 | 9.5 | 12.5 | 4.5 |
After valuable metals are recovered by acid leaching of positive and negative mixed powder materials of the waste lithium ion battery, a great amount of metal ions and residual medicaments in the metallurgical process are contained in waste graphite slag, and efficient removal of the metal ions and other impurities in the graphite slag is a key point for recycling. According to the invention, large particle aggregates and impurities in waste graphite slag are removed by a crushing and screening method, the particle size is reduced by mechanical grinding, the specific surface area is increased, the interlayer structure of graphite is broken, and the removal path of metal ions embedded in the graphite is shortened; the water-soluble impurities and a small amount of metal elements in the waste graphite slag are removed by water washing; alkaline leaching is carried out by sodium hydroxide solution to remove aluminum element, a small amount of lithium element and phosphorus-containing impurities; removing organic volatile matters and fluorine elements in the graphite slag by roasting; the method solves the problem that metal ions in the acid leaching waste graphite slag are difficult to remove efficiently, and realizes impurity removal and purification of the waste graphite slag and secondary recovery of valuable metals.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The method for purifying and removing impurities from acid leaching graphite waste residues of waste lithium battery materials is characterized by comprising the following steps of:
s1, crushing massive acid leaching graphite waste residues, and screening to obtain fine-grained graphite residues;
s2, placing the fine-fraction graphite slag obtained in the step S1 into water for stirring, and after the stirring is completed, carrying out solid-liquid separation to obtain primary treatment graphite slag and sulfate solution;
s3, placing the primary treated graphite waste residue obtained in the step S2 into an alkaline solution for heating, and after the heating is completed, carrying out solid-liquid separation to obtain secondary treated graphite waste residue and a solution containing aluminum, lithium and phosphorus;
s4, performing anaerobic roasting on the secondary treatment graphite waste residue obtained in the step S3 to obtain graphite waste residue with fluorine-containing organic matters removed;
adding graphite waste residue with fluorine-containing organic matters removed into an electrolytic tank, adopting an electrochemical deintercalation method to deintercalate lithium, nickel, cobalt and manganese which are embedded in the graphite waste residue into a solution, carrying out solid-liquid separation to obtain pure graphite and leaching solution, concentrating, regulating the pH value of the leaching solution to 7.2-8.5, recovering nickel, cobalt and manganese, and then recovering lithium through carbonate precipitation.
2. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residues according to claim 1, wherein in S1, the mesh size used for screening is smaller than 125 μm.
3. The method for purifying and removing impurities from acid leached graphite waste of waste lithium battery materials according to claim 1, wherein in S2, the ratio of fine fraction graphite waste to water is 1g:3-20ml.
4. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residues according to claim 1, wherein in the step S2, the stirring time is 30-90min.
5. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residue according to claim 1, wherein in S3, the ratio of the once treated graphite waste residue to alkaline solution is 1g:15-30ml, and the concentration of the alkaline solution is 2mol/L.
6. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residues according to claim 1, wherein in the step S3, the heating temperature is 30-80 ℃, and the stirring time is 30-90min.
7. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residue according to claim 1, wherein in S3, the alkaline solution used includes, but is not limited to, sodium hydroxide and potassium hydroxide.
8. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residues according to claim 1, wherein in S4, the anaerobic roasting temperature is 500-800 ℃ and the roasting time is 30-60min.
9. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residue according to claim 1, wherein in S4, the electrochemical deintercalation method is to place the graphite waste residue from which fluorine-containing organic matters are removed at the anode end of an electrolytic tank, and the electrode material is platinum; the electrolyte is dilute sulfuric acid solution of 0.3-0.5 mol/L.
10. The method for purifying and removing impurities from waste lithium battery material acid leaching graphite waste residues according to claim 1, wherein in S4, the electrochemical deintercalation process voltage is 10-15V, the current is 0.2-0.4A, and the electrolysis time is 60-120min.
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