CN114515651A - Compound inhibitor and preparation method and application thereof - Google Patents
Compound inhibitor and preparation method and application thereof Download PDFInfo
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- CN114515651A CN114515651A CN202210077140.3A CN202210077140A CN114515651A CN 114515651 A CN114515651 A CN 114515651A CN 202210077140 A CN202210077140 A CN 202210077140A CN 114515651 A CN114515651 A CN 114515651A
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- graphite
- flotation
- concentrate
- compound inhibitor
- mass ratio
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 228
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 166
- 239000010439 graphite Substances 0.000 claims abstract description 166
- 239000012141 concentrate Substances 0.000 claims abstract description 57
- 238000005188 flotation Methods 0.000 claims abstract description 52
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000002699 waste material Substances 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 19
- 238000007885 magnetic separation Methods 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 42
- 229910017052 cobalt Inorganic materials 0.000 abstract description 21
- 239000010941 cobalt Substances 0.000 abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052759 nickel Inorganic materials 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 8
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 15
- 239000004571 lime Substances 0.000 description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 14
- 235000011941 Tilia x europaea Nutrition 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000007770 graphite material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229940094933 n-dodecane Drugs 0.000 description 7
- 239000004604 Blowing Agent Substances 0.000 description 6
- 238000005273 aeration Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical group CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- -1 nickel-cobalt metal oxide Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a compound inhibitor and a preparation method and application thereof, wherein the compound inhibitor comprises the following preparation raw materials: sulfites, alkalis and hypochlorites. In the graphite flotation process, the compound inhibitor can effectively inhibit metal elements such as nickel and cobalt from entering graphite concentrate, so that the content of the metal elements in the graphite concentrate is reduced; on the other hand, in the graphite recovery process provided by combining the compound inhibitor, activated carbon (adsorbent and reducing agent) is added into flotation graphite concentrate pulp for adsorption for a period of time before magnetizing roasting, so that nickel-cobalt oxide can be efficiently and accurately reduced; thereby further reducing the metal content in the purified graphite.
Description
Technical Field
The invention relates to the technical field of environmental protection and battery recovery, and particularly relates to a compound inhibitor and a preparation method and application thereof.
Background
With the rapid development of new energy automobiles in recent years, the demand and market reserve of lithium ion batteries are rapidly increased. However, the lithium ion battery is subject to scrapping treatment after 3-5 years of service, contains toxic, harmful, flammable and explosive organic electrolyte and more high-price metals, and if the lithium ion battery is not properly treated, not only is the environment polluted, but also the resource is wasted. The existing waste lithium battery recovery technology is mainly used for recovering the anode electrode material. The recycling of negative electrode graphite is of little concern to the industry and academia. Although some technologies propose graphite recovery and impurity removal technologies in waste lithium batteries, the recovery technologies are all at laboratory level, and a single negative electrode piece is obtained through manual disassembly and then separation, impurity removal and purification of graphite and copper foil are carried out. There are also processes proposed for graphite recovery from spent lithium batteries in industry, but the longer flotation flow in such processes usually requires multiple concentration and scavenging combinations. These techniques are difficult to apply to actual industrial production. And the graphite recovery process has long flow and complex treatment process.
In the related art, different inhibitors are screened to control the metal elements to enter the graphite flotation concentrate, but part of copper, nickel, cobalt, manganese and the like still enter the graphite product along with foams. If the materials cannot be removed, not only the quality of the graphite product is affected, but also the waste of resources is caused.
In summary, there is a need to develop a compound inhibitor which can realize the efficient removal of metal elements.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a compound inhibitor which can realize the high-efficiency removal of metal elements.
The invention also provides a preparation method of the compound inhibitor.
The invention also provides application of the compound inhibitor in a graphite flotation process.
The invention also provides a graphite flotation method, and high-grade graphite is prepared by using the method.
The invention also provides application of the compound inhibitor in graphite flotation of waste lithium ion battery electrode materials.
The invention also provides application of the compound inhibitor in recycling the negative electrode of the waste lithium ion battery.
The invention also provides a method for recovering graphite in the negative electrode of the waste lithium ion battery.
The invention provides a compound inhibitor in a first aspect, which comprises the following preparation raw materials: sulfites, alkalis and hypochlorites.
According to at least one embodiment of the present invention, the following advantageous effects are provided:
according to the compound inhibitor, the hydrophilic hydroxide (combined action of alkali and sulfite) is formed on the surface of the metal element particles (nickel, cobalt, manganese and the like), so that the metal elements in the waste battery material are converted into the hydrophilic hydroxide, the hydrophilicity of the surface of the metal element particles is improved, the metal element particles are inhibited from entering graphite concentrate, and the content of the metal elements in the graphite concentrate is greatly reduced.
According to some embodiments of the invention, the base comprises at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
According to some embodiments of the invention, the alkali comprises lime.
Ca formed by lime2+And [ Ca (OH) ]]+The collecting agent is preferentially adsorbed on the surface of nickel cobalt oxide, and the adsorption of the collecting agent on the surface of the collecting agent is inhibited; in addition, lime can adjust the pH value of the ore pulp to make the solution alkaline.
According to some embodiments of the invention, the mass ratio of the sulfite, the base and the hypochlorite is 1:1 to 100:1 to 50.
The concentration is controlled within the range, so that the lower dosage of the medicament is ensured, and the lower content of the metal impurities in the flotation graphite concentrate can be ensured.
According to some embodiments of the invention, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1 to 50: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the base and the hypochlorite is 1:1 to 25: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the base and the hypochlorite is 1:20 to 25: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1 to 100:1 to 40.
According to some embodiments of the invention, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1 to 100: 25-40.
According to some embodiments of the invention, the mass ratio of the sulfite, the base and the hypochlorite is 1:20 to 25: 25-40.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1 to 50: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1 to 25: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:20 to 25: 1 to 50.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1 to 100:1 to 40.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1 to 100: 25-40.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1:20 to 25: 25-40.
According to some embodiments of the invention, the mass ratio of the sulfite, the lime and the hypochlorite is 1: 20: 40.
according to some embodiments of the invention, the mass ratio of the sodium sulfite, the lime and the hypochlorite is 1: 20: 40.
according to some embodiments of the invention, the sulfite comprises at least one of sodium sulfite, potassium sulfite, calcium sulfite, sodium bisulfite, potassium bisulfite, and calcium hydrogen sulfite.
According to some embodiments of the invention, the hypochlorite comprises at least one of sodium hypochlorite, calcium hypochlorite, and potassium hypochlorite.
The second aspect of the invention provides a preparation method of the compound inhibitor, which comprises the following steps: mixing the sulfite, the alkali and the hypochlorite to obtain the sodium hypochlorite.
The third aspect of the invention provides an application of the compound inhibitor in a graphite flotation process.
The fourth aspect of the invention provides a graphite flotation method, which comprises the following steps: and sequentially adding the compound inhibitor, the collecting agent and the foaming agent into the graphite raw material for flotation to obtain graphite concentrate.
According to at least one embodiment of the present invention, the following advantageous effects are provided:
the preparation steps of the method are simple to operate, and the graphite concentrate can be effectively recycled only through a simple flotation process.
According to some embodiments of the invention, the graphite feedstock comprises an electrode material of a spent lithium ion battery.
According to some embodiments of the invention, the graphite feedstock is subjected to a sieving process.
According to some embodiments of the invention, the screen size of the sieving treatment is 100 mesh to 100 mesh.
According to some embodiments of the invention, the graphite feedstock is further subjected to a calcination process.
According to some embodiments of the invention, the temperature of the calcination process is from 200 ℃ to 550 ℃.
The flotation effect is influenced because the organic binder is arranged on the surfaces of the positive and negative active material particles in the graphite raw material, and the organic binder can be effectively removed in the temperature range; in addition, partial electrolyte remained in the graphite raw material influences the flotation foaming performance, and can be effectively removed in the temperature range.
According to some embodiments of the invention, the temperature increase rate of the calcination treatment is 5 ℃/min to 10 ℃/min.
According to some embodiments of the invention, the time of the calcination treatment is 1h to 2 h.
According to some embodiments of the invention, the collector comprises a hydrocarbon compound.
According to some embodiments of the invention, the hydrocarbon compound is C10～C22The hydrocarbon compound of (1).
According to some embodiments of the invention, the hydrocarbon compound is C11～C17Of (a) an alkane.
According to some embodiments of the invention, the hydrocarbon compound is n-dodecane.
According to some embodiments of the invention, the collector is at least one of kerosene, diesel oil and n-dodecane.
According to some embodiments of the invention, the blowing agent comprises an alcoholic blowing agent.
According to some embodiments of the invention, the alcoholic foaming agent comprises at least one of terpineol oil, methyl isobutyl carbinol, and No. 2 oil.
According to some embodiments of the invention, the solid to liquid ratio in the flotation process is between 25g and 100 g: 100 mL.
The solid-liquid ratio is controlled in the range, so that the optimal flotation effect is ensured, and the maximum production efficiency can be ensured.
According to some embodiments of the invention, the solid to liquid ratio in the flotation process is between 35g and 100 g: 100 mL.
According to some embodiments of the invention, the solid to liquid ratio in the flotation process is between 35g and 70 g: 100 mL.
According to some embodiments of the invention, the mass ratio of the compound inhibitor to the calcined graphite raw material is 500g to 10000 g: 1 t.
According to some embodiments of the invention, the mass ratio of the compound inhibitor to the calcined graphite raw material is 3000 g-10000 g: 1 t.
According to some embodiments of the invention, the mass ratio of the compound inhibitor to the calcined graphite raw material is 4000g to 10000 g: 1 t.
According to some embodiments of the invention, the mass ratio of the compound inhibitor to the calcined graphite raw material is 4000 g-6000 g: 1 t.
According to some embodiments of the invention, the mass ratio of the collector to the calcined graphite raw material is 10g to 500 g: 1 t.
According to some embodiments of the invention, the mass ratio of the collector to the calcined graphite raw material is 100g to 500 g: 1 t.
According to some embodiments of the invention, the mass ratio of the collector to the calcined graphite raw material is 100g to 200 g: 1 t.
According to some embodiments of the invention, the mass ratio of the collector to the calcined graphite raw material is 150g to 200 g: 1 t.
According to some embodiments of the invention, the mass ratio of the blowing agent to the calcined graphite raw material is 10g to 500 g: 1 t.
According to some embodiments of the invention, the mass ratio of the blowing agent to the calcined graphite raw material is 80g to 500 g: 1 t.
According to some embodiments of the invention, the mass ratio of the blowing agent to the calcined graphite raw material is 80g to 200 g: 1 t.
According to some embodiments of the invention, the mass ratio of the blowing agent to the calcined graphite raw material is 80g to 100 g: 1 t.
According to some embodiments of the invention, the agitation speed for flotation is 1600r/min to 1800 r/min.
According to some embodiments of the invention, the aeration rate for said flotation is between 160L/min and 180L/min.
According to some embodiments of the invention, the time of flotation is 2min to 10 min.
According to some embodiments of the invention, the time of flotation is 4min to 10 min.
According to some embodiments of the invention, the time of flotation is 4min to 6 min.
According to some embodiments of the invention, the graphite concentrate is subjected to reduction, magnetizing roasting and magnetic separation to obtain purified graphite.
The reduction roasting is a magnetizing roasting process, and the nickel-cobalt oxide has magnetism after being reduced.
According to some embodiments of the invention, the reducing agent in the reduction process is activated carbon.
According to some embodiments of the invention, the activated carbon is added to the graphite concentrate for mixing.
According to some embodiments of the invention, the mixing is by magnetic stirring.
According to some embodiments of the invention, the mass ratio of the activated carbon to the graphite concentrate is 1-4: 50.
Within the range, the mass ratio can ensure that the residual metal oxides in the graphite concentrate are fully reduced in the magnetizing roasting process, and meanwhile, the waste of reducing agents (such as activated carbon and the like) is not caused.
According to some embodiments of the invention, the time of mixing is between 10min and 30 min.
According to some embodiments of the invention, the temperature of the magnetizing bake is 500 ℃ to 800 ℃.
The temperature of the magnetizing roasting can ensure that the nickel-cobalt oxide is fully reduced in the temperature range, thereby being beneficial to subsequent magnetic separation and ensuring the quality of the purified graphite.
According to some embodiments of the invention, the temperature rise rate of the magnetizing roast is 5 ℃/min to 10 ℃/min.
According to some embodiments of the invention, the temperature rise rate of the magnetizing bake is 10 ℃/min.
According to some embodiments of the invention, the holding time for the magnetizing roasting is 1h to 3 h.
According to some embodiments of the invention, the magnetic field strength of the magnetic separation is 3000Gs to 5000 Gs.
The magnetic field intensity can be controlled within the range to ensure that the magnetized substances are fully removed, and the quality of the purified graphite is improved.
According to some embodiments of the invention, the magnetic field strength of the magnetic separation is 3500Gs to 5000 Gs.
The fifth aspect of the invention provides application of the compound inhibitor in graphite flotation of waste lithium ion battery negative electrode materials.
The sixth aspect of the invention also provides application of the compound inhibitor in recycling the anode material of the waste lithium ion battery.
The seventh aspect of the invention also provides a method for recovering graphite from the negative electrode material of the waste lithium ion battery, which comprises the following steps:
s1, calcining the waste lithium ion battery negative electrode material and then floating to obtain graphite concentrate;
and S2, adding activated carbon into the graphite concentrate obtained in the step S1, dispersing, carrying out solid-liquid separation, drying, and carrying out magnetizing roasting-magnetic separation.
According to some embodiments of the invention, the waste lithium ion battery negative electrode material is subjected to a sieving treatment.
According to some embodiments of the invention, the screen size of the sieving treatment is 100 mesh to 100 mesh.
According to some embodiments of the invention, the temperature of the calcination is from 200 ℃ to 550 ℃.
According to some embodiments of the invention, the temperature rise rate of the calcination is from 5 ℃/min to 10 ℃/min.
According to some embodiments of the invention, the calcination is for a time period of 1h to 2 h.
According to some embodiments of the invention, the dispersing is magnetic stirring.
According to at least one embodiment of the invention, the following beneficial effects are provided:
according to the method for recovering graphite from the waste lithium ion batteries, the activated carbon with both adsorbability and reducibility is added into the flotation pulp and stirred for a period of time, so that nickel-cobalt metal oxide in graphite concentrate can be effectively adsorbed, meanwhile, the activated carbon is also used as a reducing agent in magnetizing roasting, and the nickel-cobalt oxide can be more efficiently and accurately reduced by utilizing the stirring adsorption step; thereby improving the magnetizing roasting efficiency.
Drawings
Fig. 1 is a process flow diagram of waste graphite recovery in example 1 of the present invention.
Figure 2 is an XRD pattern of graphite concentrate obtained by flotation in example 1 of the present invention.
Fig. 3 is an SEM image of graphite concentrate flotated according to example 2 of the present invention.
Fig. 4 is an XRD pattern of the purified graphite obtained in example 3 of the present invention.
FIG. 5 is an SEM photograph of the purified graphite obtained in example 3 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Specific examples of the present invention are described in detail below.
In the embodiment of the invention, the graphite in the raw materials and the purified products is measured by a carbon-sulfur instrument, and the metal content is measured by ICP.
Example 1
The embodiment is a method for recovering graphite from a negative electrode material of a waste lithium ion battery, as shown in fig. 1, and the method comprises the following steps:
s1, screening the graphite-containing waste lithium ion battery negative electrode material (the raw material is from Hunan Bangpo circulation science and technology Co., Ltd.) through a 100-mesh sieve to obtain a graphite material.
S2, roasting the graphite material (the mass percent of graphite is about 40%, and the mass percent of nickel and cobalt elements is about 35%) in the step S1, heating to 200 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 1h to obtain the roasted graphite.
S3, carrying out flotation on the calcined graphite in the step S2 at a solid-to-liquid ratio of 70g/100 mL.
Wherein the collecting agent is n-dodecane, and the using amount (namely the mass ratio of the collecting agent to the roasted graphite) is 200 g/t; the foaming agent is methyl isobutyl methane, the dosage (namely the mass ratio of the foaming agent to the roasted graphite) is 100g/t, the dosage of the compound inhibitor (namely the mass ratio of the compound inhibitor to the roasted graphite) is 4000g/t (sodium sulfite: lime (national drug group chemical reagent company, analytical purity): the mass ratio of calcium hypochlorite and sodium hypochlorite is 1:20 (20+ 20)); the rotating speed of the flotation machine is 1800r/min, the aeration quantity is 160L/h, and the flotation time is 4 min; obtaining graphite concentrate and tailings.
The carbon content of the graphite concentrate obtained in the step is 90.6%, and the nickel and cobalt content is 2.4%.
And S4, adding activated carbon (analytically pure by Tianjin Deng chemical reagent factory) to the graphite concentrate obtained in the step S3 (the ratio of the graphite concentrate to the activated carbon is 100:3), stirring for 15min on a magnetic stirrer, and filtering and drying to obtain dried graphite concentrate. Placing the dried graphite concentrate into a sealed container, heating to 700 ℃ at a speed of 10 ℃/min in a muffle furnace, and preserving heat for 1.5 h; obtaining the roasted material.
And S5, carrying out magnetic separation on the roasted material obtained in the step S4 in a magnetic separation tube, and obtaining purified graphite with the magnetic field intensity of 3500 Gs. The mass fraction of carbon in the purified graphite obtained in the embodiment is 96.7%, and the sum of the mass fractions of the nickel element and the cobalt element is less than 0.3%.
The XRD of the graphite concentrate produced in step S3 of this example is shown in fig. 2; as can be seen from fig. 2, the graphite concentrate obtained in this example has a high purity.
Example 2
The embodiment is a method for recovering graphite from a waste lithium ion battery negative electrode material, which comprises the following steps:
s1, screening the graphite-containing waste lithium ion battery negative electrode material (the raw material is from Hunan Bangpo circulation science and technology Co., Ltd.) through a 100-mesh sieve to obtain a graphite material.
S2, roasting the graphite material (the mass percent of the graphite is about 50%, and the mass percent of the nickel and the cobalt are about 30%) in the step S1, heating to 200 ℃ at the heating rate of 10 ℃/min, and then preserving heat for 1h to obtain the roasted graphite.
S3, carrying out flotation on the calcined graphite in the step S2 at a solid-to-liquid ratio of 30g/100 mL.
Wherein the collecting agent is n-dodecane, and the using amount (namely the mass ratio of the collecting agent to the roasted graphite) is 150 g/t; the foaming agent is methyl isobutyl methane, the dosage (namely the mass ratio of the foaming agent to the roasted graphite) is 80g/t, the dosage of the compound inhibitor (namely the mass ratio of the compound inhibitor to the roasted graphite) is 3000g/t (sodium sulfite: lime (national pharmaceutical group chemical reagent company, analytical purity): the mass ratio of calcium hypochlorite is 1: 25: 25); the rotating speed of the flotation machine is 1800r/min, the aeration quantity is 160L/h, and the flotation time is 4 min; obtaining graphite concentrate and tailings.
The carbon content of the graphite concentrate obtained in the step is 93.5%, and the nickel and cobalt content is 2.2%.
And S4, adding activated carbon (analytically pure by Tianjin Deng chemical reagent factory) to the graphite concentrate obtained in the step S3 (the ratio of the graphite concentrate to the activated carbon is 20:1), stirring for 10min on a magnetic stirrer, and filtering and drying to obtain dried graphite concentrate. Placing the dried graphite concentrate into a sealed container, heating to 650 ℃ at a speed of 10 ℃/min in a muffle furnace, and preserving heat for 2 h; obtaining the roasted material.
S5, carrying out magnetic separation on the roasted material obtained in the step S4 in a magnetic separation tube, wherein the magnetic field intensity is 3500Gs, and obtaining the purified graphite. The mass fraction of carbon in the purified graphite obtained in the embodiment is 96.9%, and the sum of the mass fractions of the nickel element and the cobalt element is less than 0.2%.
The SEM image of the graphite concentrate obtained in this example S3 is shown in fig. 3, and it can be seen from fig. 3 that the graphite concentrate obtained in this example has good homogeneity.
Example 3
The embodiment is a method for recovering graphite from a waste lithium ion battery negative electrode material, which comprises the following steps:
s1, screening the graphite-containing waste lithium ion battery negative electrode material (the raw material is from Hunan Bangpo circulation science and technology Co., Ltd.) through a 100-mesh sieve to obtain a graphite material.
S2, roasting the graphite material (the mass percent of graphite is about 30%, and the mass percent of nickel and cobalt elements is about 50%) in the step S1, heating to 300 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 1.5h to obtain the roasted graphite.
S3, carrying out flotation on the graphite roasted in the step S2 at the solid-to-liquid ratio of 100g/100 mL.
Wherein the collecting agent is n-dodecane, and the using amount (namely the mass ratio of the collecting agent to the roasted graphite) is 100 g/t; the foaming agent is methyl isobutyl methane, the dosage (namely the mass ratio of the foaming agent to the roasted graphite) is 80g/t, the dosage of the compound inhibitor (namely the mass ratio of the compound inhibitor to the roasted graphite) is 6000g/t (sodium sulfite: lime (national drug group chemical agent Co., Ltd., analytically pure): the mass ratio of sodium hypochlorite is 1: 100: 50); the rotating speed of the flotation machine is 1600r/min, the aeration quantity is 180L/h, and the flotation time is 4 min; obtaining graphite concentrate and tailings.
The carbon content of the graphite concentrate obtained in the step is 88.3%, and the nickel and cobalt content is 6.5%.
And S4, adding activated carbon (analytically pure by Tianjin Deng chemical reagent factory) to the graphite concentrate obtained in the step S3 (the ratio of the graphite concentrate to the activated carbon is 25:2), stirring for 30min on a magnetic stirrer, and filtering and drying to obtain dried graphite concentrate. Placing the dried graphite concentrate into a sealed container, heating to 750 ℃ in a muffle furnace at a speed of 10 ℃/min, and preserving heat for 2 h; obtaining the roasted material.
And S5, carrying out magnetic separation on the roasted material obtained in the step S4 in a magnetic separation tube, and obtaining purified graphite with the magnetic field intensity of 3500 Gs. The mass fraction of carbon in the purified graphite obtained in the embodiment is 92.5%, and the sum of the mass fractions of the nickel element and the cobalt element is less than 0.5%.
The XRD and SEM images of the purified graphite obtained in the procedure of this example are shown in fig. 4 and 5, and it can be seen from fig. 4 and 5 that the purified graphite obtained in this example has high purity and uniform particles.
Example 4
The embodiment is a method for recovering graphite from a waste lithium ion battery negative electrode material, which comprises the following steps:
s1, screening the graphite-containing waste lithium ion battery negative electrode material (the raw material is from Hunan Bangpo circulation science and technology Co., Ltd.) through a 100-mesh sieve to obtain a graphite material.
S2, roasting the graphite material (the mass percent of graphite is about 40%, and the mass percent of nickel and cobalt elements is about 35%) in the step S1, heating to 200 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 1h to obtain the roasted graphite.
S3, floating the graphite roasted in the step S2 at a solid-to-liquid ratio of 70g/100 mL.
Wherein the collecting agent is n-dodecane, and the using amount (namely the mass ratio of the collecting agent to the roasted graphite) is 200 g/t; the foaming agent is methyl isobutyl methane, the using amount (namely the mass ratio of the foaming agent to the roasted graphite) is 100g/t, the rotating speed of a flotation machine is 1800r/min, the aeration quantity is 160L/h, and the flotation time is 4 min; obtaining graphite concentrate and tailings.
The carbon content of the graphite concentrate obtained in the step is 84.3%, and the nickel and cobalt content is 8.1%.
And S4, drying the graphite concentrate obtained in the step S3, adding activated carbon (the ratio of the graphite concentrate to the activated carbon is 100:3), and physically and uniformly mixing to obtain a mixture. Placing the mixture in a sealed container, heating to 700 ℃ in a muffle furnace at a speed of 10 ℃/min, and preserving heat for 1.5 h; obtaining the roasted material.
And S5, carrying out magnetic separation on the roasted material obtained in the step S4 in a magnetic separation tube, and obtaining purified graphite with the magnetic field intensity of 3500 Gs. The mass fraction of carbon in the purified graphite obtained in this example was 97%, and the sum of the mass fractions of nickel and cobalt was 6%.
Example 5
The embodiment is a method for recovering graphite from a waste lithium ion battery negative electrode material, which comprises the following steps:
s1, screening the graphite-containing waste lithium ion battery negative electrode material (the raw material is from Hunan Bangpo cycle Co., Ltd.) through a 100-mesh sieve to obtain a graphite material.
S2, roasting the graphite material (the mass percent of graphite is about 40%, and the mass percent of nickel and cobalt elements is about 35%) in the step S1, heating to 200 ℃ at a heating rate of 10 ℃/min, and then preserving heat for 1h to obtain the roasted graphite.
S3, carrying out flotation on the calcined graphite in the step S2 at a solid-to-liquid ratio of 70g/100 mL.
Wherein the collecting agent is n-dodecane, and the using amount (namely the mass ratio of the collecting agent to the roasted graphite) is 200 g/t; the foaming agent is methyl isobutyl methane, the dosage (namely the mass ratio of the foaming agent to the roasted graphite) is 100g/t, the dosage of the compound inhibitor (namely the mass ratio of the compound inhibitor to the roasted graphite) is 4000g/t (sodium sulfite: lime (national pharmaceutical group chemical reagent company, analytical purity): the mass ratio of calcium hypochlorite is 1: 20: 40); the rotating speed of the flotation machine is 1800r/min, the aeration quantity is 160L/h, and the flotation time is 4 min; obtaining graphite concentrate and tailings.
The carbon content of the graphite concentrate obtained in the step after flotation is 89.5%, and the nickel and cobalt content is 3.2%.
And S4, drying the graphite concentrate obtained in the step S3 to obtain dried graphite concentrate. Adding activated carbon (analytical pure in Tianjin Deng chemical reagent factory) into the dried graphite concentrate, and physically mixing to obtain a mixture (the ratio of the dried graphite concentrate to the activated carbon is 100: 3); placing the mixture in a sealed container, heating to 700 ℃ at a speed of 10 ℃/min in a muffle furnace, and preserving heat for 1.5 h; obtaining the roasted material.
And S5, carrying out magnetic separation on the roasted material obtained in the step S4 in a magnetic separation tube, and obtaining purified graphite with the magnetic field intensity of 3500 Gs. In the purified graphite obtained in the present example, the mass fraction of carbon was 95%, and the sum of the mass fractions of nickel and cobalt was 1%.
The difference between embodiment 4 of the present invention and embodiment 1 is that: example 4 adding a reducing agent, namely activated carbon, in magnetizing roasting without adding a compound inhibitor in a physical uniform mixing manner;
the difference between embodiment 4 of the present invention and embodiment 1 is that: example 5 adding reducing agent activated carbon in a physical uniform mixing manner during the magnetizing roasting process;
compared with the embodiment 1 and the embodiment 4-5, the compound inhibitor has a good inhibiting effect on nickel and cobalt in the graphite flotation process of the waste lithium battery; according to the graphite recovery process provided by the invention, before the magnetic separation of the flotation graphite concentrate, activated carbon is added for adsorption for a period of time, so that the magnetizing roasting efficiency is improved, the magnetic separation effect is further improved, and the nickel and cobalt content in the purified graphite is further reduced.
In the graphite flotation process, the compound inhibitor can effectively inhibit elements such as nickel and cobalt from entering graphite concentrate, and the action mechanism is as follows: the compound inhibitor forms hydrophilic nickel-cobalt hydroxide on the surfaces of the nickel-cobalt-manganese particles, so that the inhibiting effect is achieved; on the other hand, in the graphite recovery process provided by combining the compound inhibitor, activated carbon (adsorbent and reducing agent) is added into flotation graphite concentrate pulp before magnetizing roasting to adsorb nickel-cobalt oxide which can be more efficiently and accurately reduced for a period of time, so that the content of metal in purified graphite is further reduced.
In conclusion, according to the method for recovering graphite from waste lithium ion batteries, the activated carbon with both adsorbability and reducibility is added into the flotation pulp and stirred for a period of time, so that nickel-cobalt metal oxide in graphite concentrate can be effectively adsorbed, meanwhile, the activated carbon is also used as a reducing agent in magnetizing roasting, and the nickel-cobalt oxide can be more efficiently and accurately reduced by utilizing the stirring adsorption step; thereby improving the magnetizing roasting efficiency.
While the embodiments of the present invention have been described in detail with reference to the specific embodiments, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A compound inhibitor is characterized in that: the compound inhibitor comprises the following preparation raw materials: sulfites, alkalis and hypochlorites.
2. The built inhibitor according to claim 1, which is characterized in that: the mass ratio of the sulfite to the alkali to the hypochlorite is 1: 1-100: 1-50.
3. The built inhibitor according to claim 1, which is characterized in that: the base includes at least one of sodium hydroxide, potassium hydroxide, and calcium hydroxide.
4. A process for preparing a built inhibitor according to any one of claims 1 to 3, characterized in that: mixing the sulfite, the alkali and the hypochlorite to obtain the sodium hypochlorite.
5. A graphite flotation method is characterized by comprising the following steps: the method comprises the following steps:
the compound inhibitor, the collector and the foaming agent of any one of claims 1 to 3 are sequentially added into a graphite raw material for flotation to obtain graphite concentrate.
6. The method of graphite flotation according to claim 5, characterized in that: the collector comprises a hydrocarbon compound; preferably, the foaming agent comprises an alcoholic foaming agent.
7. The method of graphite flotation according to claim 5, characterized in that: and further comprises post-treatment of the graphite concentrate.
8. The method of graphite flotation according to claim 7, characterized in that: the post-treatment comprises reduction, magnetizing roasting and magnetic separation; preferably, the temperature of the magnetizing roasting is 500-800 ℃; preferably, the magnetic field intensity of the magnetic separation is 3000 Gs-5000 Gs.
9. The method of graphite flotation according to claim 8, characterized in that: the reducing agent in the reduction process is activated carbon; preferably, the mass ratio of the activated carbon to the graphite concentrate is 1-4: 50.
10. The use of the compound inhibitor as defined in any one of claims 1 to 3 in the recovery of negative electrode materials of waste lithium ion batteries.
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| WO2023138261A1 (en) * | 2022-01-24 | 2023-07-27 | 宜昌邦普循环科技有限公司 | Compound inhibitor, preparation method therefor, and use thereof |
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