WO2023138261A1 - Compound inhibitor, preparation method therefor, and use thereof - Google Patents

Compound inhibitor, preparation method therefor, and use thereof Download PDF

Info

Publication number
WO2023138261A1
WO2023138261A1 PCT/CN2022/138529 CN2022138529W WO2023138261A1 WO 2023138261 A1 WO2023138261 A1 WO 2023138261A1 CN 2022138529 W CN2022138529 W CN 2022138529W WO 2023138261 A1 WO2023138261 A1 WO 2023138261A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphite
present application
flotation
compound inhibitor
concentrate
Prior art date
Application number
PCT/CN2022/138529
Other languages
French (fr)
Chinese (zh)
Inventor
刘江山
蔡勇
阮丁山
周游
***
李长东
Original Assignee
宜昌邦普循环科技有限公司
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宜昌邦普循环科技有限公司, 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司 filed Critical 宜昌邦普循环科技有限公司
Publication of WO2023138261A1 publication Critical patent/WO2023138261A1/en

Links

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

Definitions

  • the embodiments of the present application relate to the technical fields of environmental protection and battery recycling, such as a compound inhibitor and its preparation method and application.
  • lithium-ion batteries In recent years, with the rapid development of new energy vehicles, the demand and market holdings of lithium-ion batteries have risen sharply. However, lithium-ion batteries will be scrapped after 3 to 5 years of service. They contain toxic, harmful, flammable and explosive organic electrolytes, and also contain a lot of high-priced metals. If they are not handled properly, they will not only cause environmental pollution, but also be a waste of resources. Relevant waste lithium battery recycling technologies are mostly aimed at the recovery of positive electrode materials. The recovery of negative electrode graphite has received little attention from the industry and academia.
  • the embodiment of the present application provides a compound inhibitor, which can achieve efficient removal of metal elements.
  • the embodiment of the present application also provides the preparation method of the above compound inhibitor.
  • the embodiment of the present application also provides the application of the above compound inhibitor in the graphite flotation process.
  • the embodiment of the present application also provides a kind of method of graphite flotation, utilizes this method to make high-grade graphite.
  • the embodiment of the present application also provides the application of the compound inhibitor mentioned above in the flotation of graphite in waste lithium-ion battery electrode materials.
  • the embodiment of the present application also provides the application of the above-mentioned compound inhibitor in the recovery of the negative electrode of the waste lithium-ion battery.
  • the embodiment of the present application also provides a method for recovering graphite from the negative electrode of the waste lithium ion battery.
  • the first aspect of the present application provides a compound inhibitor, which comprises the following preparation raw materials: sulfite, alkali and hypochlorite.
  • the composite inhibitor provided in the embodiment of the present application by forming hydrophilic hydroxides on the surface of metal element particles (nickel, cobalt and manganese, etc.) (alkali and sulfites work together to convert the metal elements in waste battery materials into hydrophilic hydroxides), improves the hydrophilicity of the surface of the metal element particles, thereby preventing the metal element particles from entering the graphite concentrate, thereby greatly reducing the content of metal elements in the graphite concentrate.
  • metal element particles nickel, cobalt and manganese, etc.
  • the alkali includes at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
  • the alkali includes lime.
  • the Ca 2+ and [Ca(OH)] + that can be formed by lime are preferentially adsorbed on the surface of nickel-cobalt oxide, which inhibits the adsorption of collectors on its surface; in addition, lime can adjust the pH of the pulp to make the solution alkaline.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:1-50.
  • Controlling this range can ensure that the content of metal impurities in the flotation graphite concentrate is low while ensuring that the dosage of the agent is low.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-50:1-50.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-25:1-50.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:20-25:1-50.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:1-40.
  • the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:25-40.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-50:1-50.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-25:1-50.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:20-25:1-50.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-100:1-40.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-100:25-40.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:20-25:25-40.
  • the mass ratio of the sulfite, the lime and the hypochlorite is 1:20:40.
  • the mass ratio of the sodium sulfite, the lime and the hypochlorite is 1:20:40.
  • the sulfite includes at least one of sodium sulfite, potassium sulfite, calcium sulfite, sodium bisulfite, potassium bisulfite and calcium bisulfite.
  • the hypochlorite includes at least one of sodium hypochlorite, calcium hypochlorite and potassium hypochlorite.
  • the second aspect of the present application provides the preparation method of the above compound inhibitor, comprising the following steps: mixing the sulfite, the alkali and the hypochlorite to obtain the compound inhibitor.
  • the third aspect of the present application provides the application of the compound inhibitor mentioned above in the graphite flotation process.
  • the fourth aspect of the present application provides a graphite flotation method, which includes the following steps: sequentially adding the above compound inhibitor, collector and foaming agent to graphite raw materials for flotation to obtain graphite concentrate.
  • the preparation steps of the present application are simple to operate, and the effective recovery of graphite concentrate can be realized only through a simple flotation process.
  • the graphite raw material includes electrode materials of waste lithium-ion batteries.
  • the graphite raw material is sieved.
  • the sieve size of the sieving treatment is 100 mesh to 100 mesh.
  • the graphite raw material is also calcined.
  • the temperature of the calcination treatment is 200°C-550°C.
  • the organic binder on the surface of the positive and negative active material particles in the graphite raw material will affect the flotation effect, the organic binder can be effectively removed in this temperature range; in addition, there is still some electrolyte remaining in the graphite raw material that affects the flotation foaming performance, and it can also be effectively removed in this temperature range.
  • the heating rate of the calcination treatment is 5° C./min ⁇ 10° C./min.
  • the time of the calcination treatment is 1 h to 2 h.
  • the collector includes hydrocarbon compounds.
  • the hydrocarbon compound is a C 10 -C 22 hydrocarbon compound.
  • the hydrocarbon compound is a C 11 -C 17 alkane.
  • the hydrocarbon compound is n-dodecane.
  • the collector is at least one of kerosene, diesel oil and n-dodecane.
  • the foaming agent includes an alcohol foaming agent.
  • the alcohol foaming agent includes at least one of pine oil, methyl isobutyl carbinol and No. 2 oil.
  • the solid-to-liquid ratio in the flotation process is 25g ⁇ 100g:100mL.
  • Solid-liquid ratio control in this range can ensure the best flotation effect and the maximum production efficiency at the same time.
  • the solid-to-liquid ratio in the flotation process is 35g ⁇ 100g:100mL.
  • the solid-to-liquid ratio in the flotation process is 35g ⁇ 70g:100mL.
  • the mass ratio of the compounded inhibitor to the calcined graphite raw material is 500g ⁇ 10000g:1t.
  • the mass ratio of the compounded inhibitor to the calcined graphite raw material is 3000g ⁇ 10000g:1t.
  • the mass ratio of the compounded inhibitor to the calcined graphite raw material is 4000g-10000g:1t.
  • the mass ratio of the compounded inhibitor to the calcined graphite raw material is 4000g-6000g:1t.
  • the mass ratio of the collector to the calcined graphite raw material is 10g ⁇ 500g:1t.
  • the mass ratio of the collector to the calcined graphite raw material is 100g ⁇ 500g:1t.
  • the mass ratio of the collector to the calcined graphite raw material is 100g ⁇ 200g:1t.
  • the mass ratio of the collector to the calcined graphite raw material is 150g-200g:1t.
  • the mass ratio of the foaming agent to the calcined graphite raw material is 10g ⁇ 500g:1t.
  • the mass ratio of the foaming agent to the calcined graphite raw material is 80g ⁇ 500g:1t.
  • the mass ratio of the foaming agent to the calcined graphite raw material is 80g ⁇ 200g:1t.
  • the mass ratio of the foaming agent to the calcined graphite raw material is 80g ⁇ 100g:1t.
  • the stirring speed of the flotation is 1600r/min ⁇ 1800r/min.
  • the aeration rate of the flotation is 160L/min ⁇ 180L/min.
  • the time for the flotation is 2 minutes to 10 minutes.
  • the flotation time is 4 minutes to 10 minutes.
  • the flotation time is 4 minutes to 6 minutes.
  • the graphite concentrate is subjected to reduction, magnetization roasting and magnetic separation to obtain purified graphite.
  • Reduction roasting is magnetization roasting process, nickel cobalt oxide is magnetic after reduction.
  • the reducing agent in the reduction process is activated carbon.
  • the activated carbon is added to the graphite concentrate and mixed.
  • the mixing method is magnetic stirring.
  • the mass ratio of the activated carbon to the graphite concentrate is 1 ⁇ 4:50.
  • the mass ratio within this range can ensure that the residual metal oxides in the graphite concentrate are fully reduced during the magnetization roasting, and at the same time, the reducing agent (activated carbon, etc.) will not be wasted.
  • the mixing time is 10 minutes to 30 minutes.
  • the temperature of the magnetization calcination is 500°C-800°C.
  • the temperature of magnetization roasting in this temperature range can ensure the full reduction of nickel-cobalt oxide, which is beneficial to the subsequent magnetic separation and guarantees the quality of purified graphite.
  • the heating rate of the magnetization roasting is 5° C./min ⁇ 10° C./min.
  • the heating rate of the magnetization baking is 10° C./min.
  • the holding time of the magnetization roasting is 1 h to 3 h.
  • the magnetic field strength of the magnetic separation is 3000Gs-5000Gs.
  • Controlling the magnetic field strength within this range can ensure the full removal of magnetized substances and improve the quality of purified graphite.
  • the magnetic field strength of the magnetic separation is 3500Gs ⁇ 5000Gs.
  • the fifth aspect of the present application provides the application of the compound inhibitor mentioned above in the flotation of graphite in the negative electrode material of the waste lithium ion battery.
  • the sixth aspect of the present application also provides the application of the above-mentioned compound inhibitor in the recovery of the negative electrode material of the waste lithium ion battery.
  • the seventh aspect of the present application also provides a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
  • step S2 Add activated carbon to the graphite concentrate obtained in step S1 to disperse, separate solid and liquid, and perform magnetization roasting-magnetic separation after drying.
  • the waste lithium ion battery negative electrode material has been sieved.
  • the sieve size of the sieving treatment is 100 mesh to 100 mesh.
  • the temperature of the calcination is 200°C to 550°C.
  • the heating rate of the calcination is 5° C./min ⁇ 10° C./min.
  • the calcination time is 1 h to 2 h.
  • the dispersion is magnetic stirring.
  • activated carbon having both adsorptive and reducing properties is added to the flotation pulp and stirred for a period of time, which can effectively adsorb nickel-cobalt metal oxides in graphite concentrate, and at the same time, activated carbon is used as a reducing agent in magnetization roasting.
  • this stirring and adsorption step can reduce nickel-cobalt oxides more efficiently and accurately; thereby improving the efficiency of magnetization roasting.
  • Fig. 1 is the process flow diagram of waste and old graphite recovery in the embodiment 1 of the present application.
  • Figure 2 is the XRD pattern of the graphite concentrate obtained by flotation in Example 1 of the present application.
  • Fig. 3 is the SEM image of the graphite concentrate obtained by flotation in Example 2 of the present application.
  • Fig. 4 is the XRD pattern of the purified graphite prepared in Example 3 of the present application.
  • Graphite in the raw materials and purified products in the embodiments of the present application is measured by a carbon-sulfur meter, and the metal content is tested by ICP.
  • This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, as shown in Figure 1, comprising the following steps:
  • step S2 the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
  • step S3 Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
  • the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the calcined graphite) is 200g/t;
  • the foaming agent is methyl isobutyl methane, the consumption (i.e. the mass ratio of the foaming agent to the calcined graphite) is 100g/t, and the compound inhibitor dosage (i.e.
  • the mass ratio of the compound inhibitor to the calcined graphite is 4000g/t (sodium sulfite: lime (Sinopharm Chemical Reagent Co., Ltd., analytically pure): (calcium hypochlorite+time The mass ratio of sodium chlorate) is 1:20:(20+20)); the rotating speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
  • the carbon content in the graphite concentrate after flotation obtained in this step is 90.6%, and the nickel+cobalt content is 2.4%.
  • step S4 activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 100:3), placed on a magnetic stirrer and stirred for 15min, then filtered and dried to obtain dried graphite concentrate. Put the dried graphite concentrate in a sealed container, raise the temperature to 700°C at 10°C/min in a muffle furnace, and keep it warm for 1.5h; the roasted material is obtained.
  • activated carbon Tianjin Dengfeng Chemical Reagent Factory, analytically pure
  • the roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite.
  • the mass fraction of carbon in the purified graphite obtained in this embodiment is 96.7%, and the sum of the mass fractions of nickel element and cobalt element is ⁇ 0.3%.
  • the XRD of the graphite concentrate prepared in step S3 of this embodiment is shown in Figure 2; it can be known from Figure 2 that the graphite concentrate prepared in this embodiment has a higher purity.
  • This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
  • step S2 the graphite material in step S1 (the mass percentage of graphite is about 50%, and the mass percentage of nickel+cobalt element is about 30%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
  • step S3 Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 30g/100mL.
  • the collector is n-dodecane
  • the consumption i.e. the mass ratio of the collector to the roasted graphite
  • the foaming agent is methyl isobutyl methane
  • the consumption i.e. the mass ratio of the foamer to the roasted graphite
  • the compound inhibitor consumption i.e.
  • the mass ratio of the compound inhibitor to the roasted graphite is 3000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of calcium hypochlorite is 1:25:25); the rotation speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
  • the carbon content in the graphite concentrate after flotation obtained in this step is 93.5%, and the nickel+cobalt content is 2.2%.
  • step S4 activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 20:1), placed on a magnetic stirrer and stirred for 10min, then filtered and dried to obtain dried graphite concentrate. Place the dried graphite concentrate in a sealed container, raise the temperature to 650°C at 10°C/min in a muffle furnace, and keep it warm for 2 hours; the roasted material is obtained.
  • activated carbon Tianjin Dengfeng Chemical Reagent Factory, analytically pure
  • step S5 The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite.
  • the mass fraction of carbon in the purified graphite obtained in this example is 96.9%, and the sum of the mass fractions of nickel and cobalt is ⁇ 0.2%.
  • the SEM image of the graphite concentrate prepared in Example S3 is shown in FIG. 3 , and it can be known from FIG. 3 that the graphite concentrate prepared in this example has good uniformity.
  • This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
  • the graphite material in step S1 (the mass percentage of graphite is about 30%, and the mass percentage of nickel+cobalt element is about 50%) is roasted, and the temperature is raised to 300 ° C at a heating rate of 10 ° C / min, and then kept for 1.5 hours to obtain graphite after roasting.
  • step S3 Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 100g/100mL.
  • the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the roasted graphite) is 100g/t; the foaming agent is methyl isobutyl methane, and the consumption (i.e. the mass ratio of the foaming agent to the roasted graphite) is 80g/t, and the compound inhibitor consumption (i.e.
  • the mass ratio of the compound inhibitor to the roasted graphite is 6000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of sodium hypochlorite is 1:100:50); the rotation speed of the flotation machine is 1600r/min, the gas filling rate is 180L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
  • the carbon content in the graphite concentrate after flotation obtained in this step is 88.3%, and the nickel+cobalt content is 6.5%.
  • activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 25:2), placed on a magnetic stirrer and stirred for 30min, then filtered and dried to obtain dried graphite concentrate. Put the dried graphite concentrate in a sealed container, raise the temperature to 750°C at 10°C/min in a muffle furnace, and keep it warm for 2 hours; the roasted material is obtained.
  • the roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite.
  • the mass fraction of carbon in the purified graphite obtained in this embodiment is 92.5%, and the sum of the mass fractions of nickel element and cobalt element is ⁇ 0.5%.
  • the XRD and SEM diagrams of the purified graphite prepared in the steps of this embodiment are shown in Fig. 4 and Fig. 5, and it can be known from Fig. 4 and Fig. 5 that the purified graphite prepared in this embodiment has high purity and uniform particles.
  • This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
  • step S2 the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
  • step S3 Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
  • the collector is n-dodecane
  • the consumption i.e. the mass ratio of the collector to the roasted graphite
  • the foaming agent is methyl isobutyl methane
  • the consumption i.e. the mass ratio of the foamer to the roasted graphite
  • the rotating speed of the flotation machine is 1800r/min
  • the gas filling rate is 160L/h
  • the flotation time is 4min
  • graphite concentrate and tailings are obtained.
  • the carbon content in the graphite concentrate after flotation obtained in this step is 84.3%, and the nickel+cobalt content is 8.1%.
  • step S4 After drying the graphite concentrate obtained in step S3, add activated carbon (the ratio of graphite concentrate to activated carbon is 100:3), and physically mix to obtain a mixture. Put the mixture in a sealed container, raise the temperature to 700°C at 10°C/min in a muffle furnace, and keep it warm for 1.5h; the roasted material is obtained.
  • activated carbon the ratio of graphite concentrate to activated carbon is 100:3
  • the roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite.
  • the mass fraction of carbon in the purified graphite obtained in this embodiment is 97%, and the sum of the mass fractions of nickel and cobalt is 6%.
  • This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
  • step S2 the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
  • step S3 Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
  • the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the calcined graphite) is 200g/t;
  • the foaming agent is methyl isobutyl methane, the consumption (i.e. the mass ratio of the foaming agent to the calcined graphite) is 100g/t, and the compound inhibitor dosage (i.e.
  • the mass ratio of the compound inhibitor to the calcined graphite is 4000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of calcium hypochlorite 1:20:40); the rotational speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
  • the carbon content in the graphite concentrate after flotation obtained in this step is 89.5%, and the nickel+cobalt content is 3.2%.
  • step S4 Dry the graphite concentrate obtained in step S3 to obtain the dried graphite concentrate.
  • Activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) was added to the dried graphite concentrate and mixed physically to obtain a mixture (the ratio of dried graphite concentrate to activated carbon was 100:3); the mixture was placed in a sealed container, and the temperature was raised to 700°C in a muffle furnace at 10°C/min, and kept for 1.5h; the roasted material was obtained.
  • the roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite.
  • the mass fraction of carbon in the purified graphite obtained in this embodiment is 95%, and the sum of the mass fractions of nickel element and cobalt element is 1%.
  • Example 4 is that the reductant activated carbon is added in a physical mixing manner in the magnetization roasting without compounding inhibitor;
  • Example 5 The difference between Example 5 and Example 1 of the present application lies in that in Example 5, the reductant activated carbon is added by physical mixing during the magnetization roasting process;
  • Example 1 of the present application has a good inhibitory effect on nickel and cobalt elements in the graphite flotation process in waste lithium batteries;
  • the graphite recovery process provided by the application before the magnetic separation of flotation graphite concentrate, first adds activated carbon for adsorption for a period of time, which improves the magnetization roasting efficiency, and then improves the magnetic separation effect, and further reduces the content of nickel and cobalt in the purified graphite.
  • the compound inhibitor of the present application can effectively inhibit elements such as nickel and cobalt from entering the graphite concentrate.
  • the mechanism of action is: the compound inhibitor forms hydrophilic nickel-cobalt hydroxide on the surface of the nickel-cobalt-manganese particles, thereby achieving the inhibitory effect; on the other hand, in the graphite recovery process proposed in combination with the compound inhibitor, adding activated carbon (adsorbent & reducing agent) to the flotation graphite concentrate slurry for adsorption for a period of time before magnetization roasting can more efficiently and accurately reduce the nickel-cobalt oxide, thereby further reducing the metal content in the purified graphite.
  • activated carbon adsorbent & reducing agent
  • the method for recovering graphite from waste lithium-ion batteries of the present application involves adding activated carbon with both adsorptive and reducing properties into the flotation pulp and stirring for a period of time, which can effectively adsorb nickel-cobalt metal oxides in graphite concentrates.
  • activated carbon is also used as a reducing agent in magnetization roasting. Using this stirring and adsorption step can reduce nickel-cobalt oxides more efficiently and accurately; thereby improving the efficiency of magnetization roasting.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A compound inhibitor, a preparation method therefor, and a use thereof. The compound inhibitor comprises the following raw materials for preparation: a sulfite, a base, and hypochlorite. In a graphite flotation process, the compound inhibitor can effectively inhibit metal elements, such as nickel and cobalt, from entering a graphite concentrate, thereby reducing the content of metal elements in the graphite concentrate.

Description

一种复配抑制剂及其制备方法和应用A kind of compound inhibitor and its preparation method and application 技术领域technical field
本申请实施例涉及环境保护与电池回收技术领域，例如一种复配抑制剂及其制备方法和应用。The embodiments of the present application relate to the technical fields of environmental protection and battery recycling, such as a compound inhibitor and its preparation method and application.
背景技术Background technique
近年来随着新能源汽车的迅猛发展，锂离子电池的需求量和市场保有量急剧上升。然而锂离子电池在经过3年～5年的服役期后将面临报废处理，其中含有有毒有害易燃易爆的有机电解液，同时还含有较多高价金属，如果处理不当，不仅造成环境污染同时也是一种资源浪费。相关废旧锂电池回收技术多针对正极电极材料的回收。负极石墨的回收则很少受到业界和学术界关注。虽然也有一些技术提出了废旧锂电池中石墨回收及除杂技术，但是这些回收技术均为实验室级别，通过手工拆解得到单一的负极片再进行石墨和铜箔的分离除杂提纯。也有针对工业中废旧锂电池石墨回收提出的工艺，但是这类工艺中浮选流程较长通常需要多次精选和扫选组合。这些技术难以应用到实际工业生产中。且石墨回收工艺流程长和处理工艺复杂。In recent years, with the rapid development of new energy vehicles, the demand and market holdings of lithium-ion batteries have risen sharply. However, lithium-ion batteries will be scrapped after 3 to 5 years of service. They contain toxic, harmful, flammable and explosive organic electrolytes, and also contain a lot of high-priced metals. If they are not handled properly, they will not only cause environmental pollution, but also be a waste of resources. Relevant waste lithium battery recycling technologies are mostly aimed at the recovery of positive electrode materials. The recovery of negative electrode graphite has received little attention from the industry and academia. Although there are some technologies that have proposed graphite recovery and impurity removal technologies in waste lithium batteries, these recovery technologies are all laboratory-level, and a single negative electrode sheet is obtained by manual disassembly, and then the graphite and copper foil are separated, impurity-removed and purified. There are also processes proposed for the recovery of graphite from waste lithium batteries in industry, but the flotation process in this type of process is long and usually requires multiple selection and scavenging combinations. These techniques are difficult to apply to actual industrial production. Moreover, the graphite recovery process is long and the treatment process is complicated.
相关技术中通过筛选不同的抑制剂来控制金属元素进入石墨浮选精矿中，但仍会有部分铜、镍、钴和锰等随泡沫进入到石墨产品中。若不能将这些物质脱除，不仅会影响石墨产品的品质，还会造成资源的浪费。In the related art, different inhibitors are screened to control the entry of metal elements into the graphite flotation concentrate, but some copper, nickel, cobalt and manganese will still enter the graphite product with the foam. If these substances cannot be removed, it will not only affect the quality of graphite products, but also cause a waste of resources.
综上，有必要开发一种复配抑制剂，该抑制剂能够实现金属元素的高效脱除。In summary, it is necessary to develop a compound inhibitor that can achieve efficient removal of metal elements.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请实施例提供了一种复配抑制剂，该抑制剂能够实现金属元素的高效脱除。The embodiment of the present application provides a compound inhibitor, which can achieve efficient removal of metal elements.
本申请实施例还提供了上述复配抑制剂的制备方法。The embodiment of the present application also provides the preparation method of the above compound inhibitor.
本申请实施例还提供了上述复配抑制剂在石墨浮选过程中的应用。The embodiment of the present application also provides the application of the above compound inhibitor in the graphite flotation process.
本申请实施例还提供了一种石墨浮选的方法，利用该方法制得了高品位的 石墨。The embodiment of the present application also provides a kind of method of graphite flotation, utilizes this method to make high-grade graphite.
本申请实施例还提供了上述复配抑制剂在废旧锂离子电池电极材料中石墨浮选中的应用。The embodiment of the present application also provides the application of the compound inhibitor mentioned above in the flotation of graphite in waste lithium-ion battery electrode materials.
本申请实施例还提供了上述复配抑制剂在废旧锂离子电池负极回收中的应用。The embodiment of the present application also provides the application of the above-mentioned compound inhibitor in the recovery of the negative electrode of the waste lithium-ion battery.
本申请实施例还提供了一种废旧锂离子电池负极中石墨回收的方法。The embodiment of the present application also provides a method for recovering graphite from the negative electrode of the waste lithium ion battery.
本申请第一方面提供了一种复配抑制剂，所述复配抑制剂包括以下制备原料：亚硫酸盐、碱和次氯酸盐。The first aspect of the present application provides a compound inhibitor, which comprises the following preparation raw materials: sulfite, alkali and hypochlorite.
根据本申请的至少一种实施方式，具备如下有益效果：According to at least one embodiment of the present application, it has the following beneficial effects:
本申请实施例提供的复配抑制剂，通过在金属元素颗粒(镍、钴和锰等)表面形成亲水性的氢氧化物(碱和亚硫酸盐共同作用，使得废旧电池材料中金属元素转化为亲水性氢氧化物)，提高金属元素颗粒表面的亲水性，从而实现了抑制金属元素颗粒进入石墨精矿中，从而大大降低了石墨精矿中金属元素的含量。The composite inhibitor provided in the embodiment of the present application, by forming hydrophilic hydroxides on the surface of metal element particles (nickel, cobalt and manganese, etc.) (alkali and sulfites work together to convert the metal elements in waste battery materials into hydrophilic hydroxides), improves the hydrophilicity of the surface of the metal element particles, thereby preventing the metal element particles from entering the graphite concentrate, thereby greatly reducing the content of metal elements in the graphite concentrate.
根据本申请的一些实施方式，所述碱包括氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。According to some embodiments of the present application, the alkali includes at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
根据本申请的一些实施方式，所述碱包括石灰。According to some embodiments of the present application, the alkali includes lime.
石灰能够形成的Ca 2+和[Ca(OH)] +优先吸附在镍钴氧化物表面，抑制捕收剂在其表面吸附；另外石灰能够调节矿浆pH使溶液呈碱性。 The Ca 2+ and [Ca(OH)] + that can be formed by lime are preferentially adsorbed on the surface of nickel-cobalt oxide, which inhibits the adsorption of collectors on its surface; in addition, lime can adjust the pH of the pulp to make the solution alkaline.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:1～100：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:1-50.
将控制在此范围在保证药剂使用量较低的同时可以保证浮选石墨精矿中金属杂质含量较低。Controlling this range can ensure that the content of metal impurities in the flotation graphite concentrate is low while ensuring that the dosage of the agent is low.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:1～50：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-50:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:1～25：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-25:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:20～25：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:20-25:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质 量比为1:1～100：1～40。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:1-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:1～100：25～40。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:25-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:20～25：25～40。According to some embodiments of the present application, the mass ratio of the sulfite, the alkali and the hypochlorite is 1:20-25:25-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:1～50：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-50:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:1～25：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-25:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:20～25：1～50。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:20-25:1-50.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:1～100：1～40。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-100:1-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:1～100：25～40。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:1-100:25-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:20～25：25～40。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:20-25:25-40.
根据本申请的一些实施方式，所述亚硫酸盐、所述石灰和所述次氯酸盐的质量比为1:20：40。According to some embodiments of the present application, the mass ratio of the sulfite, the lime and the hypochlorite is 1:20:40.
根据本申请的一些实施方式，所述亚硫酸钠、所述石灰和所述次氯酸盐的质量比为1:20：40。According to some embodiments of the present application, the mass ratio of the sodium sulfite, the lime and the hypochlorite is 1:20:40.
根据本申请的一些实施方式，所述亚硫酸盐包亚硫酸钠、亚硫酸钾、亚硫酸钙、亚硫酸氢钠、亚硫酸氢钾和亚硫酸氢钙中的至少一种。According to some embodiments of the present application, the sulfite includes at least one of sodium sulfite, potassium sulfite, calcium sulfite, sodium bisulfite, potassium bisulfite and calcium bisulfite.
根据本申请的一些实施方式，所述的次氯酸盐包括次氯酸钠、次氯酸钙和次氯酸钾中的至少一种。According to some embodiments of the present application, the hypochlorite includes at least one of sodium hypochlorite, calcium hypochlorite and potassium hypochlorite.
本申请第二方面提供了上述复配抑制剂的制备方法，包括以下步骤：将所述亚硫酸盐、所述碱和所述次氯酸盐混合，即得。The second aspect of the present application provides the preparation method of the above compound inhibitor, comprising the following steps: mixing the sulfite, the alkali and the hypochlorite to obtain the compound inhibitor.
本申请第三方面提供了上述复配抑制剂在石墨浮选过程中的应用。The third aspect of the present application provides the application of the compound inhibitor mentioned above in the graphite flotation process.
本申请第四方面提供了一种石墨浮选的方法，包括以下步骤：将上述的复配抑制剂、捕收剂和起泡剂依次添加至石墨原料中进行浮选，得到石墨精矿。The fourth aspect of the present application provides a graphite flotation method, which includes the following steps: sequentially adding the above compound inhibitor, collector and foaming agent to graphite raw materials for flotation to obtain graphite concentrate.
根据本申请的至少一种实施方式，具备如下有益效果：According to at least one embodiment of the present application, it has the following beneficial effects:
本申请的制备步骤操作简单，仅需要通过简单的浮选过程即可实现石墨精矿的有效回收。The preparation steps of the present application are simple to operate, and the effective recovery of graphite concentrate can be realized only through a simple flotation process.
根据本申请的一些实施方式，所述石墨原料包括废旧锂离子电池的电极材料。According to some embodiments of the present application, the graphite raw material includes electrode materials of waste lithium-ion batteries.
根据本申请的一些实施方式，所述石墨原料经过筛分处理。According to some embodiments of the present application, the graphite raw material is sieved.
根据本申请的一些实施方式，所述筛分处理的筛网尺寸为100目～100目。According to some embodiments of the present application, the sieve size of the sieving treatment is 100 mesh to 100 mesh.
根据本申请的一些实施方式，所述石墨原料还经过煅烧处理。According to some embodiments of the present application, the graphite raw material is also calcined.
根据本申请的一些实施方式，所述煅烧处理的温度为200℃～550℃。According to some embodiments of the present application, the temperature of the calcination treatment is 200°C-550°C.
由于石墨原料中正负极活性材料颗粒表面具有有机粘结剂会影响浮选效果，在此温度区间能够有效去除有机粘结剂；另外石墨原料中还残存有部分电解液影响浮选起泡性能，在此温度区间亦能有效去除。Since the organic binder on the surface of the positive and negative active material particles in the graphite raw material will affect the flotation effect, the organic binder can be effectively removed in this temperature range; in addition, there is still some electrolyte remaining in the graphite raw material that affects the flotation foaming performance, and it can also be effectively removed in this temperature range.
根据本申请的一些实施方式，所述煅烧处理的升温速率为5℃/min～10℃/min。According to some embodiments of the present application, the heating rate of the calcination treatment is 5° C./min˜10° C./min.
根据本申请的一些实施方式，所述煅烧处理的时间为1h～2h。According to some embodiments of the present application, the time of the calcination treatment is 1 h to 2 h.
根据本申请的一些实施方式，所述捕收剂包括烃类化合物。According to some embodiments of the present application, the collector includes hydrocarbon compounds.
根据本申请的一些实施方式，所述烃类化合物为C 10～C 22的烃类化合物。 According to some embodiments of the present application, the hydrocarbon compound is a C 10 -C 22 hydrocarbon compound.
根据本申请的一些实施方式，所述烃类化合物为C 11～C 17的烷烃。 According to some embodiments of the present application, the hydrocarbon compound is a C 11 -C 17 alkane.
根据本申请的一些实施方式，所述烃类化合物为正十二烷。According to some embodiments of the present application, the hydrocarbon compound is n-dodecane.
根据本申请的一些实施方式，所述捕收剂为煤油、柴油和正十二烷中的至少一种。According to some embodiments of the present application, the collector is at least one of kerosene, diesel oil and n-dodecane.
根据本申请的一些实施方式，所述起泡剂包括醇类起泡剂。According to some embodiments of the present application, the foaming agent includes an alcohol foaming agent.
根据本申请的一些实施方式，所述醇类起泡剂包括松醇油、甲基异丁基甲醇和2号油中的至少一种。According to some embodiments of the present application, the alcohol foaming agent includes at least one of pine oil, methyl isobutyl carbinol and No. 2 oil.
根据本申请的一些实施方式，所述浮选过程中的固液比为25g～100g：100mL。According to some embodiments of the present application, the solid-to-liquid ratio in the flotation process is 25g˜100g:100mL.
固液比控制在此范围保证最佳浮选效果的同时能够保证最大的生产效率。Solid-liquid ratio control in this range can ensure the best flotation effect and the maximum production efficiency at the same time.
根据本申请的一些实施方式，所述浮选过程中的固液比为35g～100g：100mL。According to some embodiments of the present application, the solid-to-liquid ratio in the flotation process is 35g˜100g:100mL.
根据本申请的一些实施方式，所述浮选过程中的固液比为35g～70g：100mL。According to some embodiments of the present application, the solid-to-liquid ratio in the flotation process is 35g˜70g:100mL.
根据本申请的一些实施方式，所述复配抑制剂与煅烧处理后石墨原料的质量比为500g～10000g：1t。According to some embodiments of the present application, the mass ratio of the compounded inhibitor to the calcined graphite raw material is 500g˜10000g:1t.
根据本申请的一些实施方式，所述复配抑制剂与煅烧处理后石墨原料的质 量比为3000g～10000g：1t。According to some embodiments of the present application, the mass ratio of the compounded inhibitor to the calcined graphite raw material is 3000g～10000g:1t.
根据本申请的一些实施方式，所述复配抑制剂与煅烧处理后石墨原料的质量比为4000g～10000g：1t。According to some embodiments of the present application, the mass ratio of the compounded inhibitor to the calcined graphite raw material is 4000g-10000g:1t.
根据本申请的一些实施方式，所述复配抑制剂与煅烧处理后石墨原料的质量比为4000g～6000g：1t。According to some embodiments of the present application, the mass ratio of the compounded inhibitor to the calcined graphite raw material is 4000g-6000g:1t.
根据本申请的一些实施方式，所述捕收剂与煅烧处理后石墨原料的质量比为10g～500g：1t。According to some embodiments of the present application, the mass ratio of the collector to the calcined graphite raw material is 10g˜500g:1t.
根据本申请的一些实施方式，所述捕收剂与煅烧处理后石墨原料的质量比为100g～500g：1t。According to some embodiments of the present application, the mass ratio of the collector to the calcined graphite raw material is 100g˜500g:1t.
根据本申请的一些实施方式，所述捕收剂与煅烧处理后石墨原料的质量比为100g～200g：1t。According to some embodiments of the present application, the mass ratio of the collector to the calcined graphite raw material is 100g˜200g:1t.
根据本申请的一些实施方式，所述捕收剂与煅烧处理后石墨原料的质量比为150g～200g：1t。According to some embodiments of the present application, the mass ratio of the collector to the calcined graphite raw material is 150g-200g:1t.
根据本申请的一些实施方式，所述起泡剂与煅烧处理后石墨原料的质量比为10g～500g：1t。According to some embodiments of the present application, the mass ratio of the foaming agent to the calcined graphite raw material is 10g˜500g:1t.
根据本申请的一些实施方式，所述起泡剂与煅烧处理后石墨原料的质量比为80g～500g：1t。According to some embodiments of the present application, the mass ratio of the foaming agent to the calcined graphite raw material is 80g˜500g:1t.
根据本申请的一些实施方式，所述起泡剂与煅烧处理后石墨原料的质量比为80g～200g：1t。According to some embodiments of the present application, the mass ratio of the foaming agent to the calcined graphite raw material is 80g˜200g:1t.
根据本申请的一些实施方式，所述起泡剂与煅烧处理后石墨原料的质量比为80g～100g：1t。According to some embodiments of the present application, the mass ratio of the foaming agent to the calcined graphite raw material is 80g˜100g:1t.
根据本申请的一些实施方式，所述浮选的搅拌速度为1600r/min～1800r/min。According to some embodiments of the present application, the stirring speed of the flotation is 1600r/min˜1800r/min.
根据本申请的一些实施方式，所述浮选的充气量为160L/min～180L/min。According to some embodiments of the present application, the aeration rate of the flotation is 160L/min˜180L/min.
根据本申请的一些实施方式，所述浮选的时间为2min～10min。According to some embodiments of the present application, the time for the flotation is 2 minutes to 10 minutes.
根据本申请的一些实施方式，所述浮选的时间为4min～10min。According to some embodiments of the present application, the flotation time is 4 minutes to 10 minutes.
根据本申请的一些实施方式，所述浮选的时间为4min～6min。According to some embodiments of the present application, the flotation time is 4 minutes to 6 minutes.
根据本申请的一些实施方式，所述石墨精矿经过还原、磁化焙烧和磁选后，得纯化石墨。According to some embodiments of the present application, the graphite concentrate is subjected to reduction, magnetization roasting and magnetic separation to obtain purified graphite.
还原焙烧即磁化焙烧过程，镍钴氧化物经过还原后就具有磁性。Reduction roasting is magnetization roasting process, nickel cobalt oxide is magnetic after reduction.
根据本申请的一些实施方式，所述还原过程中的还原剂为活性炭。According to some embodiments of the present application, the reducing agent in the reduction process is activated carbon.
根据本申请的一些实施方式，将所述活性炭添加至所述石墨精矿中混合。According to some embodiments of the present application, the activated carbon is added to the graphite concentrate and mixed.
根据本申请的一些实施方式，所述混合的方式为磁力搅拌。According to some embodiments of the present application, the mixing method is magnetic stirring.
根据本申请的一些实施方式，所述活性炭与所述石墨精矿的质量比为1～4:50。According to some embodiments of the present application, the mass ratio of the activated carbon to the graphite concentrate is 1˜4:50.
质量比在此范围内能够保证石墨精矿中残余金属氧化物在磁化焙烧中充分还原，同时也不至于造成还原剂(活性炭等)浪费。The mass ratio within this range can ensure that the residual metal oxides in the graphite concentrate are fully reduced during the magnetization roasting, and at the same time, the reducing agent (activated carbon, etc.) will not be wasted.
根据本申请的一些实施方式，所述混合的时间为10min～30min。According to some embodiments of the present application, the mixing time is 10 minutes to 30 minutes.
根据本申请的一些实施方式，所述磁化焙烧的温度为500℃～800℃。According to some embodiments of the present application, the temperature of the magnetization calcination is 500°C-800°C.
磁化焙烧的温度在此温度区间能够保证镍钴氧化物充分还原，利于后续磁选和保证提纯石墨品质。The temperature of magnetization roasting in this temperature range can ensure the full reduction of nickel-cobalt oxide, which is beneficial to the subsequent magnetic separation and guarantees the quality of purified graphite.
根据本申请的一些实施方式，所述磁化焙烧的升温速率为5℃/min～10℃/min。According to some embodiments of the present application, the heating rate of the magnetization roasting is 5° C./min˜10° C./min.
根据本申请的一些实施方式，所述磁化焙烧的升温速率为10℃/min。According to some embodiments of the present application, the heating rate of the magnetization baking is 10° C./min.
根据本申请的一些实施方式，所述磁化焙烧的保温时间为1h～3h。According to some embodiments of the present application, the holding time of the magnetization roasting is 1 h to 3 h.
根据本申请的一些实施方式，所述磁选的磁场强度为3000Gs～5000Gs。According to some embodiments of the present application, the magnetic field strength of the magnetic separation is 3000Gs-5000Gs.
磁场强度控制在此范围内能够保证磁化物充分剔除，提升了提纯石墨品质。Controlling the magnetic field strength within this range can ensure the full removal of magnetized substances and improve the quality of purified graphite.
根据本申请的一些实施方式，所述磁选的磁场强度为3500Gs～5000Gs。According to some embodiments of the present application, the magnetic field strength of the magnetic separation is 3500Gs˜5000Gs.
本申请第五方面提供了上述复配抑制剂在废旧锂离子电池负极材料中石墨浮选中的应用。The fifth aspect of the present application provides the application of the compound inhibitor mentioned above in the flotation of graphite in the negative electrode material of the waste lithium ion battery.
本申请第六方面还提供了上述复配抑制剂在废旧锂离子电池负极材料回收中的应用。The sixth aspect of the present application also provides the application of the above-mentioned compound inhibitor in the recovery of the negative electrode material of the waste lithium ion battery.
本申请第七方面还提供了一种废旧锂离子电池负极材料中石墨的回收方法，包括以下步骤：The seventh aspect of the present application also provides a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
S1、将废旧锂离子电池负极材料煅烧后浮选，得到石墨精矿；S1. Calcining the waste lithium-ion battery anode material and then flotation to obtain graphite concentrate;
S2、将活性炭添加至步骤S1所得的石墨精矿中分散，固液分离，干燥后进行磁化焙烧-磁选。S2. Add activated carbon to the graphite concentrate obtained in step S1 to disperse, separate solid and liquid, and perform magnetization roasting-magnetic separation after drying.
根据本申请的一些实施方式，所述废旧锂离子电池负极材料经过筛分处理。According to some embodiments of the present application, the waste lithium ion battery negative electrode material has been sieved.
根据本申请的一些实施方式，所述筛分处理的筛网尺寸为100目～100目。According to some embodiments of the present application, the sieve size of the sieving treatment is 100 mesh to 100 mesh.
根据本申请的一些实施方式，所述煅烧的温度为200℃～550℃。According to some embodiments of the present application, the temperature of the calcination is 200°C to 550°C.
根据本申请的一些实施方式，所述煅烧的升温速率为5℃/min～10℃/min。According to some embodiments of the present application, the heating rate of the calcination is 5° C./min˜10° C./min.
根据本申请的一些实施方式，所述煅烧的时间为1h～2h。According to some embodiments of the present application, the calcination time is 1 h to 2 h.
根据本申请的一些实施方式，所述分散为磁力搅拌。According to some embodiments of the present application, the dispersion is magnetic stirring.
根据本申请的至少一种实施方式，具备如下有益效果：According to at least one embodiment of the present application, it has the following beneficial effects:
本申请实施例提供的废旧锂离子电池中石墨回收方法，将同时具有吸附性和还原性的活性炭加入到浮选矿浆中搅拌一段时间，能够有效的吸附石墨精矿中镍钴金属氧化物，同时活性炭又作为磁化焙烧中的还原剂，利用这个搅拌吸附步骤能够更高效精准的还原镍钴氧化物；从而提高磁化焙烧效率。In the method for recovering graphite from waste lithium-ion batteries provided in the embodiments of the present application, activated carbon having both adsorptive and reducing properties is added to the flotation pulp and stirred for a period of time, which can effectively adsorb nickel-cobalt metal oxides in graphite concentrate, and at the same time, activated carbon is used as a reducing agent in magnetization roasting. Using this stirring and adsorption step can reduce nickel-cobalt oxides more efficiently and accurately; thereby improving the efficiency of magnetization roasting.
在阅读并理解了附图和详细描述后，可以明白其他方面。Other aspects will be apparent to others upon reading and understanding the drawings and detailed description.
附图说明Description of drawings
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the description, and are used together with the embodiments of the application to explain the technical solutions herein, and do not constitute limitations to the technical solutions herein.
图1为本申请实施例1中的废旧石墨回收的工艺流程图。Fig. 1 is the process flow diagram of waste and old graphite recovery in the embodiment 1 of the present application.
图2为本申请实施例1浮选得到的石墨精矿的XRD图。Figure 2 is the XRD pattern of the graphite concentrate obtained by flotation in Example 1 of the present application.
图3为本申请实施例2浮选得到的石墨精矿的SEM图。Fig. 3 is the SEM image of the graphite concentrate obtained by flotation in Example 2 of the present application.
图4为本申请实施例3制得的提纯石墨的XRD图。Fig. 4 is the XRD pattern of the purified graphite prepared in Example 3 of the present application.
图5为本申请实施例3制得的提纯石墨的SEM图。Fig. 5 is the SEM image of the purified graphite prepared in Example 3 of the present application.
具体实施方式Detailed ways
以下将结合实施例对本申请的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本申请的目的、特征和效果。显然，所描述的实施例只是本申请的一部分实施例，而不是全部实施例，基于本申请的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本申请保护的范围。The idea and technical effects of the present application will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present application. Apparently, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative efforts all belong to the scope of protection of the present application.
本申请的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。In the description of the present application, descriptions referring to the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific examples", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
下面详细描述本申请的具体实施例。Specific embodiments of the present application are described in detail below.
本申请实施例方式中原料和提纯产品中石墨采用碳硫仪测定，金属含量采用ICP测试。Graphite in the raw materials and purified products in the embodiments of the present application is measured by a carbon-sulfur meter, and the metal content is tested by ICP.
实施例1Example 1
本实施例为一种废旧锂离子电池负极材料中石墨的回收方法，如图1所示，包括以下步骤：This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, as shown in Figure 1, comprising the following steps:
S1、将含有石墨的废旧锂离子电池负极材料(原料来自湖南邦普循环科技有限公司)过100目筛筛分，得石墨物料。S1. Sieve the graphite-containing waste lithium-ion battery anode material (raw material from Hunan Bangpu Recycling Technology Co., Ltd.) through a 100-mesh sieve to obtain graphite material.
S2、将步骤S1中石墨物料(石墨的质量百分数为40％左右，镍+钴元素的质量百分数在35％左右)进行焙烧处理，以10℃/min升温速率升温至200℃，然后保温1h，得焙烧后石墨。S2, the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
S3、将步骤S2中焙烧后的石墨以固液比70g/100mL进行浮选。S3. Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
其中，捕收剂为正十二烷，用量(即捕收剂与焙烧后石墨的质量比)为200g/t；起泡剂为甲基异丁基甲烷，用量(即起泡剂与焙烧后石墨的质量比)为100g/t，复配抑制剂用量(即复配抑制剂与焙烧后石墨的质量比)为4000g/t(亚硫酸钠：石灰(国药集团化学试剂有限公司，分析纯)：(次氯酸钙+次氯酸钠)的质量比为1：20：(20+20))；浮选机的转速1800r/min，充气量160L/h，浮选时间4min；得到石墨精矿和尾渣。Wherein, the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the calcined graphite) is 200g/t; the foaming agent is methyl isobutyl methane, the consumption (i.e. the mass ratio of the foaming agent to the calcined graphite) is 100g/t, and the compound inhibitor dosage (i.e. the mass ratio of the compound inhibitor to the calcined graphite) is 4000g/t (sodium sulfite: lime (Sinopharm Chemical Reagent Co., Ltd., analytically pure): (calcium hypochlorite+time The mass ratio of sodium chlorate) is 1:20:(20+20)); the rotating speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
本步骤得到的浮选后石墨精矿中碳含量在90.6％，镍+钴含量在2.4％。The carbon content in the graphite concentrate after flotation obtained in this step is 90.6%, and the nickel+cobalt content is 2.4%.
S4、将活性炭(天津市登峰化学试剂厂，分析纯)添加至步骤S3得到的石墨精矿(石墨精矿和活性炭的比例为100:3)，置于磁力搅拌器上搅拌15min，然后过滤烘干，得到烘干石墨精矿。将烘干石墨精矿置于密封容器，在马弗炉中以10℃/min升温至700℃，保温1.5h；得焙烧物料。S4, activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 100:3), placed on a magnetic stirrer and stirred for 15min, then filtered and dried to obtain dried graphite concentrate. Put the dried graphite concentrate in a sealed container, raise the temperature to 700°C at 10°C/min in a muffle furnace, and keep it warm for 1.5h; the roasted material is obtained.
S5、将步骤S4得到的焙烧物料在磁选管中进行磁选，磁场强度3500Gs，得到提纯石墨。本实施例中得到的提纯石墨中碳质量分数为96.7％，镍元素和钴元素质量分数之和<0.3％。S5. The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite. The mass fraction of carbon in the purified graphite obtained in this embodiment is 96.7%, and the sum of the mass fractions of nickel element and cobalt element is <0.3%.
本实施例步骤S3中制得的石墨精矿的XRD见图2；从图2中得知，本实施例制得的石墨精矿纯度较高。The XRD of the graphite concentrate prepared in step S3 of this embodiment is shown in Figure 2; it can be known from Figure 2 that the graphite concentrate prepared in this embodiment has a higher purity.
实施例2Example 2
本实施例为一种废旧锂离子电池负极材料中石墨的回收方法，包括以下步骤：This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
S1、将含有石墨的废旧锂离子电池负极材料(原料来自湖南邦普循环科技有限公司)过100目筛筛分，得石墨物料。S1. Sieve the graphite-containing waste lithium-ion battery anode material (raw material from Hunan Bangpu Recycling Technology Co., Ltd.) through a 100-mesh sieve to obtain graphite material.
S2、将步骤S1中石墨物料(石墨的质量百分数为50％左右，镍+钴元素的质量百分数在30％左右)进行焙烧处理，以10℃/min升温速率升温至200℃，然后保温1h，得焙烧后石墨。S2, the graphite material in step S1 (the mass percentage of graphite is about 50%, and the mass percentage of nickel+cobalt element is about 30%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
S3、将步骤S2中焙烧后的石墨以固液比30g/100mL进行浮选。S3. Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 30g/100mL.
其中，捕收剂为正十二烷，用量(即捕收剂与焙烧后石墨的质量比)为150g/t；起泡剂为甲基异丁基甲烷，用量(即起泡剂与焙烧后石墨的质量比)为80g/t，复配抑制剂用量(即复配抑制剂与焙烧后石墨的质量比)为3000g/t(亚硫酸钠：石灰(国药集团化学试剂有限公司，分析纯)：次氯酸钙的质量比为1：25：25)；浮选机的转速1800r/min，充气量160L/h，浮选时间4min；得到石墨精矿和尾渣。Wherein, the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the roasted graphite) is 150g/t; the foaming agent is methyl isobutyl methane, the consumption (i.e. the mass ratio of the foamer to the roasted graphite) is 80g/t, and the compound inhibitor consumption (i.e. the mass ratio of the compound inhibitor to the roasted graphite) is 3000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of calcium hypochlorite is 1:25:25); the rotation speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
本步骤得到的浮选后石墨精矿中碳含量在93.5％，镍+钴含量在2.2％。The carbon content in the graphite concentrate after flotation obtained in this step is 93.5%, and the nickel+cobalt content is 2.2%.
S4、将活性炭(天津市登峰化学试剂厂，分析纯)添加至步骤S3得到的石墨精矿(石墨精矿和活性炭的比例为20:1)，置于磁力搅拌器上搅拌10min，然后过滤烘干，得到烘干石墨精矿。将烘干石墨精矿置于密封容器，在马弗炉中以10℃/min升温至650℃，保温2h；得焙烧物料。S4, activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 20:1), placed on a magnetic stirrer and stirred for 10min, then filtered and dried to obtain dried graphite concentrate. Place the dried graphite concentrate in a sealed container, raise the temperature to 650°C at 10°C/min in a muffle furnace, and keep it warm for 2 hours; the roasted material is obtained.
S5、将步骤S4得到的焙烧物料在磁选管中进行磁选，磁场强度3500Gs，得到提纯石墨。本实施例中得到的提纯石墨中碳质量分数为96.9％，镍元素和钴元素质量分数之和<0.2％。S5. The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite. The mass fraction of carbon in the purified graphite obtained in this example is 96.9%, and the sum of the mass fractions of nickel and cobalt is <0.2%.
本实施例S3制得的石墨精矿的SEM图见图3，从图3中得知，本实施例制得的石墨精矿均匀性好。The SEM image of the graphite concentrate prepared in Example S3 is shown in FIG. 3 , and it can be known from FIG. 3 that the graphite concentrate prepared in this example has good uniformity.
实施例3Example 3
本实施例为一种废旧锂离子电池负极材料中石墨的回收方法，包括以下步骤：This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
S1、将含有石墨的废旧锂离子电池负极材料(原料来自湖南邦普循环科技有限公司)过100目筛筛分，得石墨物料。S1. Sieve the graphite-containing waste lithium-ion battery anode material (raw material from Hunan Bangpu Recycling Technology Co., Ltd.) through a 100-mesh sieve to obtain graphite material.
S2、将步骤S1中石墨物料(石墨的质量百分数为30％左右，镍+钴元素的质量百分数在50％左右)进行焙烧处理，以10℃/min升温速率升温至300℃，然后保温1.5h，得焙烧后石墨。S2, the graphite material in step S1 (the mass percentage of graphite is about 30%, and the mass percentage of nickel+cobalt element is about 50%) is roasted, and the temperature is raised to 300 ° C at a heating rate of 10 ° C / min, and then kept for 1.5 hours to obtain graphite after roasting.
S3、将步骤S2中焙烧后的石墨以固液比100g/100mL进行浮选。S3. Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 100g/100mL.
其中，捕收剂为正十二烷，用量(即捕收剂与焙烧后石墨的质量比)为100g/t；起泡剂为甲基异丁基甲烷，用量(即起泡剂与焙烧后石墨的质量比)为80g/t，复配抑制剂用量(即复配抑制剂与焙烧后石墨的质量比)为6000g/t(亚硫酸钠：石灰(国药集团化学试剂有限公司，分析纯)：次氯酸钠的质量比为1：100：50)；浮选机的转速1600r/min，充气量180L/h，浮选时间4min；得到石墨精矿和尾渣。Wherein, the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the roasted graphite) is 100g/t; the foaming agent is methyl isobutyl methane, and the consumption (i.e. the mass ratio of the foaming agent to the roasted graphite) is 80g/t, and the compound inhibitor consumption (i.e. the mass ratio of the compound inhibitor to the roasted graphite) is 6000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of sodium hypochlorite is 1:100:50); the rotation speed of the flotation machine is 1600r/min, the gas filling rate is 180L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
本步骤得到的浮选后石墨精矿中碳含量在88.3％，镍+钴含量在6.5％。The carbon content in the graphite concentrate after flotation obtained in this step is 88.3%, and the nickel+cobalt content is 6.5%.
S4、将活性炭(天津市登峰化学试剂厂，分析纯)添加至步骤S3得到的石墨精矿(石墨精矿和活性炭的比例为25:2)，置于磁力搅拌器上搅拌30min，然后过滤烘干，得到烘干石墨精矿。将烘干石墨精矿置于密封容器，在马弗炉中以10℃/min升温至750℃，保温2h；得焙烧物料。S4, activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) is added to the graphite concentrate obtained in step S3 (the ratio of graphite concentrate and activated carbon is 25:2), placed on a magnetic stirrer and stirred for 30min, then filtered and dried to obtain dried graphite concentrate. Put the dried graphite concentrate in a sealed container, raise the temperature to 750°C at 10°C/min in a muffle furnace, and keep it warm for 2 hours; the roasted material is obtained.
S5、将步骤S4得到的焙烧物料在磁选管中进行磁选，磁场强度3500Gs，得到提纯石墨。本实施例中得到的提纯石墨中碳质量分数为92.5％，镍元素和钴元素质量分数之和<0.5％。S5. The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite. The mass fraction of carbon in the purified graphite obtained in this embodiment is 92.5%, and the sum of the mass fractions of nickel element and cobalt element is <0.5%.
本实施例步骤制得的提纯石墨的XRD和SEM图见图4和图5，从图4和图5中得知，本实施例制得的提纯石墨纯度高且颗粒均匀。The XRD and SEM diagrams of the purified graphite prepared in the steps of this embodiment are shown in Fig. 4 and Fig. 5, and it can be known from Fig. 4 and Fig. 5 that the purified graphite prepared in this embodiment has high purity and uniform particles.
实施例4Example 4
本实施例为一种废旧锂离子电池负极材料中石墨的回收方法，包括以下步骤：This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
S1、将含有石墨的废旧锂离子电池负极材料(原料来自湖南邦普循环科技有限公司)过100目筛筛分，得石墨物料。S1. Sieve the graphite-containing waste lithium-ion battery anode material (raw material from Hunan Bangpu Recycling Technology Co., Ltd.) through a 100-mesh sieve to obtain graphite material.
S2、将步骤S1中石墨物料(石墨的质量百分数为40％左右，镍+钴元素的质量百分数在35％左右)进行焙烧处理，以10℃/min升温速率升温至200℃，然后保温1h，得焙烧后石墨。S2, the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
S3、将步骤S2中焙烧后的石墨以固液比70g/100mL进行浮选。S3. Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
其中，捕收剂为正十二烷，用量(即捕收剂与焙烧后石墨的质量比)为200g/t；起泡剂为甲基异丁基甲烷，用量(即起泡剂与焙烧后石墨的质量比)为100g/t，浮选机的转速1800r/min，充气量160L/h，浮选时间4min；得到石墨精矿和尾渣。Wherein, the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the roasted graphite) is 200g/t; the foaming agent is methyl isobutyl methane, and the consumption (i.e. the mass ratio of the foamer to the roasted graphite) is 100g/t, the rotating speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
本步骤得到的浮选后石墨精矿中碳含量在84.3％，镍+钴含量在8.1％。The carbon content in the graphite concentrate after flotation obtained in this step is 84.3%, and the nickel+cobalt content is 8.1%.
S4、将步骤S3得到的石墨精矿烘干后加入活性炭(石墨精矿和活性炭的比例为100:3)，物理混匀得到混合料。将混合料置于密封容器，在马弗炉中以 10℃/min升温至700℃，保温1.5h；得焙烧物料。S4. After drying the graphite concentrate obtained in step S3, add activated carbon (the ratio of graphite concentrate to activated carbon is 100:3), and physically mix to obtain a mixture. Put the mixture in a sealed container, raise the temperature to 700°C at 10°C/min in a muffle furnace, and keep it warm for 1.5h; the roasted material is obtained.
S5、将步骤S4得到的焙烧物料在磁选管中进行磁选，磁场强度3500Gs，得到提纯石墨。本实施例中得到的提纯石墨中碳质量分数为97％，镍元素和钴元素质量分数之和为6％。S5. The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite. The mass fraction of carbon in the purified graphite obtained in this embodiment is 97%, and the sum of the mass fractions of nickel and cobalt is 6%.
实施例5Example 5
本实施例为一种废旧锂离子电池负极材料中石墨的回收方法，包括以下步骤：This embodiment is a method for recovering graphite in a waste lithium-ion battery negative electrode material, comprising the following steps:
S1、将含有石墨的废旧锂离子电池负极材料(原料来自湖南邦普循环有限公司)过100目筛筛分，得石墨物料。S1. Sieve the waste lithium-ion battery negative electrode material containing graphite (raw material from Hunan Bangpu Recycling Co., Ltd.) through a 100-mesh sieve to obtain graphite material.
S2、将步骤S1中石墨物料(石墨的质量百分数为40％左右，镍+钴元素的质量百分数在35％左右)进行焙烧处理，以10℃/min升温速率升温至200℃，然后保温1h，得焙烧后石墨。S2, the graphite material in step S1 (the mass percentage of graphite is about 40%, and the mass percentage of nickel+cobalt element is about 35%) is subjected to roasting treatment, and the temperature is raised to 200 ° C at a heating rate of 10 ° C / min, and then kept for 1 h to obtain graphite after roasting.
S3、将步骤S2中焙烧后的石墨以固液比70g/100mL进行浮选。S3. Flotating the graphite calcined in step S2 with a solid-to-liquid ratio of 70g/100mL.
其中，捕收剂为正十二烷，用量(即捕收剂与焙烧后石墨的质量比)为200g/t；起泡剂为甲基异丁基甲烷，用量(即起泡剂与焙烧后石墨的质量比)为100g/t，复配抑制剂用量(即复配抑制剂与焙烧后石墨的质量比)为4000g/t(亚硫酸钠：石灰(国药集团化学试剂有限公司，分析纯)：次氯酸钙的质量比为1：20：40)；浮选机的转速1800r/min，充气量160L/h，浮选时间4min；得到石墨精矿和尾渣。Wherein, the collector is n-dodecane, and the consumption (i.e. the mass ratio of the collector to the calcined graphite) is 200g/t; the foaming agent is methyl isobutyl methane, the consumption (i.e. the mass ratio of the foaming agent to the calcined graphite) is 100g/t, and the compound inhibitor dosage (i.e. the mass ratio of the compound inhibitor to the calcined graphite) is 4000g/t (sodium sulfite: lime (Sinopharm Group Chemical Reagent Co., Ltd., analytically pure): the mass ratio of calcium hypochlorite 1:20:40); the rotational speed of the flotation machine is 1800r/min, the gas filling rate is 160L/h, and the flotation time is 4min; graphite concentrate and tailings are obtained.
本步骤得到的浮选后石墨精矿中碳含量在89.5％，镍+钴含量在3.2％。The carbon content in the graphite concentrate after flotation obtained in this step is 89.5%, and the nickel+cobalt content is 3.2%.
S4、将步骤S3得到的石墨精矿烘干，得到烘干石墨精矿。将活性炭(天津市登峰化学试剂厂，分析纯)添加至烘干石墨精矿中物理混匀得到混合料(烘干石墨精矿与活性炭的比例为100:3)；将混合料置于密封容器，在马弗炉中以10℃/min升温至700℃，保温1.5h；得焙烧物料。S4. Dry the graphite concentrate obtained in step S3 to obtain the dried graphite concentrate. Activated carbon (Tianjin Dengfeng Chemical Reagent Factory, analytically pure) was added to the dried graphite concentrate and mixed physically to obtain a mixture (the ratio of dried graphite concentrate to activated carbon was 100:3); the mixture was placed in a sealed container, and the temperature was raised to 700°C in a muffle furnace at 10°C/min, and kept for 1.5h; the roasted material was obtained.
S5、将步骤S4得到的焙烧物料在磁选管中进行磁选，磁场强度3500Gs，得到提纯石墨。本实施例中得到的提纯石墨中碳质量分数为95％，镍元素和钴元素质量分数之和为1％。S5. The roasted material obtained in step S4 is subjected to magnetic separation in a magnetic separation tube with a magnetic field strength of 3500Gs to obtain purified graphite. The mass fraction of carbon in the purified graphite obtained in this embodiment is 95%, and the sum of the mass fractions of nickel element and cobalt element is 1%.
本申请实施例4与实施例1的差别在于：实施例4为未加复配抑制剂同时磁化焙烧中还原剂活性炭采用物理混匀方式添加；The difference between Example 4 of the present application and Example 1 is that: Example 4 is that the reductant activated carbon is added in a physical mixing manner in the magnetization roasting without compounding inhibitor;
本申请实施例5与实施例1的差别在于：实施例5在磁化焙烧过程中采用物理混匀方式加入还原剂活性炭；The difference between Example 5 and Example 1 of the present application lies in that in Example 5, the reductant activated carbon is added by physical mixing during the magnetization roasting process;
通过本申请实施例1和实施例4～5对比可知，本申请的复配抑制剂对废旧锂电池中石墨浮选过程中镍元素和钴元素有较好的抑制作用；本申请提供的石墨回收工艺，在浮选石墨精矿磁选前，先加入活性炭吸附一段时间，提高了磁化焙烧效率，进而改善了磁选效果，进一步降低提纯石墨中镍钴含量。Through the comparison of Example 1 of the present application with Examples 4-5, it can be seen that the compound inhibitor of the present application has a good inhibitory effect on nickel and cobalt elements in the graphite flotation process in waste lithium batteries; the graphite recovery process provided by the application, before the magnetic separation of flotation graphite concentrate, first adds activated carbon for adsorption for a period of time, which improves the magnetization roasting efficiency, and then improves the magnetic separation effect, and further reduces the content of nickel and cobalt in the purified graphite.
在石墨浮选过程中，本申请的复配抑制剂能够有效抑制镍钴等元素进入石墨精矿中，其作用机理为：复配抑制剂在镍钴锰颗粒表面形成亲水性的镍钴氢氧化物，从而达到抑制效果；另一方面结合该复配抑制剂提出的石墨回收工艺中，在磁化焙烧前将活性炭(吸附剂&还原剂)加入浮选石墨精矿矿浆中吸附一段时间能够更高效和精准的还原镍钴氧化物，从而进一步降低提纯石墨中金属含量。In the graphite flotation process, the compound inhibitor of the present application can effectively inhibit elements such as nickel and cobalt from entering the graphite concentrate. The mechanism of action is: the compound inhibitor forms hydrophilic nickel-cobalt hydroxide on the surface of the nickel-cobalt-manganese particles, thereby achieving the inhibitory effect; on the other hand, in the graphite recovery process proposed in combination with the compound inhibitor, adding activated carbon (adsorbent & reducing agent) to the flotation graphite concentrate slurry for adsorption for a period of time before magnetization roasting can more efficiently and accurately reduce the nickel-cobalt oxide, thereby further reducing the metal content in the purified graphite.
综上所述，本申请的废旧锂离子电池中石墨回收方法，将同时具有吸附性和还原性的活性炭加入到浮选矿浆中搅拌一段时间，能够有效的吸附石墨精矿中镍钴金属氧化物，同时活性炭又作为磁化焙烧中的还原剂，利用这个搅拌吸附步骤能够更高效精准的还原镍钴氧化物；从而提高磁化焙烧效率。To sum up, the method for recovering graphite from waste lithium-ion batteries of the present application involves adding activated carbon with both adsorptive and reducing properties into the flotation pulp and stirring for a period of time, which can effectively adsorb nickel-cobalt metal oxides in graphite concentrates. At the same time, activated carbon is also used as a reducing agent in magnetization roasting. Using this stirring and adsorption step can reduce nickel-cobalt oxides more efficiently and accurately; thereby improving the efficiency of magnetization roasting.
上面结合具体实施方式对本申请实施例作了详细说明，但是本申请不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本申请宗旨的前提下作出各种变化。此外，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。The embodiments of the present application have been described in detail above in conjunction with specific implementation methods, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge of those of ordinary skill in the art without departing from the gist of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other under the condition of no conflict.

Claims (14)

  1. 一种复配抑制剂，其中，所述复配抑制剂包括以下制备原料：亚硫酸盐、碱和次氯酸盐。A compound inhibitor, wherein, the compound inhibitor includes the following preparation raw materials: sulfite, alkali and hypochlorite.
  2. 根据权利要求1所述的复配抑制剂，其中，所述亚硫酸盐、所述碱和所述次氯酸盐的质量比为1:1～100:1～50。The compound inhibitor according to claim 1, wherein the mass ratio of the sulfite, the alkali and the hypochlorite is 1:1-100:1-50.
  3. 根据权利要求1所述的复配抑制剂，其中，所述碱包括氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。The compound inhibitor according to claim 1, wherein the alkali comprises at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
  4. 一种制备如权利要求1至3任一项所述的复配抑制剂的方法，其包括：将所述亚硫酸盐、所述碱和所述次氯酸盐混合，即得。A method for preparing the compound inhibitor according to any one of claims 1 to 3, which comprises: mixing the sulfite, the alkali and the hypochlorite to obtain.
  5. 一种石墨浮选的方法，其包括以下步骤：A method for graphite flotation, comprising the following steps:
    将权利要求1至3任一项所述的复配抑制剂、捕收剂和起泡剂依次添加至石墨原料中进行浮选，得到石墨精矿。The composite depressant, collector and foaming agent described in any one of claims 1 to 3 are sequentially added to graphite raw materials for flotation to obtain graphite concentrate.
  6. 根据权利要求5所述的石墨浮选的方法，其中，所述捕收剂包括烃类化合物。The method for graphite flotation according to claim 5, wherein the collector comprises hydrocarbon compounds.
  7. 根据权利要求5所述的石墨浮选的方法，其中，所述起泡剂包括醇类起泡剂。The method for graphite flotation according to claim 5, wherein the foaming agent comprises an alcoholic foaming agent.
  8. 根据权利要求5所述的石墨浮选的方法，其中，还包括对所述石墨精矿进行后处理。The method for graphite flotation according to claim 5, further comprising post-processing the graphite concentrate.
  9. 根据权利要求8所述的石墨浮选的方法，其中，所述后处理包括还原、磁化焙烧和磁选。The method for graphite flotation according to claim 8, wherein said post-treatment comprises reduction, magnetization roasting and magnetic separation.
  10. 根据权利要求9所述的石墨浮选的方法，其中，所述磁化焙烧的温度为500℃～800℃。The graphite flotation method according to claim 9, wherein the temperature of the magnetization roasting is 500°C-800°C.
  11. 根据权利要求9所述的石墨浮选的方法，其中，所述磁选的磁场强度为3000Gs～5000Gs。The graphite flotation method according to claim 9, wherein the magnetic field strength of the magnetic separation is 3000Gs-5000Gs.
  12. 根据权利要求9所述的石墨浮选的方法，其中，所述还原过程中的还原剂为活性炭。The method for graphite flotation according to claim 9, wherein the reducing agent in the reduction process is activated carbon.
  13. 根据权利要求12所述的石墨浮选的方法，其中，所述活性炭与所述石墨精矿的质量比为1～4:50。The method for graphite flotation according to claim 12, wherein the mass ratio of the activated carbon to the graphite concentrate is 1-4:50.
  14. 一种如权利要求1至3任一项所述的复配抑制剂在废旧锂离子电池负极材料回收中的应用。A kind of compound inhibitor as described in any one of claim 1 to 3 is used in the application of waste lithium ion battery negative electrode material recovery.
PCT/CN2022/138529 2022-01-24 2022-12-13 Compound inhibitor, preparation method therefor, and use thereof WO2023138261A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210077140.3A CN114515651A (en) 2022-01-24 2022-01-24 Compound inhibitor and preparation method and application thereof
CN202210077140.3 2022-01-24

Publications (1)

Publication Number Publication Date
WO2023138261A1 true WO2023138261A1 (en) 2023-07-27

Family

ID=81596233

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/138529 WO2023138261A1 (en) 2022-01-24 2022-12-13 Compound inhibitor, preparation method therefor, and use thereof

Country Status (2)

Country Link
CN (1) CN114515651A (en)
WO (1) WO2023138261A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114515651A (en) * 2022-01-24 2022-05-20 宜昌邦普循环科技有限公司 Compound inhibitor and preparation method and application thereof
CN117096485A (en) * 2023-08-11 2023-11-21 中南大学 Method for selectively separating and regenerating graphite from waste battery black powder

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443071A (en) * 2011-11-16 2012-05-09 广西大学 Composite modified starch as hematite reverse flotation inhibitor and preparation method thereof
CN103894276A (en) * 2014-03-03 2014-07-02 武平紫金矿业有限公司 Grinding separation technology for silver-containing polymetallic ore
DE102014014894A1 (en) * 2014-10-13 2016-04-14 Adensis Gmbh Process for the recovery of active material from the cathodes of lithium-ion batteries
CN106540816A (en) * 2016-11-08 2017-03-29 长春黄金研究院 Suppress the flotation composite inhibitor and its using method of pyrite under a kind of low alkalinity
CN108400400A (en) * 2018-02-07 2018-08-14 中南大学 A kind of reuse method of applying waste lithium ionic power battery
CN111484008A (en) * 2020-04-16 2020-08-04 中国恩菲工程技术有限公司 Composite regulator for graphite flotation in waste lithium ion batteries and recovery method of graphite in waste lithium ion batteries
CN111495608A (en) * 2020-05-14 2020-08-07 沈阳有色金属研究院有限公司 Flotation process for efficiently recovering lead, zinc and sulfur in multi-metal sulfide ore
CN112670614A (en) * 2020-12-29 2021-04-16 广东省科学院资源综合利用研究所 Physical sorting method for positive and negative electrode materials of waste lithium iron phosphate batteries
CN114515651A (en) * 2022-01-24 2022-05-20 宜昌邦普循环科技有限公司 Compound inhibitor and preparation method and application thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1062819A (en) * 1976-12-07 1979-09-18 Stephen J. Thorndyke Flotation separation of copper and nickel sulfides
US4120697A (en) * 1977-04-15 1978-10-17 Amax Inc. Segregation-separation of copper from nickel in copper-nickel sulfide concentrates
CN102218376B (en) * 2011-01-27 2013-01-30 湖南有色金属研究院 Method for high-efficiency floatation and separation of molybdenum and nickel and recovery of molybdenum and nickel from high carbon nickel-molybdenum ore to obtain molybdenum concentrate and nickel-molybdenum bulk concentrate
CN102794234A (en) * 2012-09-12 2012-11-28 长春黄金研究院 Compound inhibiting agent capable of effectively separating copper and sulfur at low-alkalinity condition
CN103072975B (en) * 2012-12-28 2014-11-12 中南大学 Low-grade aphanitic graphite dressing and purifying method
CN104069952B (en) * 2014-06-06 2016-08-31 武汉理工大学 The inhibitor of gangue mineral and application thereof in a kind of graphite ore
CN104475261A (en) * 2014-12-11 2015-04-01 中国科学院过程工程研究所 Method for recovering low-grade copper-zinc mineral from cyanidation tailings
CN105381868B (en) * 2015-12-22 2017-12-05 中国地质科学院矿产综合利用研究所 Physical beneficiation phosphorus reduction method for skarn type high-phosphorus molybdenum ore
CN107262263B (en) * 2017-05-27 2019-10-25 中国矿业大学 A method of separating cobalt acid lithium and graphite from waste lithium ion electrode material
CN108672092A (en) * 2018-05-16 2018-10-19 东北大学 The process for effectively purifying of the low grade shepardite of high-silicon high calcium high ferro
CN109713394B (en) * 2019-01-18 2021-08-06 中国矿业大学 Method for separating lithium cobaltate and graphite in waste electrode material
CN109811125B (en) * 2019-01-21 2020-11-10 湖南邦普循环科技有限公司 Method for recovering ferro-phosphorus alloy and lithium compound from waste lithium iron phosphate material
CN111129635A (en) * 2019-12-17 2020-05-08 湖南凯地众能科技有限公司 Method and device for separating anode material and cathode material of waste lithium battery
CN111233019A (en) * 2020-04-11 2020-06-05 兰州理工大学 Environment-friendly treatment method for waste cathode and aluminum ash of aluminum electrolysis cell
CN112551597B (en) * 2020-12-09 2022-04-15 中南大学 Comprehensive recycling method for anode and cathode of waste NCM (negative polarity-positive) ternary battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443071A (en) * 2011-11-16 2012-05-09 广西大学 Composite modified starch as hematite reverse flotation inhibitor and preparation method thereof
CN103894276A (en) * 2014-03-03 2014-07-02 武平紫金矿业有限公司 Grinding separation technology for silver-containing polymetallic ore
DE102014014894A1 (en) * 2014-10-13 2016-04-14 Adensis Gmbh Process for the recovery of active material from the cathodes of lithium-ion batteries
CN106540816A (en) * 2016-11-08 2017-03-29 长春黄金研究院 Suppress the flotation composite inhibitor and its using method of pyrite under a kind of low alkalinity
CN108400400A (en) * 2018-02-07 2018-08-14 中南大学 A kind of reuse method of applying waste lithium ionic power battery
CN111484008A (en) * 2020-04-16 2020-08-04 中国恩菲工程技术有限公司 Composite regulator for graphite flotation in waste lithium ion batteries and recovery method of graphite in waste lithium ion batteries
CN111495608A (en) * 2020-05-14 2020-08-07 沈阳有色金属研究院有限公司 Flotation process for efficiently recovering lead, zinc and sulfur in multi-metal sulfide ore
CN112670614A (en) * 2020-12-29 2021-04-16 广东省科学院资源综合利用研究所 Physical sorting method for positive and negative electrode materials of waste lithium iron phosphate batteries
CN114515651A (en) * 2022-01-24 2022-05-20 宜昌邦普循环科技有限公司 Compound inhibitor and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114515651A (en) * 2022-01-24 2022-05-20 宜昌邦普循环科技有限公司 Compound inhibitor and preparation method and application thereof
CN117096485A (en) * 2023-08-11 2023-11-21 中南大学 Method for selectively separating and regenerating graphite from waste battery black powder

Also Published As

Publication number Publication date
CN114515651A (en) 2022-05-20

Similar Documents

Publication Publication Date Title
WO2022193781A1 (en) Regeneration method for waste ternary positive electrode material, and use thereof
CN110224123B (en) High-voltage lithium cobalt oxide cathode material and preparation method and application thereof
CN113072052B (en) Waste lithium iron phosphate lithium supplement repair method and application
CN112808226A (en) Aluminum-based lithium ion sieve and preparation method and application thereof
CN110010990B (en) Method for preparing nickel-cobalt-manganese ternary material with aluminum oxide coating layer by taking retired lithium ion battery as raw material
WO2023138261A1 (en) Compound inhibitor, preparation method therefor, and use thereof
CN109182732A (en) Waste and old ternary lithium battery stagewise recovery method
CN114130375B (en) Preparation method of membranous lithium ion sieve adsorbent
CN111943285A (en) Nano lithium-rich manganese-based positive electrode material, precursor and base material thereof, and preparation method
CN113293312B (en) Preparation method of composite porous electrode material for lithium extraction
WO2023024593A1 (en) Method for recovering mixed waste of lithium nickel cobalt manganate and lithium iron phosphate
CN113764765A (en) Recovery method and recovery equipment for positive active material of lithium ion battery
CN109686967A (en) A kind of lithium-rich manganese-based anode material and preparation method thereof
CN101777639A (en) Method for preparing lithium battery anode material precursor
CN104437445B (en) The chromic method adsorbed by desorbing gas anion lamellar compound
WO2023160016A1 (en) Method for preparing ternary precursor from microbubbles by pre-oxidation and application of ternary precursor
WO2023207247A1 (en) Porous spherical cobalt oxide particle and preparation method therefor
CN112316928A (en) Cellulose lithium ion sieve composite membrane and preparation method and application thereof
CN116555564A (en) Electrochemical lithium extraction electrode and electrochemical lithium extraction method
WO2024036906A1 (en) Lithium-ion battery positive electrode material and preparation method therefor
CN115745021A (en) Method for removing residual lithium in high-nickel ternary cathode material
CN113943021A (en) Regenerated lithium cobaltate and repairing method and application thereof
WO2024021276A1 (en) Coating method for lithium nickel cobalt manganese oxide positive electrode material
CN112125351A (en) Ternary precursor and preparation method thereof, ternary material and preparation method thereof, and lithium ion battery
CN115624958B (en) Film for extracting lithium from salt lake brine, preparation method thereof and lithium extraction method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22921685

Country of ref document: EP

Kind code of ref document: A1