WO2024207141A1 - 一种全链条一体化处理废旧电池定向循环过程中废渣的方法 - Google Patents

一种全链条一体化处理废旧电池定向循环过程中废渣的方法 Download PDF

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WO2024207141A1
WO2024207141A1 PCT/CN2023/085919 CN2023085919W WO2024207141A1 WO 2024207141 A1 WO2024207141 A1 WO 2024207141A1 CN 2023085919 W CN2023085919 W CN 2023085919W WO 2024207141 A1 WO2024207141 A1 WO 2024207141A1
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Prior art keywords
roasting
feature
nickel
iron
solid waste
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PCT/CN2023/085919
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English (en)
French (fr)
Inventor
李兴昌
郑宇�
刘勇奇
巩勤学
李长东
程青云
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to PCT/CN2023/085919 priority Critical patent/WO2024207141A1/zh
Priority to CN202380008586.3A priority patent/CN116710580A/zh
Publication of WO2024207141A1 publication Critical patent/WO2024207141A1/zh
Anticipated expiration legal-status Critical
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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 present application relates to the field of battery technology, and in particular to a method for processing waste residues in a directional recycling process of waste batteries in an integrated manner throughout the entire chain.
  • Waste lithium-ion batteries have the dual attributes of hazardous waste and available resources. Using different recycling processes to achieve efficient recycling and reuse of waste lithium-ion batteries is of great significance to environmental protection and resource regeneration.
  • high-nickel ternary materials the demand for nickel has increased year by year, but nickel resources are currently in short supply. Recycling valuable metals from waste batteries, such as nickel and iron resources, and realizing the directional circulation of such resources, re-entering the battery end, and building a "full-chain integrated industrial park" has become the primary choice for most lithium battery positive electrode material manufacturers to reduce costs and increase efficiency.
  • the sodium ferroaluminate method for iron removal is widely used in industry. It is mainly because sodium ferroaluminate is precipitated in a crystalline state, has good precipitation performance, coarse slag particles, and relatively good filtering performance, and there are few metals entrained in the slag at the same time, which can better solve the sulfate balance problem, and the operating conditions are simple, and it is easy to achieve (normal pressure and medium temperature). At the same time, when using the sodium ferroaluminate method for iron removal, aluminum ions will also appear hydrolysis precipitation and be removed therewith in the process of adjusting pH.
  • nickel-containing industrial solid waste In addition to iron-aluminum slag, a large amount of nickel-containing industrial solid waste will inevitably be generated during the wet recycling process of waste batteries, such as nickel-containing waste treatment sludge, nickel-cobalt slag and other industrial solid wastes. These solid wastes contain a large amount of heavy metal elements. If they are directly landfilled without treatment, it will not only cause a waste of nickel resources, but these industrial solid wastes will also dissolve nickel heavy metal elements and enter the soil and water, causing serious pollution to the ecological environment.
  • the purpose of this application includes providing a method for treating waste slag in the directional recycling process of waste batteries with a full-chain integration, which can effectively reuse the iron-aluminum slag and nickel-containing industrial solid waste involved in the treatment process of waste batteries, thereby avoiding the waste of nickel resources and iron resources, and avoiding or reducing the pollution caused by the above-mentioned substances to the environment.
  • the present application provides a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, comprising the following steps:
  • the calcined raw materials of iron-aluminum slag and nickel-containing industrial solid waste are first calcined to obtain nickel oxide and iron oxide; then, a second calcination is performed under reducing conditions to obtain nickel element and iron element;
  • the temperature of the first calcination is not less than 600°C.
  • the first roasting includes at least one of the following features:
  • Feature 1 The temperature of the first calcination is 600-950°C;
  • the first roasting time is 30min-60min;
  • Feature 3 The first roasting is carried out in a tube furnace or muffle furnace;
  • Feature 4 The particle size of the iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting does not exceed 0.15 mm;
  • Feature 5 The mass ratio of iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting is 1:0.2-1:1.
  • the second roasting includes at least one of the following features:
  • Feature 1 The temperature of the second calcination is 800-1350°C;
  • the second roasting time is 45min-120min;
  • Feature 3 The second roasting is carried out in a tube furnace or muffle furnace;
  • Feature 4 The second roasting is carried out in the presence of a reducing agent
  • Feature 6 The second roasting process is also assisted by microwave treatment.
  • feature four includes at least one of the following sub-features:
  • Sub-feature 1 the reducing agent includes a biomass reducing agent; further, the biomass reducing agent includes straw biomass;
  • Sub-characteristic 2 The mass of the reducing agent is 5%-20% of the total mass of the iron-aluminum slag and nickel-containing industrial solid waste.
  • feature five includes at least one of the following sub-features:
  • the high temperature stabilizer includes at least one of silicon dioxide, aluminum oxide, calcium oxide and magnesium oxide;
  • Sub-characteristic 2 The mass of the high-temperature stabilizer is 2%-5% of the total mass of the iron-aluminum slag and nickel-containing industrial solid waste.
  • the microwave power used in the microwave treatment is 3KW-5KW.
  • the process before the first roasting, further includes mixing at least one of a flux and a roasting aid with the ferroaluminum slag and the nickel-containing industrial solid waste.
  • the flux comprises at least one of the following features:
  • the flux includes a sodium-based flux
  • Feature 2 The mass of the flux is 2%-10% of the total mass of the iron-aluminum slag and nickel-containing industrial solid waste.
  • the flux includes at least one of sodium sulfate, sodium carbonate and sodium chloride.
  • the roasting aid includes at least one of the following characteristics:
  • the roasting aid includes a metal salt
  • the mass of the roasting aid is 1%-6% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • the roasting aid includes at least one of sodium molybdate, sodium chromate, ammonium vanadate, sodium titanate, sodium cuprate, sodium manganate and sodium plumbate.
  • the material mixing includes at least one of the following characteristics:
  • the process before the first roasting, further includes pre-treating the nickel-containing industrial solid waste and the iron-aluminum slag;
  • Pre-processing includes at least one of the following features:
  • Feature 1 Crushing nickel-containing industrial solid waste and iron and aluminum slag to reach a preset particle size
  • Feature 2 Pre-activation of nickel-containing industrial solid waste and iron-aluminum slag.
  • the crushing includes at least one of the following features:
  • the volume ratio of the grinding balls used in the sand milling process to the material to be milled is 3:1-30:1.
  • the pre-activation treatment includes: mixing nickel-containing industrial solid waste and iron-aluminum slag with a surfactant.
  • the surfactant comprises at least one of the following features:
  • the surfactant includes at least one of a polycarboxylate water reducer and an alkylbenzene sulfonate;
  • Feature 2 The mass of the surfactant is 0.3%-0.7% of the total mass of the nickel-containing industrial solid waste and iron-aluminum slag.
  • the surfactant comprises a polycarboxylate water reducer.
  • the pre-activated material is dried.
  • drying includes at least one of the following features:
  • Drying temperature is 100°C-150°C, and/or drying time is 4h-8h.
  • the treatment method further comprises: recovering acidic gas generated during the first roasting and/or the second roasting.
  • the recovery method includes: recovering the acid gas with an acid solution.
  • the acid solution includes at least one of the following characteristics:
  • the acid solution includes a sulfuric acid solution
  • Feature 2 The concentration of the acid solution is 95%-98%.
  • the acidic gas is treated by catalytic oxidation and then recovered by an acid solution.
  • the catalyst comprises vanadium pentoxide.
  • the processing method further comprises: separating the roasting solid product after the second roasting to obtain a magnetic nickel-titanium material and a non-magnetic roasting slag.
  • the separation includes at least one of the following features:
  • Feature 1 The separation is carried out by magnetic separation; further, the magnetic field strength used for magnetic separation is 50mT-500mT;
  • the non-magnetic calcined slag is subjected to acid leaching.
  • the acid leaching includes at least one of the following features:
  • Feature 1 The liquid-to-solid ratio of the acid solution used for acid leaching to the non-magnetic roasted slag is 8mL:1g-10mL:1g;
  • Acid leaching temperature is 70°C-90°C
  • Acid leaching time is 1h-2h
  • Feature 4 The acid solution with recovered acid gas is used as leaching solution to acid-leach the non-magnetic roasted slag.
  • the method further comprises: recovering valuable metal elements in the leaching solution obtained after acid leaching; and/or using the leached residue obtained after acid leaching for the next round of roasting or as construction residue or for landfill treatment.
  • the solution provided by the present application is to obtain nickel oxide and iron oxide by first roasting the roasting raw materials of iron-aluminum slag and nickel-containing industrial solid waste; and then to obtain nickel and iron elements by second roasting under reducing conditions.
  • the method can effectively reuse the iron-aluminum slag and nickel-containing industrial solid waste involved in the treatment of waste batteries, which not only avoids the waste of nickel resources and iron resources, but also avoids or reduces the pollution caused by the above substances to the environment, and can be regarded as an effective method for recycling waste batteries.
  • FIG1 is a process flow chart of the method for the full-chain integrated treatment of waste residues in the directional recycling process of waste batteries provided in the present application.
  • the present application proposes a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, which may include the following steps:
  • the calcined raw materials of iron-aluminum slag and nickel-containing industrial solid waste are calcined for the first time to obtain nickel oxide and iron oxide; then they are calcined for the second time under reducing conditions to obtain nickel element and iron element.
  • the temperature of the first calcination is not less than 600°C.
  • the above method can effectively reuse the iron-aluminum slag and nickel-containing industrial solid waste involved in the treatment process of waste batteries, which not only avoids the waste of nickel resources and iron resources, but also avoids or reduces the pollution caused by the above substances to the environment. It is an effective method for recycling waste batteries.
  • At least one of a flux and a roasting aid may be mixed with the ferroaluminum slag and the nickel-containing industrial solid waste.
  • the flux is mixed with ferroaluminum slag and nickel-containing industrial solid waste before the first roasting; in other embodiments, the roasting aid is mixed with ferroaluminum slag and nickel-containing industrial solid waste before the first roasting; in other embodiments, the flux, roasting aid, ferroaluminum slag and nickel-containing industrial solid waste are mixed before roasting.
  • roasting aids before the first roasting it can react with oxides in iron-aluminum slag and nickel-containing solid waste during the first roasting process to promote the reaction.
  • the flux may include a sodium-based flux, such as at least one of sodium sulfate, sodium carbonate, and sodium chloride.
  • the present application uses the above substances as flux, which can react with impurities in the roasted materials to form volatile compounds, thereby promoting the removal of impurities and improving the quality of the product.
  • the above active flux can also increase the fluidity and uniformity of the furnace charge, making the reaction more uniform and sufficient.
  • the mass of the flux can be 2%-10% of the total mass of the ferroaluminum slag and nickel-containing industrial solid waste, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., or it can be any other value within the range of 2%-10%.
  • the amount of flux is less than 2% of the total mass of ferroaluminum slag and nickel-containing industrial solid waste, the expected effect cannot be achieved, which is not conducive to the recovery of nickel and iron metals; if the amount of flux is higher than 10% of the total mass of ferroaluminum slag and nickel-containing industrial solid waste, it may cause the melting point to be too low and the viscosity to be too high, thereby affecting the quality and yield of the roasted product. In addition, too much flux may affect the balance of the reaction, resulting in an increase in the impurity content in the generated metal element. Therefore, in actual production, the appropriate amount of flux added should be determined according to the specific situation to ensure that the reaction can achieve the best effect. The amount added should be determined according to the reaction conditions, the nature of the raw materials and the needs of the roasting process, and should be properly controlled and adjusted.
  • the roasting aid may include a metal salt, such as at least one of sodium molybdate, sodium chromate, ammonium vanadate, sodium titanate, sodium cuprate, sodium manganate, and sodium plumbate.
  • a metal salt such as at least one of sodium molybdate, sodium chromate, ammonium vanadate, sodium titanate, sodium cuprate, sodium manganate, and sodium plumbate.
  • the present application adopts the above-mentioned metal salt as a roasting aid, which can react with the oxides in the iron-aluminum slag and nickel-containing solid waste during the roasting process to generate metals and oxides, thereby promoting the reaction and improving the yield and quality of the product.
  • the above-mentioned metal salt can be decomposed into corresponding metal oxides and oxygen, oxidizing the nickel and iron in the raw materials into high-valent states of nickel and iron, and accelerating the reaction.
  • the metal ions in the above-mentioned metal salt can also combine with the impurity ions in the iron oxide aluminum slag to form insoluble compounds, which is convenient for the removal of impurities.
  • the above-mentioned metal salt can also play the role of catalyst and fluxing to a certain extent, which is conducive to lowering the reaction temperature and accelerating the reaction.
  • the above sodium molybdate can react with metal oxides such as copper, lead, and zinc to generate corresponding metal molybdates, thereby promoting the reduction of metals and improving the purity and quality of the product.
  • Sodium chromate can react with metal oxides such as iron, nickel, and copper to generate corresponding metal chromates, which promotes the reduction and reaction of metals.
  • Ammonium vanadate can be decomposed into V 2 O 5 and NH 3 during the roasting process, and V 2 O 5 can react with oxides to generate vanadates, which promotes the reaction.
  • Sodium titanate can be decomposed into TiO 2 and Na 2 O during the roasting process, and TiO 2 can be used as a high-temperature stabilizer to prevent sintering and crystallization of other substances.
  • Sodium cuprate can promote the redox reaction of metals such as copper, lead, and zinc, and improve the reduction degree of minerals.
  • Sodium manganate can promote the oxidation reaction of metals such as iron and copper, and improve the efficiency of the roasting reaction.
  • Sodium plumbate can promote the redox reaction of metals such as copper and lead, and improve the reduction degree of minerals.
  • the mass of the roasting aid can be 1%-6% of the total mass of the nickel-containing industrial solid waste and iron-aluminum slag, such as 1%, 2%, 3%, 4%, 5% or 6%, etc., or any other value within the range of 1%-6%.
  • the amount of roasting aid used is less than 1% of the total mass of ferroaluminum slag and nickel-containing industrial solid waste, the expected effect cannot be achieved, which is not conducive to the recovery of nickel and iron metals; if the amount of roasting aid used is higher than 6% of the total mass of ferroaluminum slag and nickel-containing industrial solid waste, it may cause instability of the reaction system and reduce the quality of the product.
  • the mixing of the above materials can be carried out under the condition of 45r/min-90r/min, and the speed can be, for example, 45r/min, 50r/min, 55r/min, 60r/min, 65r/min, 70r/min, 75r/min, 80r/min, 85r/min or 90r/min, or any other value within the range of 45r/min-90r/min.
  • the above mixing can be carried out in a high-speed mixer.
  • the mixing time may be 5 min-30 min, such as 5 min, 10 min, 15 min, 20 min, 25 min or 30 min, etc., or any other value within the range of 5 min-30 min.
  • the speed of a high-speed mixer is one of the important factors that affect the mixing effect and product quality. Choosing the right speed can ensure the uniformity and quality stability of the mixed materials.
  • the mixing effect of the iron-aluminum slag and nickel-containing solid waste after drying and screening is best in this speed range. Too low a speed will lead to uneven mixing between materials and materials, materials and additives, while too high a speed will lead to serious dust flying and accumulation.
  • the process before the first roasting, the process further includes pre-treating the nickel-containing industrial solid waste and the iron-aluminum slag.
  • Pretreatment may include, for example, crushing nickel-containing industrial solid waste and iron-aluminum slag to achieve a preset particle size.
  • the crushing process is conducive to making the mixing between the materials more uniform, facilitating the roasting reaction, and making the reaction more sufficient and thorough.
  • the material may be selectively sieved, and the mesh size may match the preset particle size. For example, if the preset particle size is 0.15 mm, the mesh size may be 100 mesh.
  • the crushing can be carried out under the condition of 300r/min-1000r/min (such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000r/min, etc.).
  • the crushing time can be 60min-300min, such as 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min or 300min, etc.
  • the crushing can be carried out by sand grinding, which has at least the following advantages over other crushing methods (such as jaw crusher, roll crusher or impact crusher, etc.):
  • the volume ratio of the grinding balls used in the sand milling process to the material to be ground can be 3:1-30:1, such as 3:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 22:1, 25:1, 28:1 or 30:1, or any other value within the range of 3:1-30:1.
  • the sand grinding balls achieve powder refinement and mixing through friction and collision with the raw powder, and the ball-to-material volume ratio is one of the important factors affecting the sand grinding effect and the final particle size of the sand grinding.
  • Different materials and processes require different ball-to-material volume ratios.
  • the higher the ball-to-material volume ratio the more friction and collision times the ball-to-material will have with the raw powder during sand grinding, and the better the powder refinement effect will be, but it will also increase energy consumption and wear.
  • the present application takes into account energy consumption and grinding effect, and sets the volume ratio of grinding balls to the material to be ground within the range of 3:1-30:1, which not only ensures that the energy consumption is within an acceptable range, but also optimizes the particle size distribution of the corresponding material.
  • the proportion of grinding material with a particle size less than 0.15 mm is about 80%, and increasing the ball-to-material ratio can increase this proportion. Reducing the ball-to-material ratio can reduce the corresponding energy consumption and wear.
  • the pre-treatment may include, for example, pre-activating nickel-containing industrial solid waste and iron-aluminum slag.
  • the pre-activation treatment includes: mixing the nickel-containing industrial solid waste and iron-aluminum slag with a surfactant, which can improve the uniformity and rate of the reaction between the substances during the first roasting process.
  • the above-mentioned surfactant may include at least one of polycarboxylate water-reducing agent and alkylbenzene sulfonate (preferably including polycarboxylate water-reducing agent).
  • polycarboxylate water-reducing agent By adopting polycarboxylate water-reducing agent, the viscosity and surface tension of iron-aluminum slag and nickel-containing solid waste can be effectively reduced, and its fluidity and dispersibility can be improved, thereby improving the uniformity and rate of the reaction.
  • polycarboxylate water-reducing agent also has certain water retention and water reduction properties, which can help control the moisture content and temperature of the roasting reaction and ensure the stability and effect of the reaction.
  • a hydrophilic film can be formed on the surface of the iron-aluminum slag, so that its surface tension is reduced and dispersibility is enhanced, thereby improving the wettability and dispersibility of the iron-aluminum slag.
  • the above-mentioned surfactant can also enhance the interfacial activity between the surface of the iron-aluminum slag and the reaction medium, accelerate the reaction, and improve the uniformity and rate of the reaction.
  • the mass of the surfactant can be 0.3%-0.7% of the total mass of nickel-containing industrial solid waste and iron-aluminum slag, such as 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65% or 0.7%, etc., or it can be any other value within the range of 0.3%-0.7%.
  • the mass of the surfactant is less than 0.3% of the total mass of nickel-containing industrial solid waste and iron-aluminum slag, the expected effect cannot be achieved.
  • the dispersing effect is greatly reduced. Specifically, the dispersing effect of surfactants can reduce the surface tension and viscosity of iron-aluminum slag, making it easier to disperse and flow. Too low an addition amount will lead to poor dispersion effect, which will enhance the interaction between iron-aluminum slag particles, thereby reducing the stability of the product and being unfavorable for the recovery of nickel and iron metals.
  • Reduce the reaction rate If the amount of surfactant (taking polycarboxylate water-reducing agent as an example) added is too high, the surface of the iron-aluminum slag will be covered with too many polycarboxylate molecules, which will reduce the contact frequency of the reactants on the surface of the iron-aluminum slag, thereby reducing the reaction rate.
  • Reduce the product yield If the amount of polycarboxylate water-reducing agent added is too high, it may inhibit the roasting reaction and cause the yield of the roasting product to decrease.
  • Affect product quality If the amount of polycarboxylate water-reducing agent added is too high, the polycarboxylate molecules in the iron-aluminum slag may aggregate together to form colloidal particles, thus affecting product quality.
  • the pretreatment may include only a crushing treatment or only a preactivation treatment; in other embodiments, the pretreatment may include both a crushing treatment and a preactivation treatment.
  • the pre-activated material can be dried.
  • drying can be carried out by air drying, which is more conducive to heat and mass transfer than other drying methods and can evaporate the moisture in the material more quickly and efficiently.
  • the drying temperature may be 100°C-150°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, or any other value within the range of 100°C-150°C.
  • the drying time can be 4 h to 8 h, such as 4 h, 5 h, 6 h, 7 h or 8 h, etc., or any other value within the range of 4 h to 8 h.
  • the temperature of the first roasting is not less than 600° C., so that at least a portion of the nickel-containing substances (such as free nickel, etc.) in the nickel-containing solid waste is converted into nickel oxide.
  • the temperature of the first calcination may be 600-950°C, such as 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C or 950°C, or any other value within the range of 600-9500°C, or further 840-950°C.
  • the nickel-containing substance in the nickel-containing solid waste includes nickel sulfate
  • the nickel sulfate usually loses all crystal water at 280°C, begins to decompose at 840°C, releases sulfur trioxide, and turns into nickel oxide.
  • the sodium ferrosite contained in the ferroaluminum slag will completely decompose into iron oxide at 800°C. Therefore, controlling the first roasting temperature at 840-950°C can ensure that the two industrial solid wastes of nickel sulfate and sodium ferrosite generate nickel oxide (NiO) and iron oxide (FeO, Fe 2 O 3 ) during the first roasting process.
  • NiO nickel oxide
  • FeO, Fe 2 O 3 iron oxide
  • the time of the first calcination may be 30 min-60 min, such as 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min, etc., or may be any other value within the range of 30 min-60 min.
  • the oxidation roasting reaction of the material is not complete enough, the roasting cannot achieve the expected effect, and it is not conducive to the enrichment and recovery of nickel and iron metals; if the first roasting time is longer than 60 minutes, the oxidation roasting reaction will reach the maximum value over time, and continued roasting will have little effect on the oxidation reaction of nickel and iron metals. If the time is too long, a lot of energy will be consumed, which is not conducive to energy saving and environmental protection.
  • the first roasting can be performed in a tube furnace or a muffle furnace to facilitate the collection of acidic gases generated during the first roasting.
  • it is not excluded to use other roasting equipment for the first roasting, and no further restrictions are made here.
  • the particle size of the iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting may not exceed 0.15 mm, such as 0.15 mm, 0.12 mm, 0.10 mm, 0.08 mm or 0.05 mm, etc., or may be other particle sizes within the range of not more than 0.15 mm.
  • the situation that the particle size of the iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting exceeds 0.15 mm is not excluded.
  • the mass ratio of the first roasted iron-aluminum slag and the nickel-containing industrial solid waste can be 1:0.2-1:1, such as 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, or it can be any other value within the range of 1:0.2-1:1.
  • A. Composition and content of ferroaluminum slag and nickel-containing solid waste The composition and content of ferroaluminum slag and nickel-containing solid waste are different, and their effects on reaction effect and product quality are also different. For example, when the nickel content in nickel-containing solid waste is high, the proportion of nickel-containing solid waste can be increased to increase the nickel content of the product.
  • B. Calcination temperature and time The ratio of iron-aluminum slag and nickel-containing solid waste also needs to consider the calcination temperature and time. Within a certain temperature and time range, the ratio of iron-aluminum slag and nickel-containing solid waste will affect the degree and rate of the reaction. Generally speaking, the ratio of nickel-containing solid waste can be appropriately increased at high temperature to increase the reaction rate.
  • composition of iron-aluminum slag also needs to be considered. If the aluminum content in the iron-aluminum slag is high, the proportion of nickel-containing solid waste can be appropriately increased to improve the reaction effect and product quality.
  • Ni-containing solid waste Toxic and hazardous substances may exist in nickel-containing solid waste, and its stability needs to be considered. If the nickel-containing solid waste is unstable, its proportion can be reduced to reduce the impact on the environment.
  • the temperature of the second calcination may be 800-1350°C, such as 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C or 1350°C, etc., or any other value within the range of 800-1350°C.
  • the corresponding oxides of nickel and iron can be reduced to metal elements.
  • the second calcination time can be 45min-120min, such as 45min, 60min, 75min, 90min, 105min or 120min. etc., or any other value within the range of 45min-120min.
  • the second roasting time is shorter than 45 minutes, the oxidation roasting reaction of the material is not complete enough, and the roasting cannot achieve the expected effect, which is not conducive to the enrichment and recovery of nickel and iron metals; if the second roasting time is longer than 120 minutes, the oxidation roasting reaction will reach a maximum value with the passage of time, and continued roasting will have little effect on the oxidation reaction of nickel and iron metals. If the roasting time is too long, a large amount of energy will be consumed, which is not conducive to energy saving and environmental protection.
  • the second roasting can be carried out in a tube furnace or a muffle furnace to facilitate the collection of acidic gases generated during the second roasting process.
  • it is not excluded to use other roasting equipment for the second roasting, and no further limitation is made here.
  • the second calcination may be performed in the presence of a reducing agent, that is, the reducing condition may be provided by the reducing agent.
  • the reducing agent may include a biomass reducing agent, for example, may include straw biomass.
  • Biomass is a renewable reducing agent that can release combustible gases through roasting reactions, while also reducing carbon dioxide emissions during the roasting process; secondly, biomass also contains some organic acids and organic matter, which can react with some components in iron-aluminum slag and nickel-containing solid waste to promote the reaction.
  • straw biomass can, on the one hand, reduce the processing cost of reducing metal oxides to metal elements, and on the other hand, is conducive to the recycling of waste biomass reducing agents, which is green and environmentally friendly.
  • the mass of the reducing agent can be 5%-20% of the total mass of the iron-aluminum slag and nickel-containing industrial solid waste, such as 5%, 8%, 10%, 12%, 15%, 18% or 20%, etc., or it can be any other value within the range of 5%-20%.
  • the mass of the reducing agent is lower than 5% of the total mass of the ferroaluminum slag and nickel-containing industrial solid waste, the expected effect cannot be achieved, and the nickel and iron oxides cannot be fully reduced to single substances, which is not conducive to the recovery of nickel and iron metals; if the mass of the reducing agent is higher than 20% of the total mass of the ferroaluminum slag and nickel-containing industrial solid waste, in the second stage roasting process, the excess flux may affect the balance of the reaction, and a large amount of biomass reducing agent will still remain after the reduction reaction, resulting in an increase in the impurity content in the entire roasting product.
  • a high temperature stabilizer may also be added during the second roasting process.
  • the stability and reaction rate of the reaction system can be improved, the material can be prevented from caking, and the quality and yield of the product can be improved.
  • the high temperature stabilizer may include, for example, at least one of silicon dioxide, aluminum oxide, calcium oxide, and magnesium oxide.
  • This application uses the above substances as high temperature stabilizers, which can have the following effects:
  • Effect 1 Improve the fluidity of materials:
  • the above-mentioned high-temperature stabilizer can promote the fluidity of materials during the second roasting process, making the materials more evenly distributed in the reaction equipment, thereby improving the roasting efficiency and output;
  • Effect 2 Improve product quality:
  • the above-mentioned high temperature stabilizer can control the chemical environment of the reaction system to a certain extent, avoid unnecessary side reactions and the generation of impurities, thereby improving the purity and quality of the product;
  • the above-mentioned high temperature stabilizer can enhance the thermal stability of the material and prevent the material from desorption at high temperature. Loss and deformation, thus ensuring the stability and safety of the roasting process.
  • the mass of the high-temperature stabilizer can be 2%-5% of the total mass of the iron-aluminum slag and nickel-containing industrial solid waste, such as 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, etc., or it can be any other value within the range of 2%-5%.
  • the second calcination process is further assisted by microwave treatment.
  • reaction temperature and reaction rate can be greatly increased compared to traditional or conventional calcination, making the second reduction calcination reaction more thorough.
  • the microwave power used in the microwave treatment is 3KW-5KW, such as 3KW, 3.5KW, 4KW, 4.5KW or 5KW, etc., and can also be any other value within the range of 3KW-5KW.
  • the microwave power is lower than 3KW, the material will be heated unevenly, resulting in incomplete roasting. In addition, low microwave power may cause the heating time to be too long, thereby increasing energy consumption and production costs. If the microwave power is higher than 5KW, the surface of the material will be overheated, resulting in local high temperature areas, affecting the recovery rate of the metal.
  • the acid gas generated during the first roasting and/or the second roasting is recovered.
  • the acid gas generated in the first roasting process can be recovered alone; in other embodiments, the acid gas generated in the second roasting process can be recovered alone; in other embodiments, the acid gas generated in both the first roasting and the second roasting processes can be recovered. Which method to use depends on the specific situation.
  • the recovery method may include, for example, recovering the acid gas using an acid solution.
  • the acid solution may include, for example, a sulfuric acid solution, which, in addition to being a leaching acid for roasted slag, also has the function of treating roasted tail gas and absorbing SO 3 in the tail gas.
  • a sulfuric acid solution which, in addition to being a leaching acid for roasted slag, also has the function of treating roasted tail gas and absorbing SO 3 in the tail gas.
  • Other acid solutions do not have the above two functions at the same time.
  • the concentration of the acid solution may be 95%-98%, such as 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98%, etc., or any other value within the range of 95%-98%.
  • the acid gas may be first treated by catalytic oxidation with a catalyst and then recovered by an acid solution.
  • the acidic gas (SO 2 ) can be oxidized into SO 3 , which is more conducive to the subsequent absorption of sulfuric acid solution.
  • the catalyst may include vanadium pentoxide, and may also include metal oxides, transition metal ions, activated carbon, titanium sulfate catalysts, oxide composite catalysts, and other substances that can catalytically oxidize sulfur dioxide into sulfur trioxide.
  • vanadium pentoxide has at least the following advantages:
  • It has high catalytic activity and shows good catalytic effect in the catalytic oxidation of sulfur dioxide; it has high reaction selectivity and can catalytically oxidize sulfur dioxide into sulfur trioxide without causing other side reactions; it has good durability and stability and can maintain the catalytic effect for a long time in an environment with harsh reaction conditions; the preparation method is relatively simple, the cost is relatively low, and it is easy to industrialize and apply.
  • the processing method provided in the present application may also include: separating the roasting solid product after the second roasting to obtain a magnetic nickel-titanium material and a non-magnetic roasting slag.
  • the separation can be carried out by magnetic separation.
  • other separation methods that can achieve the same separation effect can be used.
  • the magnetic field strength used for magnetic separation can be 50mT-500mT, such as 50mT, 100mT, 150mT, 200mT, 250mT, 300mT, 350mT, 400mT, 450mT or 500mT, etc., or it can be any other value within the range of 50mT-500mT.
  • the magnetic field strength is lower than 50mT, the magnetic force during metal separation will be insufficient, resulting in poor separation effect and incomplete separation of magnetic materials, affecting separation quality and yield. If the magnetic field strength is higher than 500mT, the temperature of the magnetic separator may be too high, causing the magnetic separator to overload, and the magnetic line density in the magnetic separator may be too large, causing particle aggregation or agglomeration, affecting the magnetic separation effect.
  • the Fe element in the iron-aluminum slag and the Ni element in the nickel-containing industrial solid waste can be converted into metal oxides by the first roasting, and the metal oxides generated by the first roasting can be reduced to metal elements by the second roasting.
  • the nickel and iron in the material to be processed are first oxidized by the first roasting, and the nickel and iron metal oxides are reduced to metal elements under the action of the reducing agent in the second roasting, so that the nickel and iron elements in the solid waste are separated from other substances and impurity elements, and then the nickel and iron metals can be effectively recovered by magnetic separation.
  • the roasted solid product may be crushed before separation.
  • the crushing process may be performed by grinding, for example, and the specific conditions may be the same as the conditions for crushing nickel-containing industrial solid waste and iron-aluminum slag to achieve a preset particle size.
  • non-magnetic calcined slag may be subjected to acid leaching.
  • the liquid-to-solid ratio of the acid solution used for acid leaching to the non-magnetic roasted slag can be 8mL:1g-10mL:1g, such as 8mL:1g, 8.5mL:1g, 9mL:1g, 9.5mL:1g or 10mL:1g, etc., or any other value within the range of 8mL:1g-10mL:1g.
  • liquid-to-solid ratio is less than 8 mL:1 g, it is not conducive to fully leaching the valuable metal elements; if the above liquid-to-solid ratio is higher than 10 mL:1 g, it will increase the cost.
  • the pickling temperature may be 70° C.-90° C., such as 70° C., 75° C., 80° C., 85° C. or 90° C., or any other value within the range of 70° C.-90° C.
  • the pickling time may be 1 h-2 h, such as 1 h, 1.5 h or 2 h, or any other value within the range of 1 h-2 h.
  • the acid leaching temperature is lower than 70°C or the acid leaching time is shorter than 1h, it is not conducive to fully leaching the valuable metal elements. If the acid leaching temperature is higher than 90°C or the acid leaching time is longer than 2h, it will increase energy consumption, cause waste, and reduce economic benefits. In addition, a large amount of acid wastewater and acid waste gas may be generated during the acid leaching process. If the acid leaching time is too long, it will increase the cost of waste treatment and cause environmental pollution.
  • the acid solution containing the recovered acid gas can be used as a leaching solution to leaching the non-magnetic roasted slag. Acid leaching is carried out to maximize the reuse of resources.
  • the valuable metal elements in the leaching solution obtained by acid leaching can be recovered.
  • the leached residue obtained by acid leaching can be used for the next round of roasting, or as construction slag, or for landfill treatment, etc.
  • the nickel and iron in the solid waste can be separated and recovered through the above treatment method, and the acid tail gas generated by roasting can be fully utilized.
  • the acid after absorbing the roasting tail gas can be used as leaching acid for non-magnetic roasting, and then the Al, Ni, Co, and Mn elements therein can be recovered.
  • the acid leaching residue can be returned to roasting treatment, or used as construction slag, or landfilled.
  • the entire process basically realizes recycling, and while reasonably utilizing a large amount of industrial solid waste, it also effectively recovers the valuable metal elements in the industrial solid waste.
  • the process is simple and low in cost, which is conducive to large-scale project commissioning.
  • This embodiment provides a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, which mainly includes the following steps:
  • S9 recovering Al, Ni, Co and Mn elements in the acid leaching solution and returning the acid leaching residue to the roasting process.
  • This embodiment provides a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, which mainly includes the following steps:
  • the calcined product is naturally cooled, it is poured into a sand mill for grinding, the speed of the sand mill is 300r/min, the sand milling time is 60min, the volume ratio of grinding balls to raw materials is 3:1, and the magnetic field strength is selected to be 100mT to further separate the calcined product by magnetic separation to obtain the magnetic nickel-iron alloy and non-magnetic calcined slag, the nickel metal recovery rate is 77.3%, and the iron metal recovery rate is 70.1%;
  • This embodiment provides a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, which mainly includes the following steps:
  • S9 Recover Al, Ni, Co and Mn elements in the acid leaching solution and use the acid leaching residue for landfill treatment.
  • This embodiment provides a method for treating waste residues in a directional recycling process of waste batteries in an integrated manner, which mainly includes the following steps:
  • the calcined product is naturally cooled, it is poured into a sand mill for grinding, the speed of the sand mill is 300r/min, the sand milling time is 60min, the volume ratio of grinding balls to raw materials is 10:1, and the magnetic field strength is selected to be 350mT to further separate the calcined product by magnetic separation to obtain the magnetic nickel-iron alloy and non-magnetic calcined slag, the nickel metal recovery rate is 87.3%, and the iron metal recovery rate is 75.1%;
  • S9 recovering Al, Ni, Co and Mn elements in the acid leaching solution and returning the acid leaching residue to the roasting process.
  • the difference between this embodiment and embodiment 4 is that the particle size of the iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting is 0.1 mm.
  • the nickel metal recovery rate of this embodiment is 88.5%, and the iron metal recovery rate is 77.3%.
  • the difference between this embodiment and embodiment 4 is that the mass of the flux is 10% of the total mass of the iron-aluminum slag and the nickel-containing industrial solid waste.
  • the nickel metal recovery rate of this embodiment is 89.1%, and the iron metal recovery rate is 78.2%.
  • roasting aid is sodium chromate.
  • nickel metal recovery rate of this embodiment is 86.5%, and the iron metal recovery rate is 75.7%.
  • the difference between this embodiment and embodiment 4 is that the mass of the roasting aid is 6% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • the nickel metal recovery rate of this embodiment is 87.9%, and the iron metal recovery rate is 76.1%.
  • the difference between this embodiment and embodiment 4 is that the surfactant is alkylbenzene sulfonate.
  • the nickel metal recovery rate of this embodiment is 85.3%, and the iron metal recovery rate is 78.1%.
  • the difference between this embodiment and embodiment 4 is that the mass of the surfactant is 0.7% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • the nickel metal recovery rate of this embodiment is 87.8%, and the iron metal recovery rate is 75.4%.
  • the difference between this embodiment and embodiment 4 is that the first calcination and the second calcination are both carried out in a muffle furnace.
  • the nickel metal recovery rate of this embodiment is 88.1%, and the iron metal recovery rate is 76.8%.
  • the difference between this embodiment and embodiment 4 is that the temperature of the first roasting is 600° C.
  • the nickel metal recovery rate of this embodiment is 71.3%, and the iron metal recovery rate is 70.9%.
  • the difference between this embodiment and embodiment 4 is that the temperature of the first roasting is 950° C.
  • the nickel metal recovery rate of this embodiment is 88.5%, and the iron metal recovery rate is 77.3%.
  • the difference between this embodiment and embodiment 4 is that the temperature of the second roasting is 800° C.
  • the nickel metal recovery rate of this embodiment is 82.4%, and the iron metal recovery rate is 73.2%.
  • the difference between this embodiment and embodiment 4 is that the temperature of the second roasting is 1350° C.
  • the nickel metal recovery rate of this embodiment is 89.3%, and the iron metal recovery rate is 78.9%.
  • the difference between this embodiment and embodiment 4 is that the microwave power during the second roasting process is 3 KW.
  • the nickel metal recovery rate of this embodiment is 85.7%, and the iron metal recovery rate is 73.8%.
  • the difference between this embodiment and embodiment 4 is that the microwave power during the second roasting process is 5 KW.
  • the nickel metal recovery rate of this embodiment is 89.3%, and the iron metal recovery rate is 78.6%.
  • Example 4 The difference between this comparative example and Example 4 is that the particle size of the iron-aluminum slag and nickel-containing industrial solid waste used for the first roasting is 0.5 mm.
  • Example 4 The difference between this comparative example and Example 4 is that the mass ratio of the iron-aluminum slag and the nickel-containing industrial solid waste used for the first roasting is 1:0.05.
  • Example 4 The difference between this comparative example and Example 4 is that the mass ratio of the iron-aluminum slag and the nickel-containing industrial solid waste used for the first roasting is 1:1.2.
  • Example 4 The difference between this comparative example and Example 4 is that the temperature of the first calcination is 500°C.
  • Example 4 The difference between this comparative example and Example 4 is that the temperature of the first calcination is 1000°C.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the flux is 1% of the total mass of the iron-aluminum slag and the nickel-containing industrial solid waste.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the flux is 15% of the total mass of the iron-aluminum slag and the nickel-containing industrial solid waste.
  • Example 4 The difference between this comparative example and Example 4 is that no roasting aid is used.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the roasting aid is 0.5% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the roasting aid is 8% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • Example 4 The difference between this comparative example and Example 4 is that no pre-activation treatment was performed.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the surfactant is 0.1% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the surfactant is 1% of the total mass of the nickel-containing industrial solid waste and the iron-aluminum slag.
  • Example 4 The difference between this comparative example and Example 4 is that the temperature of the second calcination is 600°C.
  • Example 4 The difference between this comparative example and Example 4 is that the temperature of the second calcination is 1500°C.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the reducing agent is 25% of the total mass of the iron-aluminum slag and the nickel-containing industrial solid waste.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the high temperature stabilizer in the second roasting process is iron-aluminum slag and nickel-containing industrial 1% of the total mass of solid waste.
  • Example 4 The difference between this comparative example and Example 4 is that the mass of the high-temperature stabilizer in the second roasting process is 8% of the total mass of the iron-aluminum slag and the nickel-containing industrial solid waste.
  • Example 4 The difference between this comparative example and Example 4 is that no microwave treatment is performed during the second roasting process.
  • Example 4 The difference between this comparative example and Example 4 is that the microwave power during the second roasting process is 1 KW.
  • Example 4 The difference between this comparative example and Example 4 is that the microwave power during the second roasting process is 10KW.
  • the method for the full-chain integrated treatment of waste slag in the directional recycling process of waste batteries provided in the present application has low cost, and can effectively reuse the iron-aluminum slag and nickel-containing industrial solid waste involved in the waste battery treatment process, thereby avoiding the waste of nickel resources and iron resources, and avoiding or reducing the pollution caused by the above-mentioned substances to the environment. It is an effective method for recycling waste batteries.
  • the method provided in the present application for the full-chain integrated treatment of waste slag in the directional recycling process of waste batteries has low cost and can effectively reuse the iron-aluminum slag and nickel-containing industrial solid waste involved in the treatment process of waste batteries, thereby avoiding the waste of nickel resources and iron resources, and avoiding or reducing the pollution caused by the above-mentioned substances to the environment. It is an effective method for recycling waste batteries.

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Abstract

本申请公开了一种全链条一体化处理废旧电池定向循环过程中废渣的方法，属于电池技术领域。该处理方法包括以下步骤：将铁铝渣和含镍工业固废的焙烧原料进行第一次焙烧，得到镍的氧化物和铁的氧化物；随后在还原条件下进行第二次焙烧，得到镍单质和铁单质。其中，第一次焙烧的温度不低于600℃。该方法成本较低，能够有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染，不失成为废旧电池回收利用的有效方法。

Description

一种全链条一体化处理废旧电池定向循环过程中废渣的方法 技术领域
本申请涉及电池技术领域，具体而言，涉及一种全链条一体化处理废旧电池定向循环过程中废渣的方法。
背景技术
近几年来随着新能源汽车市场的飞速发展，锂离子电池的广泛应用导致大量废旧锂离子电池产生，废旧锂离子电池具有危险废弃物和可用资源的双重属性，利用不同的回收工艺实现废旧锂离子电池的高效回收再利用，对环境保护和资源再生均有重要意义。随着三元材料高镍化发展，对镍的需求量逐年增高，但目前镍资源较为紧张，通过回收废旧电池中的有价金属，如镍资源和铁资源并实现此类资源的定向循环，重新进入电池端，建设“全链条一体化产业园”，成为目前多数锂电正极材料生产厂家降本增效的首要选择。
但目前资源化废旧电池过程中会产生各种金属硫酸盐溶液，这些溶液中基本都含有一定量的铁、铝离子，从溶液中除铁、除铝在锂电池回收过程中是一道非常重要的工序。
就常规方法而言，黄钠铁矾法除铁在工业中应用比较广泛。其主要因为黄钠铁矾以晶体状态沉淀，沉淀性能较好、渣粒粗、过滤性能比较好，同时渣中夹带金属少，能较好地解决硫酸盐平衡问题，而且操作条件简单，易于实现(常压中温即可)。与此同时，使用黄钠铁矾法除铁时，在调节pH的过程中铝离子也会出现水解沉淀而被随之除去。然而，使用黄钠铁矾法在除铁的过程中会产生大量的铁铝渣，铁铝渣中基本上都会夹带有毒有害元素，且化学性质不稳定，因此铁铝渣处理需要投入成本较高，常规处理方法是用石灰中和后堆存，但是堆存环境变化会导致铁铝渣发生分解反应，生成污染环境的物质。
除了铁铝渣，在废旧电池的湿法回收过程中，不可避免会产生大量的含镍工业固废，如含镍废物处理污泥、镍钴渣等工业固废，这些固废中含有大量的重金属元素，如果不经处理直接填埋，不仅会造成镍资源的浪费，而且这些工业固废会溶出镍重金属元素并进入土壤和水体，对生态环境造成严重污染。
鉴于此，特提出本申请。
发明内容
本申请的目的包括提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，可有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染。
为了实现本申请的上述目的，可采用以下技术方案：
本申请提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，包括以下步骤：
将铁铝渣和含镍工业固废的焙烧原料进行第一次焙烧，得到镍的氧化物和铁的氧化物；随后在还原条件下进行第二次焙烧，得到镍单质和铁单质；
其中，第一次焙烧的温度不低于600℃。
在可选的实施方式中，第一次焙烧包括以下特征中的至少一种：
特征一：第一次焙烧的温度为600-950℃；
特征二：第一次焙烧的时间为30min-60min；
特征三：第一次焙烧是于管式炉或马弗炉中进行；
特征四：用于第一次焙烧的铁铝渣和含镍工业固废的粒径不超过0.15mm；
特征五：用于第一次焙烧的铁铝渣和含镍工业固废的质量比为1:0.2-1:1。
在可选的实施方式中，第二次焙烧包括以下特征中的至少一种：
特征一：第二次焙烧的温度为800-1350℃；
特征二：第二次焙烧的时间为45min-120min；
特征三：第二次焙烧是于管式炉或马弗炉中进行；
特征四：第二次焙烧是于还原剂存在的条件下进行；
特征五：第二次焙烧过程中还加入有高温稳定剂；
特征六：第二次焙烧过程中还辅助有微波处理。
在可选的实施方式中，特征四包括以下子特征中的至少一种：
子特征一：还原剂包括生物质还原剂；进一步地，生物质还原剂包括秸秆类生物质；
子特征二：还原剂的质量为铁铝渣和含镍工业固废的总质量的5％-20％。
在可选的实施方式中，特征五包括以下子特征中的至少一种：
子特征一：高温稳定剂包括二氧化硅、三氧化二铝、氧化钙和氧化镁中的至少一种；
子特征二：高温稳定剂的质量为铁铝渣和含镍工业固废的总质量的2％-5％。
在可选的实施方式中，微波处理使用的微波功率为3KW-5KW。
在可选的实施方式中，在第一次焙烧之前，还包括将助熔剂和焙烧助剂中的至少一种与铁铝渣和含镍工业固废混合。
在可选的实施方式中，助熔剂包括以下特征中的至少一种：
特征一：助熔剂包括钠基助熔剂；
特征二：助熔剂的质量为铁铝渣和含镍工业固废的总质量的2％-10％。
在可选的实施方式中，助熔剂包括硫酸钠、碳酸钠和氯化钠中的至少一种。
在可选的实施方式中，焙烧助剂包括以下特征中的至少一种：
特征一：焙烧助剂包括金属盐；
特征二：焙烧助剂的质量为含镍工业固废和铁铝渣的总质量的1％-6％。
在可选的实施方式中，焙烧助剂包括钼酸钠、铬酸钠、钒酸铵、钛酸钠、铜酸钠、锰酸钠和铅酸钠中的至少一种。
在可选的实施方式中，物料混合包括以下特征中的至少一种：
特征一：混合是于45r/min-90r/min的条件下进行；
特征二：混合时间为5min-30min。
在可选的实施方式中，在第一次焙烧之前，还包括对含镍工业固废和铁铝渣进行前处理；
前处理包括以下特征中的至少一种：
特征一：将含镍工业固废和铁铝渣进行破碎以达到预设粒径；
特征二：将含镍工业固废和铁铝渣进行预活化处理。
在可选的实施方式中，破碎包括以下特征中的至少一种：
特征一：破碎采用砂磨方式进行；
特征二：破碎是于300r/min-1000r/min的条件下进行；
特征三：破碎时间为60min-300min。
在可选的实施方式中，砂磨过程中使用的磨球与待磨物料的体积比为3:1-30:1。
在可选的实施方式中，预活化处理包括：将含镍工业固废和铁铝渣与表面活性剂混合。
在可选的实施方式中，表面活性剂包括以下特征中的至少一种：
特征一：表面活性剂包括聚羧酸减水剂和烷基苯磺酸盐中的至少一种；
特征二：表面活性剂的质量为含镍工业固废和铁铝渣的总质量的0.3％-0.7％。
在可选的实施方式中，表面活性剂包括聚羧酸减水剂。
在可选的实施方式中，第一次焙烧之前，还包括将预活化处理后的物料进行干燥。
在可选的实施方式中，干燥包括以下特征中的至少一种：
特征一：干燥采用鼓风干燥方式进行；
特征二：干燥温度为100℃-150℃，和/或，干燥时间为4h-8h。
在可选的实施方式中，处理方法还包括：回收第一次焙烧和/或第二次焙烧过程中产生的酸性气体。
在可选的实施方式中，回收方式包括：用酸溶液回收酸性气体。
在可选的实施方式中，酸溶液包括以下特征中的至少一种：
特征一：酸溶液包括硫酸溶液；
特征二：酸溶液的浓度为95％-98％。
在可选的实施方式中，将酸性气体经催化剂催化氧化处理后再通过酸溶液进行回收。
在可选的实施方式中，催化剂包括五氧化二钒。
在可选的实施方式中，处理方法还包括：将第二次焙烧后的焙烧固体产物进行分离，得到磁性物镍钛物及非磁性焙烧渣。
在可选的实施方式中，分离包括以下特征中的至少一种：
特征一：分离采用磁选分离方式进行；进一步，磁选分离所用的磁场强度为50mT-500mT；
特征二：分离前，还包括对焙烧固体产物进行破碎处理。
在可选的实施方式中，对非磁性焙烧渣进行酸浸。
在可选的实施方式中，酸浸包括以下特征中的至少一种：
特征一：酸浸所用的酸溶液与非磁性焙烧渣的液固比为8mL：1g-10mL：1g；
特征二：酸浸温度为70℃-90℃；
特征三：酸浸时间为1h-2h；
特征四：将回收有酸性气体的酸溶液作为浸出液对非磁性焙烧渣进行酸浸。
在可选的实施方式中，还包括：回收酸浸后得到的浸出液中的有价金属元素；和/或，将酸浸后得到的浸出渣用于下一轮焙烧或作为建筑用渣或用于进行填埋处理。
本申请提供的方案通过将铁铝渣和含镍工业固废的焙烧原料进行第一次焙烧，可得到镍的氧化物和铁的氧化物；随后在还原条件下进行第二次焙烧，得到镍单质和铁单质。该方法能有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染，不失成为废旧电池回收利用的有效方法。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请提供的全链条一体化处理废旧电池定向循环过程中废渣的方法的工艺流程图。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本申请中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点 值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
请参照图1，本申请提出一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其可包括以下步骤：
将铁铝渣和含镍工业固废的焙烧原料进行第一次焙烧，得到镍的氧化物和铁的氧化物；随后在还原条件下进行第二次焙烧，得到镍单质和铁单质。
其中，第一次焙烧的温度不低于600℃。
通过上述方法能有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染，不失成为废旧电池回收利用的有效方法。
作为参考地，在第一次焙烧之前，可以将助熔剂和焙烧助剂中的至少一种与铁铝渣和含镍工业固废混合。
也即，在一些实施方式中，将助熔剂与铁铝渣和含镍工业固废混合后再进行第一次焙烧；在另一些实施方式中，将焙烧助剂与铁铝渣和含镍工业固废混合后再进行第一次焙烧；在其它另一些实施方式中，将助熔剂、焙烧助剂与铁铝渣和含镍工业固废混合后再焙烧。
通过在第一次焙烧之前添加助熔剂，可促进矿物在高温下的熔融和流动，促进反应的进行，并提高反应速率和产物(氧化物)质量。通过在第一次焙烧之前添加焙烧助剂，可以在第一次焙烧过程中与铁铝渣和含镍固废中的氧化物反应，促进反应进行。
在一些实施方式中，助熔剂可包括钠基助熔剂，如硫酸钠、碳酸钠和氯化钠中的至少一种。
本申请采用上述物质作为助熔剂，可与焙烧物料中的杂质反应形成易挥发的化合物，从而促进杂质的除去，提高产品的质量。并且，上述活性助熔剂还可以增加炉料的流动性和均匀性，使得反应更为均匀和充分。
示例性地，助熔剂的质量可以为铁铝渣和含镍工业固废的总质量的2％-10％，如2％、3％、4％、5％、6％、7％、8％、9％或10％等，也可以为2％-10％范围内的其它任意值。
需说明的是，若助熔剂的用量低于铁铝渣和含镍工业固废的总质量的2％，则无法达到预期的效果，不利于镍、铁金属的回收；若助熔剂的用量高于铁铝渣和含镍工业固废的总质量的10％，可能会导致熔点过低、粘度过高，从而影响焙烧产物的品质和产量。此外，过多的助熔剂可能会影响反应的平衡，导致生成的金属单质中杂质含量增加。因此，在实际生产中，应根据具体情况确定适当的助熔剂添加量，以确保反应能够达到最佳效果。添加量应该根据反应条件、原料的性质和焙烧过程的需要来确定，并进行适当的控制和调整。
在一些实施方式中，焙烧助剂可包括金属盐，如包括钼酸钠、铬酸钠、钒酸铵、钛酸钠、铜酸钠、锰酸钠和铅酸钠中的至少一种。
本申请采用上述金属盐作为焙烧助剂，可以在焙烧过程中与铁铝渣和含镍固废中的氧化物反应，生成金属和氧化物，从而促进反应进行，提高产物的收率和品质。其次，在高温下，上述金属盐可以分解为对应的金属氧化物和氧气，将原料中的镍、铁氧化成为镍、铁的高价态，加快反应进行。此外，上述金属盐中的金属离子也可以与氧化铁铝渣中的杂质离子结合，形成难溶性的化合物，便于杂质的去除。进一步地，上述金属盐还可在一定程度上起到催化剂的作用和助熔作用，有利于降低反应温度，加速反应进行。
具体的，上述钼酸钠可以与铜、铅、锌等金属氧化物反应，生成相应的金属钼酸盐，从而促进金属的还原，提高产物的纯度和品质。铬酸钠可以与铁、镍、铜等金属氧化物反应，生成相应的金属铬酸盐，促进金属的还原和反应进行。钒酸铵可在焙烧过程中分解为V2O5和NH3，V2O5可以与氧化物反应生成钒酸盐，促进反应进行。钛酸钠在焙烧过程中可以分解为TiO2和Na2O，TiO2可以作为高温稳定剂，防止其他物质的烧结和结晶。铜酸钠可以促进铜、铅、锌等金属的氧化还原反应，提高矿物的还原程度。锰酸钠可以促进铁、铜等金属的氧化反应，提高焙烧反应的效率。铅酸钠可以促进铜、铅等金属的氧化还原反应，提高矿物的还原程度。
示例性地，焙烧助剂的质量可以为含镍工业固废和铁铝渣的总质量的1％-6％，如1％、2％、3％、4％、5％或6％等，也可以为1％-6％范围内的其它任意值。
需说明的是，若焙烧助剂的用量低于铁铝渣和含镍工业固废的总质量的1％，则无法达到预期的效果，不利于镍、铁金属的回收；若焙烧助剂的用量高于铁铝渣和含镍工业固废的总质量的6％，可能会导致反应体系的不稳定性，降低产物的品质。
作为参考地，上述物料的混合可以于45r/min-90r/min的条件下进行，转速例如可以为45r/min、50r/min、55r/min、60r/min、65r/min、70r/min、75r/min、80r/min、85r/min或90r/min等，也可以为45r/min-90r/min范围内的其它任意值。示例性地，上述混合可在高速混合机中进行。
混合时间可以为5min-30min，如5min、10min、15min、20min、25min或30min等，也可以为5min-30min范围内的其它任意值。
高速混合机的转速是影响混合效果和产品质量的重要因素之一。选择合适的转速可以保证混合物料的均匀性和质量稳定性。将铁铝渣、含镍固废干燥过筛后的颗粒在这个转速区间的混合效果最好，转速过低会导致物料与物料、物料与添加剂之间混合不均匀，而转速过高则会导致严重的粉尘飞扬和聚积现象。
在一些实施方式中，在第一次焙烧之前，还包括对含镍工业固废和铁铝渣进行前处理。
前处理例如可包括将含镍工业固废和铁铝渣进行破碎以达到预设粒径。通过进行破碎处理，有利于使物料之间的混合更加均匀，便于焙烧反应的进行，使反应更加充分和彻底。破碎后可选择性地进行过筛处理，筛孔大小与预设粒径相匹配，例如，若预设粒径为0.15mm，则筛孔大小可采用100目。
作为参考地，破碎可以于300r/min-1000r/min(如300r/min、400r/min、500r/min、600r/min、700r/min、800r/min、900r/min或1000r/min等)的条件下进行。破碎时间可以为60min-300min，如60min、90min、120min、150min、180min、210min、240min、270min或300min等。
示例性地，破碎可采用砂磨方式进行，该方式较其他破碎方式(如颚式破碎机、辊式破碎机或冲击式破碎机等)至少具有以下优势：
破碎效率高，能够快速地将物料破碎成所需的粒度大小；能耗低，基于其是通过摩擦和碰撞作用来破碎物料，因此，相对于其他破碎方式而言，更加节约能耗；粉尘少，物料在砂磨机中被破碎时，砂轮和转子的旋转速度可以将粉尘和碎片迅速排出机器，降低了粉尘的产生和对环境的影响；操作简便。
砂磨过程中使用的磨球与待磨物料的体积比可以为3:1-30:1，如3:1、5:1、8:1、10:1、12:1、15:1、18:1、20:1、22:1、25:1、28:1或30:1等，也可以为3:1-30:1范围内的其它任意值。
在砂磨过程中，砂磨球料通过与原料粉末的摩擦和碰撞来实现粉末的细化和混合，而球料体积比则是影响砂磨效果和砂磨终点粒度的重要因素之一。不同的材料和工艺需要不同的球料体积比，通常球料体积比越高，砂磨过程中球料与原料粉末的摩擦和碰撞次数越多，粉末的细化效果也越好，但同时也会增加能耗和磨损。本申请考虑到能耗与研磨效果，将磨球与待磨物料的体积比在3:1-30:1这个范围内，不仅能确保能耗在可接受的范围内，而且相应的物料的粒径分布最佳。
例如，当球料比为20：1时，研磨物料粒径小于0.15mm的比例约为80％，而提高球料比可以提高该比例。减少球料比，则可以降低相应的能耗和磨损。
前处理例如可包括将含镍工业固废和铁铝渣进行预活化处理。
在可选的实施方式中，预活化处理包括：将含镍工业固废和铁铝渣与表面活性剂混合，可提高第一次焙烧过程中物质之间反应的均匀性和速率。
上述表面活性剂可包括聚羧酸减水剂和烷基苯磺酸盐中的至少一种(优选包括聚羧酸减水剂)。通过采用聚羧酸减水剂可以有效降低铁铝渣、含镍固废的黏度和表面张力，改善其流动性和分散性，从而提高反应的均匀性和速率。此外，聚羧酸减水剂还具有一定的保水性和减水性，可以帮助控制焙烧反应的水分含量和温度，保证反应的稳定性和效果。通过采用烷基苯磺酸盐，可在铁铝渣表面形成一层亲水性的薄膜，使其表面张力降低，分散性增强，从而提高铁铝渣的润湿性和分散性。在焙烧过程中，上述表面活性剂还可以增强铁铝渣表面和反应介质之间的界面活性，加速反应的进行，提高反应的均匀性和速率。
示例性地，表面活性剂的质量可以为含镍工业固废和铁铝渣的总质量的0.3％-0.7％，如0.3％、0.35％、0.4％、0.45％、0.5％、0.55％、0.6％、0.65％或0.7％等，也可以为0.3％-0.7％范围内的其它任意值。
若表面活性剂的质量低于含镍工业固废和铁铝渣的总质量的0.3％，则无法达到预期的效果， 分散作用大大降低。具体的，表面活性剂的分散作用可以降低铁铝渣的表面张力和黏度，使其更易分散和流动。添加量过低会导致分散效果不佳，使得铁铝渣颗粒之间的相互作用增强，从而降低产品的稳定性，不利于镍、铁金属的回收。
若表面活性剂的质量高于含镍工业固废和铁铝渣的总质量的0.7％，可能会出现以下影响：
降低反应速率：表面活性剂(以聚羧酸减水剂为例)的添加量过高会导致铁铝渣表面覆盖的聚羧酸分子过多，降低反应物在铁铝渣表面的接触频率，进而降低反应速率。减少产物收率：聚羧酸减水剂在过高的添加量下，可能会抑制焙烧反应的进行，导致焙烧产物的收率下降。影响产品质量：过高的聚羧酸减水剂添加量可能会导致铁铝渣中的聚羧酸分子聚集在一起，形成胶体颗粒，从而影响产品质量。
需说明的是，在一些实施方式中，预处理可仅包括破碎处理，也可仅包括预活化处理；在另一些实施方式中，预处理可既包括破碎处理，也包括预活化处理。
进一步地，第一次焙烧之前，还可将预活化处理后的物料进行干燥。
作为参考地，干燥可采用鼓风干燥方式进行，该方式较其它的干燥方式更利于传热和传质，可以更加快捷且高效地将物料中的水分蒸发掉。
示例性地，上述干燥的温度可以为100℃-150℃，如100℃、110℃、120℃、130℃、140℃或150℃等，也可以为100℃-150℃范围内的其它任意值。
干燥的时间可以为4h-8h，如4h、5h、6h、7h或8h等，也可以为4h-8h范围内的其它任意值。
本申请中，第一次焙烧的温度不低于600℃，以使含镍固废中的至少一部分含镍物质(例如游离态的镍等)转化为氧化镍。
在一些实施方式中，第一次焙烧的温度可以为600-950℃，如600℃、650℃、700℃、750℃、800℃、850℃、900℃或950℃等，也可以为600-9500℃范围内的其它任意值。进一步地可以为840-950℃。
需说明的是，当含镍固废中的含镍物质包括硫酸镍时，硫酸镍通常在280℃时会失去全部结晶水，在840℃开始分解，释放出三氧化硫，变为氧化镍。铁铝渣中所含的黄钠铁矾在800℃时会完全分解为氧化铁。因此，将第一次焙烧温度控制在840-950℃，能够确保硫酸镍和黄钠铁矾两种工业固废在第一次焙烧过程中生成镍的氧化物(NiO)和铁的氧化物(FeO、Fe2O3)。上述镍、铁的氧化物在还原条件下进行第二次焙烧，可被还原为金属单质。
第一次焙烧的时间可以为30min-60min，如30min、35min、40min、45min、50min、55min或60min等，也可以为30min-60min范围内的其它任意值。
需说明的是，若第一次焙烧时间短于30min，则物料的氧化焙烧反应进行得不够完全，焙烧无法达到预期的效果，不利于镍、铁金属的富集与回收；若第一次焙烧时间长于60min，氧化焙烧反应会随着时间的推移达到最大值，再继续焙烧对镍、铁金属的氧化反应作用效果不大，而焙烧时 间过长会消耗大量的能耗，不利于节能环保。
在一些可选的实施方式中，第一次焙烧可以于管式炉或马弗炉中进行，以利于收集第一次焙烧过程中产生的酸性气体。此外，在其它实施方式中，也不排除采用其它的焙烧设备进行上述第一次焙烧，在此不做过多限定。
在本申请中，用于第一次焙烧的铁铝渣和含镍工业固废的粒径例如可不超过0.15mm，如0.15mm、0.12mm、0.10mm、0.08mm或0.05mm等，也可以为不超过0.15mm范围内的其它粒径。此外，也不排除第一次焙烧的铁铝渣和含镍工业固废的粒径超过0.15mm的情况。
需说明的是，通过将铁铝渣和含镍工业固废的粒径控制在不超过0.15mm，更有利于铁铝渣和含镍工业固废在第一次焙烧过程中快速地均匀受热并发生反应，获得更好的焙烧效果。
在一些可选的实施方式中，第一次焙烧的铁铝渣和含镍工业固废的质量比可以为1:0.2-1:1，如1:0.2、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9或1:1等，也可以为1:0.2-1:1范围内的其它任意值。
通过将铁铝渣和含镍工业固废的质量比控制在上述范围，有利于获得更好的反应效果和产物质量。
需说明的是，考虑到铁铝渣和含镍固废中化学成分的复杂性，焙烧资源化的过程中，具体的原料配比需要根据实际情况进行优化，通常涉及以下几个方面：
A、铁铝渣和含镍固废的成分和含量：铁铝渣和含镍固废的成分和含量不同，对反应效果和产物质量的影响也不同。例如，含镍固废中的镍含量高时，可以增加含镍固废的比例，从而提高产物的镍含量。
B、焙烧温度和时间：铁铝渣和含镍固废的配比也需要考虑焙烧温度和时间。在一定的温度和时间范围内，铁铝渣和含镍固废的比例会影响反应的程度和速率。一般来说，高温下含镍固废的比例可以适当增加，以提高反应速率。
C、铁铝渣的成分：铁铝渣的成分也需要考虑。如果铁铝渣中铝含量高，可以适当增加含镍固废的比例，以提高反应效果和产物质量。
D、含镍固废的成分和稳定性：含镍固废中可能存在有毒有害物质，需要考虑其稳定性。如果含镍固废不稳定，可以减少其比例，以减少对环境的影响。
因此，根据铁铝渣和含镍固废的特性和焙烧反应的要求，可以采取不同的原料配比方案。通过合理的配比，可以实现更好的反应效果和产物质量，同时也能够节约成本。
本申请中，第二次焙烧的温度可以为800-1350℃，如800℃、900℃、1000℃、1100℃、1200℃、1300℃或1350℃等，也可以为800-1350℃范围内的其它任意值。
在上述温度范围内，能够使得镍和铁对应生成氧化物均被还原成金属单质。
第二次焙烧的时间可以为45min-120min，如45min、60min、75min、90min、105min或120min 等，也可以为45min-120min范围内的其它任意值。
需说明的是，若第二次焙烧时间短于45min，物料的氧化焙烧反应进行得不够完全，焙烧无法达到预期的效果，不利于镍、铁金属的富集与回收；若第二次焙烧时间长于120min，氧化焙烧反应会随着时间的推移达到最大值，再继续焙烧对镍、铁金属的氧化反应作用效果不大，而焙烧时间过长会消耗大量的能耗，不利于节能环保。
同理地，在一些可选的实施方式中，第二次焙烧可以于管式炉或马弗炉中进行，以利于收集第二次焙烧过程中产生的酸性气体。此外，在其它实施方式中，也不排除采用其它的焙烧设备进行上述第二次焙烧，在此不做过多限定。
作为参考地，第二次焙烧可以是于还原剂存在的条件下进行，也即，还原条件可由还原剂提供。
在一些可选地实施方式中，还原剂可包括生物质还原剂，例如可以包括秸秆类生物质。
生物质为可再生的还原剂，可以通过焙烧反应释放出可燃性气体，同时还可以减少焙烧过程中的二氧化碳排放；其次，生物质中还含有一些有机酸和有机物，可以与铁铝渣和含镍固废中的一些成分反应，促进反应的进行。
需说明的是，采用秸秆类生物质一方面能够降低将金属氧化物还原为金属单质的处理成本，另一方面有利于对废弃的生物质还原剂进行回收利用，绿色环保。
示例性地，还原剂的质量可以为铁铝渣和含镍工业固废的总质量的5％-20％，如5％、8％、10％、12％、15％、18％或20％等，也可以为5％-20％范围内的其它任意值。
需说明的是，若还原剂的质量低于铁铝渣和含镍工业固废的总质量的5％，无法达到预期的效果，镍、铁的氧化物无法充分还原为单质，不利于镍、铁金属的回收；若还原剂的质量高于铁铝渣和含镍工业固废的总质量的20％，在二段焙烧过程中，多的助熔剂可能会影响反应的平衡，且还原反应结束仍然剩余有大量的生物质还原剂，导致整个焙烧产物中的杂质含量增加。
本申请中，第二次焙烧过程中还可加入有高温稳定剂。
通过在第二次焙烧过程中加入高温稳定剂，可以改善反应体系的稳定性和反应速率，避免物料板结，提高产物的品质和产量。
作为参考地，高温稳定剂例如可包括二氧化硅、三氧化二铝、氧化钙和氧化镁中的至少一种。
本申请采用上述物质作为高温稳定剂，可具有以下效果：
效果一，改善物料的流动性：上述高温稳定剂可以促进第二次焙烧过程中物料的流动性，使得物料更加均匀地分布在反应设备内，从而提高焙烧效率和产量；
效果二，改善产物的质量：上述高温稳定剂可在一定程度上控制反应体系的化学环境，避免不必要的副反应和杂质的产生，从而提高产物的纯度和质量；
效果三，增强热稳定性：上述高温稳定剂可增强物料的热稳定性，防止物料在高温下发生脱 失和变形，从而确保焙烧过程的稳定性和安全性。
示例性地，高温稳定剂的质量可以为铁铝渣和含镍工业固废的总质量的2％-5％，如2％、2.5％、3％、3.5％、4％、4.5％或5％等，也可以为2％-5％范围内的其它任意值。
在一些可选的实施方式中，第二次焙烧过程中还辅助有微波处理。
通过在第二次焙烧中增加微波辅助技术，相较于传统或常规焙烧，可大大增加反应温度和反应速率，使得第二次还原焙烧反应更加彻底。
作为参考地，微波处理使用的微波功率为3KW-5KW，如3KW、3.5KW、4KW、4.5KW或5KW等，也可以为3KW-5KW范围内的其它任意值。
需说明的是，若微波功率低于3KW，会使得材料加热不均匀，导致焙烧不完全。此外，微波功率低可能会导致加热时间过长，从而增加能耗和生产成本。若微波功率高于5KW，会导致材料表面过度加热，从而产生局部高温区域，影响金属的回收率。
进一步地，回收第一次焙烧和/或第二次焙烧过程中产生的酸性气体。
也即，在一些实施方式中，可单独对第一次焙烧过程中产生的酸性气体进行回收；在另一些实施方式中，可单独对第二次焙烧过程中产生的酸性气体进行回收；在其它一些实施方式中，可将第一次焙烧和第二次焙烧过程中产生的酸性气体均进行回收。具体采用哪种方式可视具体情况而定。
作为参考地，回收方式例如可包括：用酸溶液回收酸性气体。
上述酸溶液例如可包括硫酸溶液，硫酸溶液的除了作为焙烧渣的浸出酸，同时具有处理焙烧尾气的作用，吸收尾气中的SO3。而其他酸溶液不同时具备上述两个作用。
示例性地，酸溶液的浓度可以为95％-98％，如95％、95.5％、96％、96.5％、97％、97.5％或98％等，也可以为95％-98％范围内的其它任意值。
在一些可选的实施方式中，可以将酸性气体先经催化剂催化氧化处理，然后再通过酸溶液进行回收。
通过先进行催化氧化处理，可将酸性气体(SO2)氧化成SO3，从而更利于后续硫酸溶液的吸收。
示例性地，上述催化剂例如可包括五氧化二钒，此外，还可以包括金属氧化物、过渡金属离子、活性炭、硫酸钛催化剂和氧化物复合催化剂等能够将二氧化硫催化氧化为三氧化硫的物质。
但相较于其他催化剂，五氧化二钒至少具有以下优势：
催化活性高，在催化氧化二氧化硫的反应中表现出良好的催化效果；反应选择性较高，可以将二氧化硫催化氧化为三氧化硫，并且不会发生其他副反应；具有较好的耐久性和稳定性，可以在反应条件较为苛刻的环境中长时间保持催化效果；制备方法较为简单，成本相对较低，易于工业化生产和应用。
进一步地，本申请提供的处理方法还可包括：将第二次焙烧后的焙烧固体产物进行分离，得到磁性物镍钛物及非磁性焙烧渣。
作为参考地，分离可采用磁选分离方式进行。此外，也不排除可以采用其它能够达到相同分离效果的分离方法。
示例性地，磁选分离所用的磁场强度可以为50mT-500mT，如50mT、100mT、150mT、200mT、250mT、300mT、350mT、400mT、450mT或500mT等，也可以为50mT-500mT范围内的其它任意值。
若磁场强度低于50mT，会使得金属分选时的磁力不足，使得分离效果变差，磁性物质分离不彻底，影响分离质量和产量；若磁场强度高于500mT，可能会导致磁选机的温度过高，使得磁选机过载，同时会使得磁选机中的磁线密度过大，从而造成粒子聚集或者聚结，影响磁选效果。
承上，本申请提供的方法中，通过第一次焙烧可将铁铝渣中的Fe元素和含镍工业固废中的Ni元素转化为金属氧化物，第二次焙烧可将第一次焙烧生成的金属氧化物还原为金属单质。具体的，第一次焙烧先将待处理物料中的镍、铁进行氧化，第二次焙烧在还原剂的作用下，将镍、铁金属氧化物还原为金属单质，使得固废中的镍、铁元素与其他物质和杂质元素进行脱离，再通过磁选分离可有效回收得到镍、铁金属。
在一些可选的实施方式中，在分离前，还可对焙烧固体产物进行破碎处理。
破碎处理例如可以采用研磨方式，具体的条件可与含镍工业固废和铁铝渣进行破碎以达到预设粒径的条件相同。
进一步地，可对非磁性焙烧渣进行酸浸。
作为参考地，酸浸所用的酸溶液与非磁性焙烧渣的液固比可以为8mL：1g-10mL：1g，如8mL：1g、8.5mL：1g、9mL：1g、9.5mL：1g或10mL：1g等，也可以为8mL：1g-10mL：1g范围内的其它任意值。
若上述液固比小于8mL：1g，不利于将有价金属元素充分浸出；若上述液固比高于10mL：1g，会增加成本。
作为参考地，酸浸温度可以为70℃-90℃，如70℃、75℃、80℃、85℃或90℃等，也可以为70℃-90℃范围内的其它任意值。酸浸时间可以为1h-2h，如1h、1.5h或2h等，也可以为1h-2h范围内的其它任意值。
若酸浸温度低于70℃或酸浸时间短于1h，不利于将有价金属元素充分浸出。若酸浸温度高于90℃或酸浸时间长于2h，会增加能耗，造成浪费，降低经济效益；此外，酸浸过程中可能产生大量的酸性废水和酸性废气，如果酸浸时间过长，将会增加废物处理的成本，同时会对环境造成污染。
在一些较佳的实施方式中，可将上述回收有酸性气体的酸溶液作为浸出液对非磁性焙烧渣进 行酸浸，从而可实现资源的最大化重复利用。
酸浸后，可回收酸浸所得的浸出液中的有价金属元素。此外，可将酸浸所得的浸出渣用于下一轮焙烧，或作为建筑用渣，或用于进行填埋处理等。
承上，通过上述处理方法可以将固废中的镍、铁进行分离和回收，同时还可以充分利用焙烧产生的酸性尾气，而吸收焙烧尾气后的酸又可作为浸出酸作用于非磁性焙烧，进而回收其中的Al、Ni、Co、Mn元素，酸浸渣可返回焙烧处理、或作为建筑用渣、或进行填埋处理。整个工艺流程基本实现了循环利用，合理利用了大量的工业固废的同时，还有效回收了工业固废中的有价金属元素，该工艺简单，成本较低，有利于工程大规模投入使用。
以下结合实施例对本申请的特征和性能作进一步的详细描述。
实施例1
本实施例提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其主要包括以下步骤：
S1、分别称量1000g含镍工业固废和1000g铁铝渣放入托盘中，并添加含镍工业固废以及铁铝渣总质量的0.3％的聚羧酸减水剂，将托盘放入鼓风干燥箱内进行脱水干燥，干燥温度为120℃，干燥时间为6h；
S2、将干燥后的含镍工业固废、铁铝渣分别进行破碎、研磨，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为3：1；
S3、将研磨后的含镍工业固废和铁铝渣两种粉料分别过100目筛网，取筛下物粉料，得到粒径为0.15mm的粉末焙烧原料；
S4、将过筛后的含镍工业固废和铁铝渣分别按重量比为0.2：1倒入高速混合机中，并添加含镍工业固废和铁铝渣总质量的2％的活性助熔剂(碳酸钠)和1％的金属焙烧助剂(钼酸钠)，设置高速混合机的转速为45r/min，混合时长为5min；
S5、将高速混合机中充分混合均匀后的工业固废粉末放入管式炉内，设置第一次焙烧温度为650℃，焙烧时间为45min；第一次焙烧结束后，向焙烧产物中添加5％的秸秆型生物质还原剂以及2％的高温稳定剂(二氧化硅)，设置第二次焙烧温度为1050℃，焙烧时间为100min，微波功率为3.5KW进行焙烧处理；
S6、将焙烧产生的酸性气体经V2O5催化氧化处理后，通入浓度为95％的硫酸回收SO3气体，SO3回收率可达到87.6％；
S7、待焙烧产物自然冷却后，倒入砂磨机内进行研磨处理，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为3：1，选择磁场强度为50mT对焙烧产物进一步磁选分离，得到所述的具有磁性的镍铁合金及非磁性的焙烧渣，镍金属回收率为73.6％，铁金属回收率为68.3％；
S8、将S6所得的硫酸对非磁性焙烧渣进行酸浸，液固比为10mL：1g，酸浸温度为75℃，浸出时间为1.5h；
S9：回收酸浸液中的Al、Ni、Co、Mn元素，将酸浸渣返回焙烧处理。
实施例2
本实施例提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其主要包括以下步骤：
S1、分别称量1000g含镍工业固废和1000g铁铝渣放入托盘中，并添加含镍工业固废以及铁铝渣总质量的0.3％的聚羧酸减水剂，将托盘放入鼓风干燥箱内进行脱水干燥，干燥温度选择120℃，干燥时间为6h；
S2、将干燥后的含镍工业固废、铁铝渣分别进行破碎、研磨，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为10：1；
S3、将研磨后的含镍工业固废和铁铝渣两种粉料分别过100目筛网，取筛下物粉料，得到粒径为0.15mm的粉末焙烧原料；
S4、将过筛后的含镍工业固废和铁铝渣分别按重量比为0.5：1倒入高速混合机中，并添加含镍工业固废和铁铝渣总质量的3％的活性助熔剂(硫酸钠)和2％的金属焙烧助剂(钼酸钠)，设置高速混合机的转速为45r/min，混合时长为5min；
S5、将高速混合机中充分混合均匀后的工业固废粉末放入管式炉内，设置第一次焙烧温度为700℃，焙烧时间为45min；第一次焙烧结束后，向焙烧产物中添加10％的秸秆型生物质还原剂以及3.5％的高温稳定剂(三氧化二铝)，设置第二次焙烧温度为1100℃，焙烧时间为100min，微波功率为3.5KW进行焙烧处理；
S6、将焙烧产生的酸性气体经V2O5催化氧化处理后，通入浓度为95％的硫酸回收SO3气体，SO3回收率可达到88.5％；
S7、待焙烧产物自然冷却后，倒入砂磨机内进行研磨处理，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为3：1，选择磁场强度为100mT对焙烧产物进一步磁选分离，得到所述的具有磁性的镍铁合金及非磁性的焙烧渣，镍金属回收率为77.3％，铁金属回收率为70.1％；
S8、将S6所得的硫酸对非磁性焙烧渣进行酸浸，液固比为10mL：1g，酸浸温度为80℃，浸出时间为2h；
S9：回收酸浸液中的Al、Ni、Co、Mn元素，将酸浸渣作为建筑用渣。
实施例3
本实施例提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其主要包括以下步骤：
S1、分别称量1000g含镍工业固废和1000g铁铝渣放入托盘中，并添加含镍工业固废以及铁铝渣总质量的0.3％的聚羧酸减水剂，将托盘放入鼓风干燥箱内进行脱水干燥，干燥温度选择120℃，干燥时间为6h；
S2、将干燥后的含镍工业固废、铁铝渣分别进行破碎、研磨，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为15：1；
S3、将研磨后的含镍工业固废和铁铝渣两种粉料分别过100目筛网，取筛下物粉料，得到粒径为0.15mm的粉末焙烧原料；
S4、将过筛后的含镍工业固废和铁铝渣分别按重量比为0.7：1倒入高速混合机中，并添加含镍工业固废和铁铝渣总质量的5％的活性助熔剂(氯化钠)和3％的金属焙烧助剂(钼酸钠)，设置高速混合机的转速为45r/min，混合时长为10min；
S5、将高速混合机中充分混合均匀后的工业固废粉末放入管式炉内，设置第一次焙烧温度为700℃，焙烧时间为45min；第一次焙烧结束后，向焙烧产物中添加10％的秸秆型生物质还原剂以及4％的高温稳定剂(氧化钙)，设置第二次焙烧温度为1100℃，焙烧时间为100min，微波功率为3.5KW进行焙烧处理；
S6、将焙烧产生的酸性气体经V2O5催化氧化处理后，通入浓度为95％的硫酸回收SO3气体，SO3回收率可达到86.4％；
S7、待焙烧产物自然冷却后，倒入砂磨机内进行研磨处理，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为3：1，选择磁场强度为200mT对焙烧产物进一步磁选分离，得到所述的具有磁性的镍铁合金及非磁性的焙烧渣，镍金属回收率为81.2％，铁金属回收率为72.9％；
S8、将S6所得的硫酸对非磁性焙烧渣进行酸浸，液固比为10mL：1g，酸浸温度为85℃，浸出时间为2h；
S9：回收酸浸液中的Al、Ni、Co、Mn元素，将酸浸渣用于填埋处理。
实施例4
本实施例提供一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其主要包括以下步骤：
S1、分别称量1000g含镍工业固废和1000g铁铝渣放入托盘中，并添加含镍工业固废以及铁铝渣总质量的0.5％的聚羧酸减水剂，将托盘放入鼓风干燥箱内进行脱水干燥，干燥温度选择120℃，干燥时间为6h；
S2、将干燥后的含镍工业固废、铁铝渣分别进行破碎、研磨，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为30：1；
S3、将研磨后的含镍工业固废和铁铝渣两种粉料分别过100目筛网，取筛下物粉料，得到粒 径为0.15mm的粉末焙烧原料；
S4、将过筛后的含镍工业固废和铁铝渣分别按重量比为1：1倒入高速混合机中，并添加含镍工业固废和铁铝渣总质量的8％的活性助熔剂(硫酸钠)和5％的金属焙烧助剂(钼酸钠)，设置高速混合机的转速为60r/min，混合时长为10min；
S5、将高速混合机中充分混合均匀后的工业固废粉末放入管式炉内，设置第一次焙烧温度为840℃，焙烧时间为60min；第一次焙烧结束后，向焙烧产物中添加20％的秸秆型生物质还原剂以及5％的高温稳定剂(氧化镁)，设置第二次焙烧温度为1250℃，焙烧时间为120min，微波功率为3.5KW进行焙烧处理；
S6、将焙烧产生的酸性气体经V2O5催化氧化处理后，通入浓度为95％的硫酸回收SO3气体，SO3回收率可达到88.5％；
S7、待焙烧产物自然冷却后，倒入砂磨机内进行研磨处理，砂磨机的转速为300r/min，砂磨时间为60min，磨球与原料的体积比为10：1，选择磁场强度为350mT对焙烧产物进一步磁选分离，得到所述的具有磁性的镍铁合金及非磁性的焙烧渣，镍金属回收率为87.3％，铁金属回收率为75.1％；
S8、将S6所得的硫酸对非磁性焙烧渣进行酸浸，液固比为10mL：1g，酸浸温度为85℃，浸出时间为2h；
S9：回收酸浸液中的Al、Ni、Co、Mn元素，将酸浸渣用于返回焙烧处理。
实施例5
本实施例与实施例4的区别在于：用于第一次焙烧的铁铝渣和含镍工业固废的粒径为0.1mm。本实施例的镍金属回收率为88.5％，铁金属回收率为77.3％。
实施例6
本实施例与实施例4的区别在于：助熔剂的质量为铁铝渣和含镍工业固废的总质量的10％。本实施例的镍金属回收率为89.1％，铁金属回收率为78.2％。
实施例7
本实施例与实施例4的区别在于：焙烧助剂为铬酸钠。本实施例的镍金属回收率为86.5％，铁金属回收率为75.7％。
实施例8
本实施例与实施例4的区别在于：焙烧助剂的质量为含镍工业固废和铁铝渣的总质量的6％。本实施例的镍金属回收率为87.9％，铁金属回收率为76.1％。
实施例9
本实施例与实施例4的区别在于：表面活性剂为烷基苯磺酸盐。本实施例的镍金属回收率为85.3％，铁金属回收率为78.1％。
实施例10
本实施例与实施例4的区别在于：表面活性剂的质量为含镍工业固废和铁铝渣的总质量的0.7％。本实施例的镍金属回收率为87.8％，铁金属回收率为75.4％。
实施例11
本实施例与实施例4的区别在于：第一次焙烧和第二次焙烧均于马弗炉中进行。本实施例的镍金属回收率为88.1％，铁金属回收率为76.8％。
实施例12
本实施例与实施例4的区别在于：第一次焙烧的温度为600℃。本实施例的镍金属回收率为71.3％，铁金属回收率为70.9％。
实施例13
本实施例与实施例4的区别在于：第一次焙烧的温度为950℃。本实施例的镍金属回收率为88.5％，铁金属回收率为77.3％。
实施例14
本实施例与实施例4的区别在于：第二次焙烧的温度为800℃。本实施例的镍金属回收率为82.4％，铁金属回收率为73.2％。
实施例15
本实施例与实施例4的区别在于：第二次焙烧的温度为1350℃。本实施例的镍金属回收率为89.3％，铁金属回收率为78.9％。
实施例16
本实施例与实施例4的区别在于：第二次焙烧过程中微波功率为3KW。本实施例的镍金属回收率为85.7％，铁金属回收率为73.8％。
实施例17
本实施例与实施例4的区别在于：第二次焙烧过程中微波功率为5KW。本实施例的镍金属回收率为89.3％，铁金属回收率为78.6％。
对比例1
本对比例与实施例4的区别在于：用于第一次焙烧的铁铝渣和含镍工业固废的粒径为0.5mm。
对比例2
本对比例与实施例4的区别在于：用于第一次焙烧的铁铝渣和含镍工业固废的质量比为1:0.05。
对比例3
本对比例与实施例4的区别在于：用于第一次焙烧的铁铝渣和含镍工业固废的质量比为1:1.2。
对比例4
本对比例与实施例4的区别在于：第一次焙烧的温度为500℃。
对比例5
本对比例与实施例4的区别在于：第一次焙烧的温度为1000℃。
对比例6
本对比例与实施例4的区别在于：未使用助熔剂。
对比例7
本对比例与实施例4的区别在于：助熔剂的质量为铁铝渣和含镍工业固废的总质量的1％。
对比例8
本对比例与实施例4的区别在于：助熔剂的质量为铁铝渣和含镍工业固废的总质量的15％。
对比例9
本对比例与实施例4的区别在于：未使用焙烧助剂。
对比例10
本对比例与实施例4的区别在于：焙烧助剂的质量为含镍工业固废和铁铝渣的总质量的0.5％。
对比例11
本对比例与实施例4的区别在于：焙烧助剂的质量为含镍工业固废和铁铝渣的总质量的8％。
对比例12
本对比例与实施例4的区别在于：未进行预活化处理。
对比例13
本对比例与实施例4的区别在于：表面活性剂的质量为含镍工业固废和铁铝渣的总质量的0.1％。
对比例14
本对比例与实施例4的区别在于：表面活性剂的质量为含镍工业固废和铁铝渣的总质量的1％。
对比例15
本对比例与实施例4的区别在于：第二次焙烧的温度为600℃。
对比例16
本对比例与实施例4的区别在于：第二次焙烧的温度为1500℃。
对比例17
本对比例与实施例4的区别在于：还原剂的质量为铁铝渣和含镍工业固废的总质量的25％。
对比例18
本对比例与实施例4的区别在于：第二次焙烧过程中未加入高温稳定剂。
对比例19
本对比例与实施例4的区别在于：第二次焙烧过程中高温稳定剂的质量为铁铝渣和含镍工业 固废的总质量的1％。
对比例20
本对比例与实施例4的区别在于：第二次焙烧过程中高温稳定剂的质量为铁铝渣和含镍工业固废的总质量的8％。
对比例21
本对比例与实施例4的区别在于：第二次焙烧过程中未辅助进行微波处理。
对比例22
本对比例与实施例4的区别在于：第二次焙烧过程中微波功率为1KW。
对比例23
本对比例与实施例4的区别在于：第二次焙烧过程中微波功率为10KW。
试验例1-17以及对比例1-23对应的金属回收率统计如表1所示。
表1金属回收率结果

由表1可以看出，本申请实施例提供的方案较对比例具有更高的镍回收率及铁回收率。
综上，本申请提供的全链条一体化处理废旧电池定向循环过程中废渣的方法成本较低，能够有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染，不失成为废旧电池回收利用的有效方法。
以上仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。
工业实用性
本申请提供的全链条一体化处理废旧电池定向循环过程中废渣的方法成本较低，能够有效地对废旧电池处理过程中所涉及的铁铝渣和含镍工业固废进行资源化重复利用，既避免了镍资源以及铁资源等的浪费，又避免或降低了上述物质对环境所造成的污染，不失成为废旧电池回收利用的有效方法。

Claims (26)

  1. 一种全链条一体化处理废旧电池定向循环过程中废渣的方法，其特征在于，包括以下步骤：
    将铁铝渣和含镍工业固废进行第一次焙烧，得到镍的氧化物和铁的氧化物；随后在还原条件下进行第二次焙烧，得到镍单质和铁单质；
    其中，第一次焙烧的温度不低于600℃。
  2. 根据权利要求1所述的方法，其特征在于，第一次焙烧包括以下特征中的至少一种：
    特征一：第一次焙烧的温度为600℃-950℃；
    特征二：第一次焙烧的时间为30min-60min；
    特征三：第一次焙烧是于管式炉中进行；
    特征四：用于第一次焙烧的铁铝渣和含镍工业固废的粒径不超过0.15mm；
    特征五：用于第一次焙烧的铁铝渣和含镍工业固废的质量比为1:0.2-1:1。
  3. 根据权利要求1或2所述的方法，其特征在于，第二次焙烧包括以下特征中的至少一种：
    特征一：第二次焙烧的温度为800-1350℃；
    特征二：第二次焙烧的时间为45min-120min；
    特征三：第二次焙烧是于管式炉中进行；
    特征四：第二次焙烧是于还原剂存在的条件下进行；
    特征五：第二次焙烧过程中还加入有高温稳定剂；
    特征六：第二次焙烧过程中还辅助有微波处理。
  4. 根据权利要求3所述的方法，其特征在于，特征四包括以下子特征中的至少一种：
    子特征一：所述还原剂包括生物质还原剂；进一步地，所述生物质还原剂包括秸秆类生物质；
    子特征二：所述还原剂的质量为铁铝渣和含镍工业固废的总质量的5％-20％；
    和/或，特征五包括以下子特征中的至少一种：
    子特征一：所述高温稳定剂包括二氧化硅、三氧化二铝、氧化钙和氧化镁中的至少一种；
    子特征二：所述高温稳定剂的质量为铁铝渣和含镍工业固废的总质量的2％-5％；
    和/或，特征六中微波处理使用的微波功率为3KW-5KW。
  5. 根据权利要求1-4任一项所述的方法，其特征在于，在第一次焙烧之前，还包括将助熔剂和焙烧助剂中的至少一种与铁铝渣和含镍工业固废混合。
  6. 根据权利要求5所述的方法，其特征在于，所述助熔剂包括以下特征中的至少一种：
    特征一：所述助熔剂包括钠基助熔剂；
    特征二：所述助熔剂的质量为铁铝渣和含镍工业固废的总质量的2％-10％；
    和/或，所述焙烧助剂包括以下特征中的至少一种：
    特征一：所述焙烧助剂包括金属盐；
    特征二：所述焙烧助剂的质量为含镍工业固废和铁铝渣的总质量的1％-6％。
  7. 根据权利要求6所述的方法，其特征在于，所述助熔剂包括硫酸钠、碳酸钠和氯化钠中的至少一种；
    和/或，所述焙烧助剂包括钼酸钠、铬酸钠、钒酸铵、钛酸钠、铜酸钠、锰酸钠和铅酸钠中的至少一种。
  8. 根据权利要求5-7任一项所述的方法，其特征在于，物料混合包括以下特征中的至少一种：
    特征一：混合是于45r/min-90r/min的条件下进行；
    特征二：混合时间为5min-30min。
  9. 根据权利要求1-8任一项所述的方法，其特征在于，在第一次焙烧之前，还包括对含镍工业固废和铁铝渣进行前处理；
    前处理包括以下特征中的至少一种：
    特征一：将含镍工业固废和铁铝渣进行破碎以达到预设粒径；
    特征二：将含镍工业固废和铁铝渣进行预活化处理。
  10. 根据权利要求9所述的方法，其特征在于，破碎包括以下特征中的至少一种：
    特征一：破碎采用砂磨方式进行；
    特征二：破碎是于300r/min-1000r/min的条件下进行；
    特征三：破碎时间为60min-300min。
  11. 根据权利要求10所述的方法，其特征在于，砂磨过程中使用的磨球与待磨物料的体积比为3:1-30:1。
  12. 根据权利要求9-11任一项所述的方法，其特征在于，预活化处理包括：将含镍工业固废和铁铝渣与表面活性剂混合。
  13. 根据权利要求12所述的方法，其特征在于，所述表面活性剂包括以下特征中的至少一种：
    特征一：所述表面活性剂包括聚羧酸减水剂和烷基苯磺酸盐中的至少一种；
    特征二：所述表面活性剂的质量为含镍工业固废和铁铝渣的总质量的0.3％-0.7％。
  14. 根据权利要求13所述的方法，其特征在于，所述表面活性剂包括聚羧酸减水剂。
  15. 根据权利要求9-14任一项所述的方法，其特征在于，第一次焙烧之前，还包括将预活化处理后的物料进行干燥。
  16. 根据权利要求15所述的方法，其特征在于，干燥包括以下特征中的至少一种：
    特征一：干燥采用鼓风干燥方式进行；
    特征二：干燥温度为100℃-150℃，和/或，干燥时间为4h-8h。
  17. 根据权利要求1-16任一项所述的方法，其特征在于，所述处理方法还包括：回收第一次焙烧和/或第二次焙烧过程中产生的酸性气体。
  18. 根据权利要求17所述的方法，其特征在于，回收方式包括：用酸溶液回收所述酸性气体。
  19. 根据权利要求18所述的方法，其特征在于，所述酸溶液包括以下特征中的至少一种：
    特征一：所述酸溶液包括硫酸溶液；
    特征二：所述酸溶液的浓度为95％-98％。
  20. 根据权利要求18或19所述的方法，其特征在于，将所述酸性气体经催化剂催化氧化处理后再通过酸溶液进行回收。
  21. 根据权利要求20所述的方法，其特征在于，所述催化剂包括五氧化二钒。
  22. 根据权利要求1-21任一项所述的方法，其特征在于，所述方法还包括：将第二次焙烧后的焙烧固体产物进行分离，得到磁性物镍钛物及非磁性焙烧渣。
  23. 根据权利要求22所述的方法，其特征在于，分离包括以下特征中的至少一种：
    特征一：分离采用磁选分离方式进行；进一步，磁选分离所用的磁场强度为50mT-500mT；
    特征二：分离前，还包括对所述焙烧固体产物进行破碎处理。
  24. 根据权利要求22或23所述的方法，其特征在于，对所述非磁性焙烧渣进行酸浸。
  25. 根据权利要求24所述的方法，其特征在于，酸浸包括以下特征中的至少一种：
    特征一：酸浸所用的酸溶液与所述非磁性焙烧渣的液固比为8mL：1g-10mL：1g；
    特征二：酸浸温度为70℃-90℃；
    特征三：酸浸时间为1h-2h；
    特征四：将回收有酸性气体的酸溶液作为浸出液对所述非磁性焙烧渣进行酸浸。
  26. 根据权利要求25所述的方法，其特征在于，还包括：回收酸浸后得到的浸出液中的有价金属元素；和/或，将酸浸后得到的浸出渣用于下一轮焙烧或作为建筑用渣或用于进行填埋处理。
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Publication number Priority date Publication date Assignee Title
CN117480267A (zh) * 2023-09-20 2024-01-30 广东邦普循环科技有限公司 一种铁铝渣与红土镍矿酸浸渣资源化利用方法
WO2025081365A1 (zh) * 2023-10-18 2025-04-24 广东邦普循环科技有限公司 全链条一体化废旧三元电池粉回收的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229481A (ja) * 2011-04-27 2012-11-22 Japan Metals & Chem Co Ltd 使用済みリチウムイオン電池類の有価物の分別回収方法
CN111411217A (zh) * 2020-04-26 2020-07-14 中国恩菲工程技术有限公司 高镁型红土镍矿还原制备镍铁产物的方法
CN115109934A (zh) * 2022-08-31 2022-09-27 湖南五创循环科技有限公司 一种废旧电池中有价金属分离提取的方法
WO2022247356A1 (zh) * 2021-05-26 2022-12-01 山东墨龙石油机械股份有限公司 一种含镍金属的冶炼方法及其应用
WO2023029898A1 (zh) * 2021-09-01 2023-03-09 格林美股份有限公司 一种从废旧锂离子电池中回收有价金属的方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW251373B (zh) * 1993-05-20 1995-07-11 Fujidenki Kagaku Kk
WO1995006948A1 (en) * 1993-08-31 1995-03-09 Fuji Electrochemical Co., Ltd. Magnetic oxide material and method of its manufacture
CN101323909B (zh) * 2008-07-17 2010-06-23 东北大学 一种微波选择性还原焙烧-稀酸浸出氧化镍矿的方法
CN101392320B (zh) * 2008-10-31 2010-07-28 东北大学 微波还原焙烧-针铁矿沉淀转化法处理含镍红土矿的方法
CN101767825B (zh) * 2009-11-23 2010-12-08 中国科学院过程工程研究所 一种由红土镍矿制备氧化铬的方法
CN102061397B (zh) * 2010-06-02 2012-10-03 四川龙蟒矿冶有限责任公司 一种从钒钛磁铁矿中回收利用钒、铬、钛、铁的方法
CN102127633B (zh) * 2011-03-03 2012-07-04 湖南长拓高科冶金有限公司 微波处理红土镍矿富集镍铁的方法
CN103801192B (zh) * 2014-02-21 2015-11-11 陕西理工学院 一种水泥窑炉烟气脱硝的工艺
CN104060114B (zh) * 2014-07-02 2016-06-15 江苏大学 一种低品位镍钼矿直接冶炼镍钼铁合金的方法
CN106086487B (zh) * 2016-08-24 2017-12-15 北京矿冶研究总院 一种低品位钼镍矿脱硫脱砷‑焙砂熔炼钼镍铁合金的方法
CN108165733A (zh) * 2018-01-02 2018-06-15 昆明理工大学 一种硅镁型红土镍矿中镍、铁、镁多金属综合回收的方法
CN113528810A (zh) * 2021-06-30 2021-10-22 广东邦普循环科技有限公司 处理红土镍矿浸出渣和黄钠铁矾渣的混合物的方法和应用
CN114318005B (zh) * 2022-01-04 2022-11-29 中南大学 一种微波处理低品位红土镍矿制备高品位镍产品的方法
CN114716269B (zh) * 2022-03-31 2023-11-10 华南理工大学 一种石棉尾矿或镍铁渣焙烧脱毒/活化制取枸溶性肥料的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229481A (ja) * 2011-04-27 2012-11-22 Japan Metals & Chem Co Ltd 使用済みリチウムイオン電池類の有価物の分別回収方法
CN111411217A (zh) * 2020-04-26 2020-07-14 中国恩菲工程技术有限公司 高镁型红土镍矿还原制备镍铁产物的方法
WO2022247356A1 (zh) * 2021-05-26 2022-12-01 山东墨龙石油机械股份有限公司 一种含镍金属的冶炼方法及其应用
WO2023029898A1 (zh) * 2021-09-01 2023-03-09 格林美股份有限公司 一种从废旧锂离子电池中回收有价金属的方法
CN115109934A (zh) * 2022-08-31 2022-09-27 湖南五创循环科技有限公司 一种废旧电池中有价金属分离提取的方法

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