CN114921653A - Ternary lithium battery material reduction device, control method and lithium recovery method - Google Patents

Ternary lithium battery material reduction device, control method and lithium recovery method Download PDF

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Publication number
CN114921653A
CN114921653A CN202210575368.5A CN202210575368A CN114921653A CN 114921653 A CN114921653 A CN 114921653A CN 202210575368 A CN202210575368 A CN 202210575368A CN 114921653 A CN114921653 A CN 114921653A
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gas
pipeline
lithium battery
ternary lithium
battery material
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CN114921653B (en
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周强
蔡金玲
蒋振宇
倪俊
尹红兵
蒋岳师
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Advanced Corp for Materials and Equipments Co Ltd
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Advanced Corp for Materials and Equipments Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a ternary lithium battery material reduction device, a control method of the ternary lithium battery material reduction device and a lithium recovery method. The ternary lithium battery material reduction device comprises a heating furnace, a conveyor belt, gas pipelines, at least two gas source pipelines and control valves arranged corresponding to the gas source pipelines. The conveyer belt includes the feeding section, reaction section and the ejection of compact section that set gradually along self direction of transfer. The gas line passes at least through the reaction zone of the conveyor. The gas duct includes a first gas inlet portion. The air source pipeline comprises at least two air source pipelines and control valves arranged corresponding to the air source pipelines, and the at least two air source pipelines are respectively connected with the first air inlet part through the corresponding control valves. And adjusting the control valve to enable the gas source pipeline for conveying the required working gas to be communicated with the first gas inlet part so as to provide the required conditions for the reduction reaction of the ternary lithium battery material. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of the ternary lithium battery material, and is wide in application range.

Description

Ternary lithium battery material reduction device, control method and lithium recovery method
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a ternary lithium battery material reduction device, a control method of the ternary lithium battery material reduction device and a lithium recovery method.
Background
The anode material of the waste ternary lithium ion battery (hereinafter referred to as ternary lithium battery material) contains heavy metals such as lithium, nickel, cobalt, manganese, copper and the like, so that the recovery value is high. Lithium recovery of ternary lithium battery materials involves reduction and leaching steps. After the ternary lithium battery material is reduced, the leaching rate of lithium can be improved more.
The conventional ternary lithium battery material reduction device can only adopt a specific reduction process, such as a process of reducing by using carbon or a process of reducing by using a specific reducing gas. Therefore, the application range of the reduction device of the ternary lithium battery material is limited, and the reduction device is easily limited by production raw materials.
Disclosure of Invention
The invention mainly aims to provide a ternary lithium battery material reduction device, a control method of the ternary lithium battery material reduction device and a lithium recovery method, and aims to solve the technical problems that the use range of the ternary lithium battery material reduction device is limited and is easily limited by production raw materials.
In order to achieve the above object, a first aspect of the present invention provides a ternary lithium battery material reduction device. The ternary lithium battery material reduction device comprises a heating furnace, a conveyor belt, gas pipelines, at least two gas source pipelines and control valves arranged corresponding to the gas source pipelines.
The heating furnace has a heating zone.
The conveyer belt comprises a feeding section, a reaction section and a discharging section which are arranged in sequence along the self conveying direction, and the reaction section passes through the heating zone of the heating furnace.
The gas pipeline is located one side of conveyer belt near the heating furnace, and the gas pipeline is at least through the reaction section of conveyer belt in order to carry out required working gas of reduction to reaction section release ternary lithium electricity material, and the gas pipeline includes the first portion of admitting air that is used for accepting working gas. The working gas is a reducing gas or a protective gas.
The gas source pipeline comprises at least two gas source pipelines and control valves arranged corresponding to the gas source pipelines, wherein the at least two gas source pipelines are respectively connected with the first gas inlet part through the corresponding control valves and are used for conveying different working gases to the gas pipelines through the first gas inlet part.
Optionally, the reducing gas comprises natural gas and ammonia knock-out gas.
The at least two gas source pipelines at least comprise a first pipeline for conveying natural gas, a second pipeline for conveying ammonia decomposition gas and a third pipeline for conveying protective gas.
Optionally, the gas conduit also passes through the feed and discharge sections of the conveyor for releasing shielding gas to the feed and discharge sections.
The gas pipeline comprises a second gas inlet part and a third gas inlet part, the second gas inlet part is used for receiving protective gas, the second gas inlet part is positioned on the part of the gas pipeline passing through the feeding section, and the third pipeline is connected with the second gas inlet part through a corresponding control valve.
The third air inlet part is positioned at the part of the air inlet pipeline passing through the discharging section, and the third pipeline is connected with the second air inlet part through a corresponding control valve.
Optionally, the system further comprises an oxygen analyzer and/or a gas flow meter, wherein the oxygen analyzer is arranged in the heating zone of the heating furnace;
the position that the gas pipeline is close to first air inlet portion is equipped with gas flowmeter, and at least one department that the gas pipeline is close to in second air inlet portion and the third air inlet portion is equipped with gas flowmeter.
Optionally, the gas conduit further comprises a tail gas outlet.
The second aspect of the present invention provides a control method for the above ternary lithium battery material reduction apparatus, including the following steps:
one of the at least two gas source pipelines is communicated with the first gas inlet part by adjusting the control valve, and working gas in the gas source pipeline is introduced into the gas pipeline;
adding a reducing agent into the ternary lithium battery material, and reducing the ternary lithium battery material in an atmosphere provided by working gas, wherein the working gas is protective gas; or
And reducing the ternary lithium battery material in an atmosphere provided by working gas, wherein the working gas is reducing gas.
Optionally, at least a first duct, a second duct and a third duct are included in the at least two gas source ducts, and the gas duct includes a second gas inlet portion and a third gas inlet portion.
The method comprises the following steps of adding a reducing agent into the ternary lithium battery material, and reducing the ternary lithium battery material in an atmosphere provided by working gas:
the third pipeline is communicated with the second air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The third pipeline is communicated with the first air inlet part by adjusting the control valve, and the protective gas in the third pipeline is in a range of 10-14 m 3 The flow rate/h is introduced into the gas line.
And placing a mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section of a conveyor belt, conveying the mixed material to a heating area through the conveyor belt, and reducing for 1.5-2.5 hours at 500-700 ℃ under the condition that protective gas in a third pipeline provides a protective gas atmosphere. Wherein the mass of the reducing agent is 9-11% of that of the ternary lithium battery material. The reducing agent is activated carbon.
Optionally, at least a first duct, a second duct and a third duct are included in the at least two gas source ducts, and the gas duct includes a second gas inlet portion and a third gas inlet portion. The reducing gas is ammonia decomposition gas.
The step of reducing the ternary lithium battery material in the atmosphere provided by the ammonia decomposition gas comprises the following steps:
the third pipeline is communicated with the second air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The second pipeline is communicated with the first air inlet part by adjusting the control valve, and the hydrogen in the ammonia decomposition gas in the second pipeline is 20-30 m 3 The flow rate/h is introduced into the gas line.
The ternary lithium battery material is placed in a feeding section of a conveying belt, conveyed to a heating area through the conveying belt and reduced for 1.5-2.5 hours at the temperature of 500-700 ℃ under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere.
Optionally, at least one of the at least two gas source pipelines includes at least a first pipeline, a second pipeline, and a third pipeline, and the gas pipeline includes a second gas inlet portion and a third gas inlet portion. The reducing gas is natural gas.
The method for reducing the ternary lithium battery material in the atmosphere provided by natural gas comprises the following steps:
the third pipeline is communicated with the second air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line.
The first pipeline is communicated with the first air inlet part by adjusting the control valve, and the natural gas in the first pipeline is 35-45 m 3 The flow rate/h is introduced into the gas line.
The mixed material obtained by mixing the ternary lithium battery material and the reducing agent is placed in a feeding section of a conveyor belt, the ternary lithium battery material is conveyed to a heating area through the conveyor belt, and the ternary lithium battery material is reduced for 1.5-2.5 hours at the temperature of 500-700 ℃ under the condition that natural gas in a first pipeline provides a reducing gas atmosphere.
In a third aspect, the present invention provides a method for recovering lithium, comprising the steps of:
the ternary lithium battery material is reduced by the control method of the ternary lithium battery material reduction device,
and leaching the reduced ternary lithium battery material for 1.5-2.5 hours in water under the condition of stirring every 10-20 minutes, wherein the mass ratio of the water to the reduced ternary lithium battery material is 14-16.
In the ternary lithium battery material reduction device, the feeding section of the conveyor belt receives the materials containing the ternary lithium battery material, and the materials are conveyed to the heating zone of the heating furnace through the reaction section of the conveyor belt. At least two air source pipelines can be communicated with the first air inlet part through adjusting the control valve, so that the working gas is conveyed to the reaction section through the air pipeline. Working gas in the at least two gas source pipelines is different, so that the control valve can be adjusted according to the requirement of the ternary lithium battery material for reduction reaction, and the gas source pipeline for conveying the required working gas is communicated with the first gas inlet part. And conveying the working gas to the reaction section through a gas pipeline to provide the required conditions for the reduction reaction of the ternary lithium battery material. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of the ternary lithium battery material, so that the ternary lithium battery material reduction device is wide in application range and not easily limited by production raw materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a ternary lithium electrical material reduction device according to an embodiment of the present disclosure;
fig. 2 is a schematic view of a control system of a ternary lithium electrical material reduction device of the ternary lithium electrical material reduction device according to an embodiment of the present disclosure;
fig. 3 is a schematic flow diagram of a switching reduction process of a ternary lithium battery material reduction device according to an embodiment of the present disclosure.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all the directional indicators (such as the upper and lower … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be based on the realization of the technical solutions by those skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination of the technical solutions should not be considered to exist, and is not within the protection scope claimed by the present invention.
In a first aspect of the present invention, a ternary lithium battery material reduction apparatus, which may be, for example, a steel belt furnace, is provided, and referring to fig. 1, includes a heating furnace 110, a conveyor belt 120, a gas pipeline 130, at least two gas source pipelines, and control valves corresponding to the gas source pipelines. The heating furnace 110 has a heating zone.
The conveyor 120 comprises a feeding section 121, a reaction section 122 and a discharging section 123 which are arranged in sequence along the conveying direction of the conveyor, and the reaction section 122 passes through the heating zone of the heating furnace 110. The conveyor belt 120 is used for conveying materials, and the materials may be ternary lithium battery materials or mixed materials of the ternary lithium battery materials and a reducing agent according to different reduction processes.
The conveyer 120 passes through the heating furnace 110, wherein the feeding section 121 and the discharging section 123 are located outside the heating furnace 110, and the reaction section 122 is located inside the heating furnace 110. The feed section 121 receives an externally supplied material. The material is transferred to the reaction section 122 and the reaction section 122 is transferred to the heating zone of the heating furnace 110, and the reduction reaction occurs in the reaction section 122. The reduced material is conveyed to the discharging section 123 for discharging.
The gas pipe 130 is disposed at a side of the conveyor belt 120 close to the heating furnace 110, and the gas pipe 130 passes through at least the reaction section 122 of the conveyor belt 120 to release the working gas required for the reduction of the ternary lithium electrical material to the reaction section 122. For example, the wall of the gas pipe 130 is provided with gas holes along the extending direction of the pipe, and the part of the gas pipe 130 in the reaction section 122 can release the internal working gas to the reaction section 122. The working gas is the gas required by the ternary lithium battery material for reduction, and the components of the working gas are different according to different reduction processes of the ternary lithium battery material. For example, when the ternary lithium electrical material is reduced using a reducing gas, the working gas is the reducing gas. As another example, when the ternary lithium battery material is reduced with a reducing agent (e.g., activated carbon), a certain protective gas needs to be provided, and the working gas is the protective gas. Therefore, the working gas is a reducing gas or a shielding gas. The reducing gas is a gas having reducing properties, and may be hydrogen (for example, hydrogen is contained in the ammonia decomposition gas, and hydrogen may be added in the form of the ammonia decomposition gas), methane (for example, the main component of natural gas is methane, and methane may be added in the form of natural gas), or carbon monoxide. The protective gas is chemically stable gas, and may be nitrogen, or inert gas such as helium, neon, argon, krypton, xenon, or radon.
The gas duct 130 includes a first gas inlet portion 131 for receiving a working gas. The working gas is provided by a gas source pipeline. The number of the air source pipelines is at least two, namely the number of the air source pipelines can be two or more than two. In all the gas source pipelines, the working gas conveyed in the gas source pipelines is different. It should be noted that the different working gases include different types of working gases, such as a protective gas for one working gas and a reducing gas for another working gas, and different compositions of the same working gas, for example, two working gases are both reducing gases, one is natural gas, and the other is ammonia decomposition gas.
The control valve and the air source pipeline are correspondingly arranged. At least two gas source pipelines are respectively connected with the first gas inlet part 131 through corresponding control valves and are used for conveying different working gases to the gas pipeline 130 through the first gas inlet part 131. The control valve can adjust the opening degree of the air supply pipeline, so that the air supply pipeline is communicated with or closed to the first air inlet portion 131, and in a state that the air supply pipeline and the first air inlet portion 131 are communicated with each other, the internal flow rate of the working air in the air supply pipeline entering the first air inlet portion 131 is adjusted. Preferably, the working gas is transported in the portion of the gas conduit 130 corresponding to the reaction section 122 in a direction opposite to the direction of transport of the material, so as to better contact the material.
In the above-mentioned ternary lithium battery material reduction apparatus, the feeding section 121 of the conveyor belt 120 receives the material including the ternary lithium battery material, and the material is conveyed to the heating zone of the heating furnace 110 through the reaction section 122 of the conveyor belt 120. The at least two gas source pipes may be adjusted by the control valve such that one of the at least two gas source pipes is in communication with the first gas inlet portion 131 to deliver the working gas to the reaction section 122 via the gas pipe 130. Working gas in the at least two gas source pipelines is different, so that the control valve can be adjusted according to the requirement of the ternary lithium battery material for reduction reaction, and the gas source pipeline for conveying the required working gas is communicated with the first gas inlet portion 131. The working gas is delivered to the reaction section 122 via the gas conduit 130 to provide the conditions required for the reduction reaction of the ternary lithium battery material. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of the ternary lithium battery material, so that the ternary lithium battery material reduction device is wide in application range and not easily limited by production raw materials.
In some embodiments, the reducing gas comprises natural gas and ammonia decomposition gas. The at least two gas source pipelines at least comprise a first pipeline for conveying natural gas, a second pipeline for conveying ammonia decomposition gas and a third pipeline for conveying protective gas.
The natural gas and the ammonia decomposition gas are used as reducing gas, the cost is relatively low, and the lithium element in the ternary lithium battery material can be efficiently reduced. Compared with hydrogen, the ammonia decomposition gas is safer and more practical. In the actual reduction process, a suitable working atmosphere can be selected as required, the corresponding one of the first pipeline, the second pipeline and the third pipeline is conducted with the first air inlet portion 131 by adjusting the control valve, and the rest of the pipelines are in a closed state with the first air inlet portion 131.
Optionally, referring to fig. 1, the gas conduit 130 also passes through the infeed section 121 and the outfeed section 123 of the conveyor 120 for releasing the shielding gas into the infeed section 121 and the outfeed section 123. The gas duct 130 comprises a second gas inlet 132 for receiving a shielding gas and a third gas inlet 133, the second gas inlet 132 being located in the portion of the gas duct passing through the feed section 121, and the third duct being connected to the second gas inlet 132 by a corresponding control valve. The third air inlet portion 133 is located at a portion of the air inlet duct passing through the discharging section 123, and the third duct is connected to the second air inlet portion 132 through a corresponding control valve.
The gas conduit 130 includes a portion that extends above the infeed section 121 and a portion above the outfeed section 123 of the conveyor 120. A corresponding control valve is arranged between the second air inlet portion 132 and the third pipeline, and after the control valve is opened, the protective gas enters the gas pipeline 130 and is released to the feeding section 121 of the conveyor belt 120, so that the material distributed by the feeding section 121 is isolated from the outside air.
Similarly, a corresponding control valve is arranged between the third air inlet portion 133 and the third pipeline, and after the control valve is opened, the protective gas enters the gas pipeline 130 and is released to the discharge section 123 of the conveyor belt 120, so that the material distributed at the feed section 121 is isolated from the outside air, and the reduced ternary lithium battery material is prevented from being oxidized under the residual heat. Of course, since the third air inlet 133 and the second air inlet 132 are connected to the third pipeline, the third air inlet 133 and the second air inlet 132 may share the same control valve, and the flow rates of the shielding gas in the inlet section 121 and the outlet section 123 are equal.
Likewise, the conveying direction of the working gas in the portion of the gas pipeline 130 corresponding to the discharge section 123 is opposite to the conveying direction of the reduced ternary lithium battery material, so that the working gas is better contacted with the reduced ternary lithium battery material.
Optionally, an oxygen analyzer and/or a gas flow meter are also included. The oxygen analyzer is disposed in a heating zone in the heating furnace 110, that is, in a furnace of the heating furnace 110. A gas flow meter is disposed at a position of the gas pipe 130 close to the first gas inlet 131, and a gas flow meter is disposed at a position of the gas pipe 130 close to at least one of the second gas inlet 132 and the third gas inlet 133.
Before the reduction process is performed, the gas pipe 130 is filled with a shielding gas to remove the air in the heating furnace 110. The oxygen analyzer may measure the oxygen concentration of the furnace 110, and when the oxygen concentration is lower, such as less than 2%, the introduction of the reducing gas or the shielding gas into the gas pipeline 130 may be started to prepare for reduction.
The gas flow meter is arranged at a position of the gas pipeline 130 close to the first gas inlet portion 131, and can indicate the flow of the protective gas of the reaction section 122, so that the reaction conditions of the ternary lithium battery material during reduction can be better controlled.
Similarly, in the case where the third air intake portion 133 and the second air intake portion 132 share the same control valve, a gas flow meter is provided at a position of the gas piping 130 near the second air intake portion 132 or the third air intake portion 133. In this way, the flow rate of the protective gas in the feeding section 121 and the discharging section 123 can be indicated by using one gas flowmeter, so that the material and the reduced ternary lithium battery material can be protected better, and the cost is reduced.
Under the condition that the third air inlet portion 133 and the third pipeline have control valves, and the second air inlet portion 132 and the third pipeline have another control valve, gas flow meters are respectively arranged at positions of the gas pipeline 130 close to the second air inlet portion 132 and the third air inlet portion 133, and can respectively indicate the flow rates of the protective gas of the feeding section 121 and the discharging section 123, so that the flow rates of the protective gas at one position of the feeding section 121 and the discharging section 123 can be independently adjusted, and the material and the reduced ternary lithium battery material can be better protected.
Optionally, the gas conduit 130 further comprises a tail gas outlet 134. The tail gas outlet 134 enables tail gas in the gas pipeline 130 to be discharged in a centralized manner, so that subsequent tail gas treatment is facilitated.
The second aspect of the present invention provides a method for controlling the ternary lithium battery material reduction device, including the following steps:
one of the at least two gas source pipelines is communicated with the first gas inlet portion 131 by adjusting the control valve, and the working gas in the gas source pipeline is introduced into the gas pipeline 130.
Adding a reducing agent into the ternary lithium battery material, and reducing the ternary lithium battery material in an atmosphere provided by working gas, wherein the working gas is protective gas; or
And reducing the ternary lithium battery material in an atmosphere provided by working gas, wherein the working gas is reducing gas.
Referring to the description of the ternary lithium battery material reduction device, it may be applicable to the reduction process of different ternary lithium battery materials. The control method of the ternary lithium battery material reduction device is suitable for the situation that the ternary lithium battery material is reduced by adding the reducing agent. The control valve is adjusted to enable the gas source pipeline for conveying the protective gas to be communicated with the first gas inlet portion 131, and the other gas source pipelines and the first gas inlet portion 131 are in a closed state. The protective gas is used as the protective gas in the reduction process of the ternary lithium battery material, so that the ternary lithium battery material is isolated from the outside air. Under the heating of the heating furnace 110, the ternary lithium battery material is reduced by the reducing agent.
Optionally, at least a first, a second and a third conduit are included in the at least two gas source conduits, and the gas conduit 130 includes a second air intake 132 and a third air intake 133.
Under the condition that the working gas introduced through the first gas inlet portion 131 is the protective gas, the reducing agent is added into the ternary lithium battery material, and the step of reducing the ternary lithium battery material includes:
the third pipeline is communicated with the second air inlet part 132 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is at 8m 3 The flow rate per hour is introduced.
The third pipeline is communicated with the third air inlet part 133 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is introduced into the gas line 130. Preferably, the protective gas is present at 8m 3 The flow rate per hour is introduced.
The third pipeline is communicated with the first air inlet part 131 by adjusting the control valve, and the protective gas in the third pipeline is in a range of 10-14 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is at 12m 3 The flow rate of/h is introduced.
And placing a mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section 121 of a conveyor belt 120, conveying the mixed material to a heating zone through the conveyor belt 120, and reducing for 1.5-2.5 hours at 500-700 ℃ under the condition that protective gas in a third pipeline provides protective gas atmosphere. Wherein the mass of the reducing agent is 9-11% of that of the ternary lithium battery material. The reducing agent is activated carbon. Preferably, the mixture is reduced at 610 ℃ for 2 hours under an atmosphere of protective gas. The mass of the reducing agent is 10% of that of the ternary lithium battery material.
Under the conditions, the lithium element in the ternary lithium battery material is reduced thoroughly, the subsequent large lithium leaching rate is improved, the energy waste caused by overhigh reduction temperature and overlong reduction time can be avoided, and the waste of protective gas (such as nitrogen) is avoided.
Optionally, at least a first, a second and a third conduit are included in the at least two gas source conduits, and the gas conduit 130 includes a second air intake 132 and a third air intake 133. The reducing gas is ammonia decomposition gas.
The step of reducing the ternary lithium battery material in an atmosphere provided by ammonia decomposition gas comprises the following steps:
the third pipeline is communicated with the second air inlet part 132 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is present at 8m 3 The flow rate per hour is introduced.
The third pipeline is communicated with the third air inlet part 133 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is present at 8m 3 The flow rate of/h is introduced.
The second pipeline is communicated with the first air inlet part 131 by adjusting the control valve, and the hydrogen in the ammonia decomposition gas in the second pipeline is controlled to be 20-30 m 3 The flow rate/h is introduced into the gas line 130. Because the volume fraction of hydrogen in the ammonia decomposition gas is about 75 percent, 35-45 m can be introduced 3 Ammonia decomposition gas of about/h, so that the flow rate of the hydrogen reaches the required amount. Preferably, the ammonia decomposition gas is 40m 3 The flow rate of/h is introduced.
And (3) placing the ternary lithium battery material in a feeding section 121 of a conveyor belt 120, conveying the ternary lithium battery material to a heating area through the conveyor belt 120, and reducing for 1.5-2.5 hours at 500-700 ℃ under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere. Preferably, the reduction is carried out at 600 ℃ for 2 hours under the condition that the ammonia decomposition gas provides a reducing gas atmosphere.
Under the conditions, the lithium element in the ternary lithium battery material is reduced thoroughly, the subsequent large lithium leaching rate is improved, the energy waste caused by overhigh reduction temperature and overlong reduction time can be avoided, and the waste of protective gas (such as nitrogen) and ammonia decomposition gas can be avoided.
Optionally, at least a first, a second and a third conduit are included in the at least two gas source conduits, and the gas conduit 130 includes a second air intake 132 and a third air intake 133. The reducing gas is natural gas.
The method for reducing the ternary lithium battery material in the atmosphere provided by natural gas comprises the following steps:
the third pipeline is communicated with the second air inlet part 132 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is 7-9 m 3 The flow rate per hour is introduced.
The third pipeline is communicated with the third air inlet part 133 by adjusting the control valve, and the protective gas in the third pipeline is 7-9 m 3 The flow rate/h is passed into the gas line 130. Preferably, the protective gas is 7-9 m 3 The flow rate per hour is introduced.
The first pipeline is communicated with the first air inlet part 131 by adjusting the control valve, and the natural gas in the first pipeline is 35-45 m 3 The flow rate/h is introduced into the gas line 130. Preferably, the natural gas is at 40m 3 The flow rate of/h is introduced.
The mixed material obtained by mixing the ternary lithium battery material and the reducing agent is placed in a feeding section 121 of a conveyor belt 120, the ternary lithium battery material is conveyed to a heating zone through the conveyor belt 120, and the ternary lithium battery material is reduced for 1.5-2.5 hours at the temperature of 500-700 ℃ under the condition that natural gas in a first pipeline provides a reducing gas atmosphere. Preferably, the reduction is carried out at 550 ℃ for 2 hours under a reducing gas atmosphere provided by natural gas.
Under the conditions, the lithium element in the ternary lithium battery material is reduced thoroughly, the subsequent large lithium leaching rate is improved, the energy waste caused by overhigh reduction temperature and overlong reduction time can be avoided, and the waste of protective gas (such as nitrogen) and natural gas can be avoided.
Alternatively, the control method of the ternary lithium battery material reduction device may be controlled by using an automatic control system shown in fig. 2.
Optionally, referring to fig. 3, when the reduction process of the ternary lithium battery material needs to be switched, and the reduction process is changed from reduction by using a reducing agent to reduction by using a reducing gas, since the gas pipeline 130 is substantially filled with a protective gas, such as nitrogen, at this time, the reducing gas may be directly introduced into the gas pipeline 130 through the first gas inlet portion 131, and the introduction of the original protective gas is stopped after a delay of 3S. In the case of changing the reduction using one reducing gas (the former reducing gas) into the reduction using the other reducing gas (the latter reducing gas), the protective gas may be introduced into the gas pipe 130 through the first gas inlet 131, the introduction of the former reducing gas may be stopped after a delay of 3S, and the latter reducing gas may be introduced.
In a third aspect, the present invention provides a method for recovering lithium, comprising the steps of:
and reducing the ternary lithium battery material by the control method of the ternary lithium battery material reduction device.
Leaching the reduced ternary lithium battery material in water for 1.5-2.5 hours under the condition of stirring every 10-20 minutes, wherein the mass ratio of the water to the reduced ternary lithium battery material is 14-16. Under the condition, the leaching rate of lithium is high.
Preferably, the reduced ternary lithium battery material is leached in water for 2 hours under the condition of stirring every 15 minutes, wherein the mass ratio of the water to the reduced ternary lithium battery material is 15.
For a further understanding of the invention, reference will now be made to the examples.
Example 1
And reducing the ternary lithium battery material by adopting a ternary lithium battery material reduction device. The gas pipeline 130 of the ternary lithium electrical material reduction device passes through the feeding section 121, the reaction section 122 and the discharging section 123 of the conveyor belt 120. The gas duct 130 includes a first air intake portion 131, a second air intake portion 132, and a third air intake portion 133. All the air source pipelines comprise a first pipeline, a second pipeline and a third pipeline.
The conditions for adjusting the control valve and the heating furnace 110 to reduce the ternary lithium battery material are as follows:
the ternary lithium battery material (also called ternary battery black powder) and 10 percent (mass fraction) of activated carbon powder are uniformly mixed to obtain a mixed material, and the thickness of the mixed material distributed on the conveyor belt 120 is 30 mm. In the reduction process, the reduction temperature is 610 ℃ and the reduction time is 2 hours. 12m of gas is introduced from the reaction section 122 3 H nitrogen, feed section 121 and discharge section 123Respectively let in 8m 3 H of nitrogen.
After the reduction is finished, the product is soaked in water, the liquid-solid ratio is 15 (water and the reduced ternary battery material), the leaching time is 120min, and the product is stirred every 15 min at normal temperature.
Example 2
The difference from example 1 is that the thickness of the mixed material on the belt 120 is 50 mm.
Example 3
The difference from the embodiment 1 is that the conditions for adjusting the control valve and the heating furnace 110 to reduce the ternary lithium battery material are as follows:
the thickness of the cloth of the ternary lithium battery material on the conveyor belt 120 is 30 mm. In the reduction process, the reduction temperature is 600 ℃, and the reduction time is 2 hours. About 40m of gas is introduced from the reaction section 122 3 H ammonia decomposition gas, ensuring that the introduction amount of hydrogen (75%) in the furnace is 25m 3 H, respectively introducing 8m of gas into the feeding section 121 and the discharging section 123 3 H of nitrogen.
Example 4
The difference from example 3 is that the thickness of the mixed material on the belt 120 is 50 mm.
Example 5
The difference from the embodiment 1 is that the conditions for adjusting the control valve and the heating furnace 110 to reduce the ternary lithium battery material are as follows:
the thickness of the cloth of the ternary lithium battery material on the conveyor belt 120 is 30 mm. In the reduction process, the reduction temperature is 550 ℃ and the reduction time is 2 hours. About 40m of gas is introduced from the reaction section 122 3 H, respectively introducing 8m of natural gas into the feeding section 121 and the discharging section 123 3 Nitrogen per hour.
Example 6
The difference from example 6 is that the mixed material has a thickness of 50mm at the cloth of the conveyor belt 120.
The leaching rate of lithium was measured for each example, see table 1.
TABLE 1 reduction substances, reduction conditions and leaching rates of the examples
Reducing substances Reduction conditions Lithium leaching rate
Example 1 Carbon (C) At 610 ℃ for 2 hours, the thickness of the cloth is 30mm 88.06％
Example 2 Carbon (C) At 610 ℃ for 2 hours, and the thickness of the cloth is 50mm 81.01％
Example 3 Hydrogen gas At 600 ℃ for 2 hours, the cloth thickness is 30mm 81.95％
Example 4 Hydrogen gas At 600 ℃ for 2 hours, the thickness of the cloth is 50mm 80.33％
Example 5 Natural gas At 550 ℃, 2 hours and the thickness of the cloth is 30mm 92.02％
Example 6 Natural gas At 550 ℃, 2 hours and 50mm of cloth thickness 90.12％
According to the data, the leaching rate of the ternary lithium battery material reduced by the ternary lithium battery material reduction device and the control method provided by the embodiment of the application is 80% at least and is higher than the leaching rate of 60% in the industry.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.

Claims (10)

1. A ternary lithium battery material reduction device is characterized by comprising:
a heating furnace having a heating zone;
the conveying belt comprises a feeding section, a reaction section and a discharging section which are sequentially arranged along the conveying direction of the conveying belt, and the reaction section passes through the heating zone of the heating furnace;
the gas pipeline is positioned on one side, close to the heating furnace, of the conveyor belt and at least passes through a reaction section of the conveyor belt so as to release working gas required by the ternary lithium battery material to be reduced to the reaction section, and the gas pipeline comprises a first gas inlet part for receiving the working gas; the working gas is reducing gas or protective gas;
the gas source pipeline comprises at least two gas source pipelines and control valves correspondingly arranged with the gas source pipelines, wherein the at least two gas source pipelines are respectively connected with the first gas inlet part through the corresponding control valves and are used for conveying different working gases to the gas pipelines through the first gas inlet part.
2. The ternary lithium electrical material reduction device of claim 1, wherein the reducing gas comprises natural gas and ammonia decomposition gas;
the at least two gas source pipelines at least comprise a first pipeline for conveying natural gas, a second pipeline for conveying ammonia decomposition gas and a third pipeline for conveying protective gas.
3. The ternary lithium electrical material reduction device of claim 2, wherein the gas conduit further passes through a feed section and a discharge section of the conveyor belt for releasing a shielding gas to the feed section and the discharge section;
the gas pipeline comprises a second gas inlet part and a third gas inlet part, the second gas inlet part is used for receiving the protective gas and is positioned at the part of the gas inlet pipeline passing through the feeding section, and the third pipeline is connected with the second gas inlet part through the corresponding control valve;
the third air inlet part is positioned at the part of the air inlet pipeline passing through the discharge section, and the third pipeline is connected with the second air inlet part through the corresponding control valve.
4. The ternary lithium electrical material reduction device of claim 3, further comprising an oxygen analyzer and/or a gas flow meter, wherein the oxygen analyzer is disposed in the heating zone of the heating furnace;
the gas flowmeter is arranged at a position, close to the first air inlet portion, of the gas pipeline, and the gas flowmeter is arranged at a position, close to at least one of the second air inlet portion and the third air inlet portion, of the gas pipeline.
5. The ternary lithium battery material reduction device according to any one of claims 1 to 4, wherein the gas pipeline further comprises a tail gas outlet.
6. A control method for a ternary lithium electrical material reduction device in accordance with any of claims 1 to 5, comprising the steps of:
one of the at least two gas source pipelines is communicated with the first gas inlet part by adjusting the control valve, and working gas in the gas source pipeline is introduced into the gas pipeline;
adding a reducing agent into a ternary lithium battery material, and reducing the ternary lithium battery material in an atmosphere provided by working gas, wherein the working gas is protective gas; or
And reducing the ternary lithium battery material in the atmosphere provided by the working gas, wherein the working gas is a reducing gas.
7. The method of claim 6, wherein the at least two gas source lines comprise at least a first line, a second line, and a third line, and the gas lines comprise a second gas inlet and a third gas inlet;
the step of adding a reducing agent into the ternary lithium battery material and reducing the ternary lithium battery material in the atmosphere provided by the working gas comprises the following steps:
the third pipeline is communicated with the second air inlet part by adjusting the control valve, and protective gas in the third pipeline is 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is communicated with the third air inlet part by 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the third pipeline is communicated with the first air inlet part by adjusting the control valve, and protective gas in the third pipeline is enabled to be 10-14 m 3 The flow rate of/h is introduced into the gas pipeline;
placing a mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section of the conveyor belt, conveying the mixed material to the heating area through the conveyor belt, and reducing for 1.5-2.5 hours at 500-700 ℃ under the condition that protective gas atmosphere is provided by protective gas in a third pipeline; the mass of the reducing agent is 9-11% of that of the ternary lithium battery material, and the reducing agent is activated carbon.
8. The method of claim 6, wherein the at least two gas source lines comprise at least a first line, a second line, and a third line, and the gas lines comprise a second gas inlet and a third gas inlet; the reducing gas is ammonia decomposition gas;
the step of reducing the ternary lithium battery material in the atmosphere provided by the ammonia decomposition gas comprises:
the third pipeline is communicated with the second air inlet portion by adjusting the control valve, and protective gas in the third pipeline is enabled to be 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is communicated with the third air inlet part by 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the second pipeline is communicated with the first air inlet part by adjusting the control valve, and the hydrogen in the ammonia decomposition gas in the second pipeline is 20-30 m 3 The flow rate of/h is introduced into the gas pipeline;
and placing the ternary lithium battery material in a feeding section of a conveying belt, conveying the ternary lithium battery material to a heating zone through the conveying belt, and reducing for 1.5-2.5 hours at 500-700 ℃ under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere.
9. The method of claim 6, wherein the at least two gas source lines comprise at least a first line, a second line, and a third line, and the gas lines comprise a second gas inlet and a third gas inlet; the reducing gas is natural gas;
the step of reducing the ternary lithium battery material in the atmosphere provided by the natural gas comprises:
the third pipeline is communicated with the second air inlet portion by adjusting the control valve, and protective gas in the third pipeline is enabled to be 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and protective gas in the third pipeline is communicated with the third air inlet part by 7-9 m 3 The flow rate of/h is introduced into the gas pipeline;
the first pipeline is communicated with the first air inlet part by adjusting the control valve, and natural gas in the first pipeline is communicated in a range of 35-45 m 3 The flow rate of/h is introduced into the gas pipeline;
will ternary lithium battery material with the miscellany material that the reductant mixes and obtains place in the feed section of conveyer belt, ternary lithium battery material warp the conveyer belt conveys the zone of heating reduces 1.5 ~ 2.5 hours under the condition that the natural gas in 500 ~ 700 ℃ in the first pipeline provided the reducing gas atmosphere.
10. A method for recovering lithium, comprising the steps of:
reducing a ternary lithium battery material by the control method of the ternary lithium battery material reduction device according to any one of claims 6 to 9,
leaching the reduced ternary lithium battery material for 1.5-2.5 hours in water under the condition of stirring every 10-20 minutes, wherein the mass ratio of the water to the reduced ternary lithium battery material is 14-16.
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CN209923401U (en) * 2019-02-25 2020-01-10 湖南五创循环科技有限公司 Hydrogenation reduction furnace for reducing lithium ion battery anode material
JPWO2020218237A1 (en) * 2019-04-23 2020-10-29
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2741357A1 (en) * 2012-12-05 2014-06-11 TSR-KAT GmbH Method for the recovery of constituents of spent lithium cells
KR20140126943A (en) * 2013-04-24 2014-11-03 타운마이닝캄파니(주) Method for recovering valuable metals from cathodic active material of used lithium battery
CN107560429A (en) * 2017-10-17 2018-01-09 湖南顶立科技有限公司 A kind of reduction furnace
CN109509931A (en) * 2018-12-25 2019-03-22 哈尔滨巴特瑞资源再生科技有限公司 A kind of lithium battery electrolytes eliminating equipment and method
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