CN114921653B - 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 PDFInfo
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- CN114921653B CN114921653B CN202210575368.5A CN202210575368A CN114921653B CN 114921653 B CN114921653 B CN 114921653B CN 202210575368 A CN202210575368 A CN 202210575368A CN 114921653 B CN114921653 B CN 114921653B
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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
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B7/006—Wet processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The application 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, a gas pipeline, at least two gas source pipelines and a control valve which is arranged corresponding to the gas source pipelines. The conveyer belt includes feeding section, reaction section and the ejection of compact section that sets gradually along self direction of transfer. The gas conduit passes at least through the reaction section of the conveyor belt. The gas duct includes a first gas inlet. The at least two air source pipelines and the control valves which are arranged corresponding to the air source pipelines are respectively connected with the first air inlet part through the corresponding control valves. The control valve is regulated to enable the air source pipeline for conveying the required working gas to be communicated with the first air inlet part so as to provide the conditions required by the reduction reaction of the ternary lithium battery material. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of ternary lithium battery materials, and is wide in application range.
Description
Technical Field
The application relates to the technical field of waste lithium batteries, 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 positive electrode 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 waste ternary lithium ion battery has higher recovery value. The lithium recovery of the ternary lithium battery material includes reduction and leaching steps. After the ternary lithium battery material is reduced, the leaching rate of lithium can be improved more.
Conventional ternary lithium battery material reduction devices can only use specific reduction processes, such as processes using carbon for reduction or processes using specific reducing gases for reduction. Therefore, the reduction device of the ternary lithium battery material has limited application range and is easy to be limited by production raw materials.
Disclosure of Invention
The application 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, so as to solve the technical problems that the use range of the ternary lithium battery material reduction device is limited and the ternary lithium battery material reduction device is easily limited by production raw materials.
In order to achieve the above object, a first aspect of the present application provides a ternary lithium electric material reduction device. The ternary lithium battery material reduction device comprises a heating furnace, a conveyor belt, a gas pipeline, at least two gas source pipelines and control valves which are arranged corresponding to the gas source pipelines.
The heating furnace has a heating zone.
The conveyor belt comprises a feeding section, a reaction section and a discharging section which are sequentially arranged along the conveying direction of the conveyor belt, wherein the reaction section passes through a heating zone of the heating furnace.
The gas pipeline is located at one side of the conveyor belt, which is close to the heating furnace, and at least passes through the reaction section of the conveyor belt to release working gas required by the reduction of the ternary lithium battery material to the reaction section, and the gas pipeline comprises a first air inlet part for receiving the working gas. The working gas is a reducing gas or a shielding gas.
The device comprises at least two air source pipelines and control valves which are arranged corresponding to the air source pipelines, wherein the at least two air source pipelines are respectively connected with the first air inlet part through the corresponding control valves and are used for conveying different working gases to the air pipelines through the first air inlet part.
Optionally, 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.
Optionally, the gas conduit also passes through the feed section and the discharge section of the conveyor belt for releasing the 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, wherein the second gas inlet part is used for receiving protective gas, the second gas inlet part is positioned at 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 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 flowmeter, wherein the oxygen analyzer is arranged in a heating zone of the heating furnace;
the position of the gas pipeline, which is close to the first air inlet part, is provided with a gas flowmeter, and at least one position of the gas pipeline, which is close to the second air inlet part and the third air inlet part, is provided with a gas flowmeter.
Optionally, the gas conduit further comprises a tail gas outlet.
The second aspect of the application provides a control method of the ternary lithium battery material reduction device, which comprises the following steps:
one air source pipeline of the at least two air source pipelines is communicated with the first air inlet part through the adjusting control valve, and working gas in the air source pipelines is introduced into the air pipelines;
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 (b)
And reducing the ternary lithium battery material in an atmosphere provided by the working gas, wherein the working gas is reducing gas.
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.
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, wherein the step of reducing the ternary lithium battery material comprises the following steps:
and the third pipeline is communicated with the second air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
And the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
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 introduced into the gas pipeline at a flow rate of 10-14 m/h.
And (3) placing a mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section of a conveying belt, conveying the mixed material to a heating area through the conveying belt, and reducing for 1.5-2.5 hours under the condition that the temperature is 500-700 ℃ and the protective gas in a third pipeline provides a protective gas atmosphere. The mass of the reducing agent is 9-11% of the mass of the ternary lithium battery material. The reducing agent is activated carbon.
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 ammonia decomposition gas.
The method for reducing the ternary lithium battery material in the atmosphere provided by the ammonia decomposition gas comprises the following steps:
and the third pipeline is communicated with the second air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
And the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
The second pipeline is communicated with the first air inlet part by adjusting the control valve, and hydrogen in ammonia decomposition gas in the second pipeline is introduced into the gas pipeline at a flow rate of 20-30 m/h.
And placing the ternary lithium battery material in a feeding section of the conveyor belt, conveying the ternary lithium battery material to a heating area through the conveyor belt, and reducing the ternary lithium battery material for 1.5-2.5 hours under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere at the temperature of 500-700 ℃.
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 comprises the following steps of:
and the third pipeline is communicated with the second air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
And the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h.
The first pipeline is communicated with the first air inlet part by adjusting the control valve, and natural gas in the first pipeline is introduced into the gas pipeline at a flow rate of 35-45 m/h.
And (3) placing a mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section of a conveying belt, conveying the ternary lithium battery material to a heating area through the conveying belt, and reducing for 1.5-2.5 hours under the condition that the temperature is 500-700 ℃ and the reducing gas atmosphere is provided by natural gas in a first pipeline.
A third aspect of the present application 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,
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.
In the ternary lithium battery material reduction device, the feeding section of the conveyor belt receives materials containing ternary lithium battery materials, and the materials reach the heating area of the heating furnace through the conveying belt conveying reaction section. The at least two air source pipelines can be communicated with the first air inlet part through adjusting the control valve, so that working gas is conveyed to the reaction section through the air pipelines. The working gases in the at least two gas source pipelines are 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 gases is communicated with the first gas inlet part. The working gas is conveyed to the reaction section through the gas pipeline to provide the conditions required by the reduction reaction of the ternary lithium battery material. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of ternary lithium battery materials, so that the ternary lithium battery material reduction device has a wide application range and is not easy to be limited by production raw materials.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a ternary lithium battery material reduction device according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a control system of a ternary lithium-ion battery material reduction device according to an embodiment of the application;
fig. 3 is a schematic flow chart of a switching reduction process of a ternary lithium battery material reduction device according to an embodiment of the application.
The achievement of the object, functional features and advantages of the present application will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present application are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions of the embodiments of the present application may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present application.
A first aspect of the present application provides a ternary lithium-ion material reduction apparatus, which may be, for example, a steel strip furnace, and referring to fig. 1, including a heating furnace 110, a conveyor belt 120, a gas pipe 130, at least two gas source pipes, and a control valve disposed corresponding to the gas source pipes. The heating furnace 110 has a heating zone.
The conveyor 120 includes a feeding section 121, a reaction section 122, and a discharging section 123 disposed in this order along the own conveying direction, the reaction section 122 traveling through the heating zone of the heating furnace 110. The conveyor 120 is used for conveying materials, which may be ternary lithium battery materials or a mixture of ternary lithium battery materials and reducing agents according to the reduction process.
The conveyor 120 passes through the furnace 110, wherein the feed section 121 and the discharge section 123 are located outside the furnace 110 and the reaction section 122 is located inside the furnace 110. The feed section 121 receives externally supplied material. The material is transferred to the reaction section 122 and transferred to the reaction section 122 to reach the heating zone of the heating furnace 110, where the reduction reaction occurs in the reaction section 122. The reduced material is transferred to the discharge section 123 for discharge.
The gas conduit 130 is located on a side of the conveyor belt 120 adjacent to the heating furnace 110, and the gas conduit 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 battery material to the reaction section 122. For example, the pipe wall of the gas pipe 130 is provided with gas holes along the extending direction of the pipe, and the gas pipe 130 can release the internal working gas to the reaction section 122 at the part of the reaction section 122. The working gas is the gas required by the reduction of the ternary lithium battery material, and the components of the working gas are different according to the reduction process of the ternary lithium battery material. For example, when the ternary lithium battery material is reduced by using a reducing gas, the working gas is the reducing gas. For another example, when the ternary lithium battery material is reduced by using a reducing agent (e.g., activated carbon), a certain protective gas needs to be provided, and the working gas is the protective gas. Thus, 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, the ammonia decomposition gas contains hydrogen, the hydrogen may be added in the form of ammonia decomposition gas), methane (for example, the main component of natural gas is methane, and the methane may be added in the form of natural gas), or carbon monoxide. The shielding gas is a gas with stable chemical properties, and can be nitrogen, or inert gases such as helium, neon, argon, krypton, xenon or radon.
The gas pipe 130 includes a first gas inlet 131 for receiving a working gas. The working gas is supplied from a gas source conduit. The number of the air source pipelines is at least two, namely, the number of the air source pipelines can be two or more. The working gas conveyed in the gas source pipeline is different in all the gas source pipelines. It should be noted that the different working gases include the case where the working gases are of different types, such as a working gas being a shielding gas, another working gas being a reducing gas, and the case where the working gases are of the same type but of different compositions, for example, both working gases are reducing gases, one being natural gas, and the other being 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 of the air source pipeline, so that the air source pipeline is conducted or closed with the first air inlet portion 131, and the internal flow of the working gas in the air source pipeline entering the first air inlet portion 131 is adjusted under the conducting state of the air source pipeline and the first air inlet portion 131. Preferably, the direction of transport of the working gas in the portion of the gas conduit 130 corresponding to the reaction section 122 is opposite to the direction of transport of the material, so as to better contact the material.
In the ternary lithium battery material reduction device, the feeding section 121 of the conveyor belt 120 receives the material containing ternary lithium battery material, and the material is conveyed by the conveyor belt 120 to the reaction section 122 to reach the heating area of the heating furnace 110. The at least two gas source pipelines can be communicated with the first gas inlet part 131 by adjusting the control valve, so that working gas is conveyed to the reaction section 122 through the gas pipeline 130. The 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 131. The working gas is delivered to the reaction section 122 via gas conduit 130 to provide the conditions required for the ternary lithium-ion material to undergo a reduction reaction. Therefore, the ternary lithium battery material reduction device can adapt to various reduction processes of ternary lithium battery materials, so that the ternary lithium battery material reduction device has a wide application range and is not easy to be limited by production raw materials.
In some embodiments, the reducing gas includes 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 gases, the cost is relatively low, and the lithium element in the ternary lithium battery material can be reduced more efficiently. The ammonia decomposition gas phase is safer and more practical than hydrogen. In the actual reduction process, a suitable working atmosphere may be selected according to the need, and corresponding pipelines of the first pipeline, the second pipeline and the third pipeline are conducted with the first air inlet portion 131 by adjusting the control valve, and the rest 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 feeding section 121 and the discharging section 123 of the conveyor belt 120 for releasing the shielding gas to the feeding section 121 and the discharging section 123. The gas pipe 130 includes a second gas inlet portion 132 for receiving the shielding gas and a third gas inlet portion 133, the second gas inlet portion 132 being located at a portion of the gas pipe passing through the feed section 121, the third pipe being connected to the second gas inlet portion 132 through a corresponding control valve. The third air inlet 133 is located at a portion of the gas pipe passing through the discharge section 123, and the third pipe is connected to the second air inlet 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 belt 120. A corresponding control valve is arranged between the second air inlet part 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 part 133 and the third pipeline, after the control valve is opened, the protective gas enters the gas pipeline 130 and is released to the discharging section 123 of the conveyor belt 120, so that the material distributed in the feeding section 121 is isolated from the outside air, and the reduced ternary lithium battery material is prevented from being oxidized under the waste heat. Of course, since the third air inlet portion 133 and the second air inlet portion 132 are both connected to the third pipe, the third air inlet portion 133 and the second air inlet portion 132 may share the same control valve, and at this time, 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 part of the gas pipeline 130 corresponding to the discharging 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 within the heating furnace 110, i.e., in a hearth of the heating furnace 110. Wherein, the gas pipeline 130 is provided with a gas flowmeter near the first air inlet portion 131, and at least one of the second air inlet portion 132 and the third air inlet portion 133 near the gas pipeline 130 is provided with a gas flowmeter.
Before the reduction process is performed, a shielding gas is introduced into the gas pipe 130 to drive off the air in the heating furnace 110. The oxygen analyzer may determine the oxygen concentration of the furnace 110, and when the oxygen concentration is low, e.g., < 2%, the introduction of the reducing gas or shielding gas into the gas line 130 may begin to prepare for reduction.
The gas flow meter is arranged at the position of the gas pipeline 130 close to the first air inlet 131, so that the flow of the shielding gas of the reaction section 122 can be indicated, and the reaction condition 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 where the gas pipe 130 is close to the second air intake portion 132 or the third air intake portion 133. In this way, the use of one gas flowmeter can simultaneously indicate the flow of the shielding gas of the feeding section 121 and the discharging section 123, so that the materials and the reduced ternary lithium battery material can be better protected, and the cost is reduced.
In the case that the third air inlet portion 133 and the third pipeline are provided with control valves, and the second air inlet portion 132 and the third pipeline are provided with another control valve, gas flow meters are respectively arranged at positions, close to the second air inlet portion 132 and the third air inlet portion 133, of the gas pipeline 130, and the shielding gas flow rates of the feeding section 121 and the discharging section 123 can be respectively indicated, so that the shielding gas flow rate at one position of the feeding section 121 and the discharging section 123 can be independently regulated, and materials and the reduced ternary lithium battery materials can be better protected.
Optionally, the gas conduit 130 further comprises a tail gas outlet 134. The exhaust outlet 134 allows the exhaust within the gas conduit 130 to be exhausted centrally for subsequent exhaust treatment.
The second aspect of the application provides a control method of the ternary lithium battery material reduction device, which comprises the following steps:
one of the at least two gas source pipelines is communicated with the first gas inlet part 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 (b)
And reducing the ternary lithium battery material in an atmosphere provided by the working gas, wherein the working gas is reducing gas.
The above description of the ternary lithium battery material reduction device can be applied to different ternary lithium battery material reduction processes. 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 shielding gas to be communicated with the first gas inlet part 131, and other gas source pipelines and the first gas inlet part 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. The reducing agent reduces the ternary lithium battery material under the heating of the heating furnace 110.
Optionally, at least two gas source pipelines include at least a first pipeline, a second pipeline, and a third pipeline, and the gas pipeline 130 includes a second gas inlet 132 and a third gas inlet 133.
In the case that the working gas introduced through the first gas inlet portion 131 is a protective gas, a reducing agent is added to 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 introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 8 m/h.
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 introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 8 m/h.
The third pipeline is communicated with the first air inlet portion 131 by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline 130 at a flow rate of 10-14 m/h. Preferably, the shielding gas is introduced at a flow rate of 12 m/h.
And (3) placing the mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section 121 of the conveyor belt 120, conveying the mixed material to a heating area through the conveyor belt 120, and reducing for 1.5-2.5 hours under the condition that the temperature is 500-700 ℃ and the protective gas in the third pipeline provides the protective gas atmosphere. The mass of the reducing agent is 9-11% of the mass of the ternary lithium battery material. The reducing agent is activated carbon. Preferably, the mixture is reduced at 610℃for 2 hours under a protective gas atmosphere. The mass of the reducing agent is 10% of the mass of the ternary lithium battery material.
Under the above conditions, the lithium element in the ternary lithium battery material is thoroughly reduced, so that the subsequent large lithium leaching rate is improved, the energy waste caused by too high reduction temperature and too long reduction time can be avoided, and the waste of protective gas (such as nitrogen) can be avoided.
Optionally, at least two gas source pipelines include at least a first pipeline, a second pipeline, and a third pipeline, and the gas pipeline 130 includes a second gas inlet 132 and a third gas inlet 133. The reducing gas is ammonia decomposition gas.
The method for 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 132 by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 8 m/h.
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 introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 8 m/h.
The second pipeline is communicated with the first air inlet part 131 by adjusting the control valve, and hydrogen in ammonia decomposition gas in the second pipeline is introduced into the gas pipeline 130 at a flow rate of 20-30 m/h. Because the volume fraction of the hydrogen in the ammonia decomposition gas is about 75%, the ammonia decomposition gas with the volume fraction of about 35-45 m/h can be introduced, so that the flow of the hydrogen reaches the required volume. Preferably, the ammonia decomposition gas is introduced at a flow rate of 40m w/h.
And placing the ternary lithium battery material in a feeding section 121 of the conveyor belt 120, conveying the ternary lithium battery material to a heating area through the conveyor belt 120, and reducing the ternary lithium battery material for 1.5-2.5 hours under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere at the temperature of 500-700 ℃. Preferably, the reduction is carried out for 2 hours at 600℃under conditions where the ammonia decomposition gas provides a reducing gas atmosphere.
Under the above conditions, the lithium element in the ternary lithium battery material is thoroughly reduced, which is favorable for improving the subsequent large lithium leaching rate, and can avoid the energy waste caused by too high reduction temperature and too long reduction time and the waste of protective gas (such as nitrogen) and ammonia decomposition gas.
Optionally, at least two gas source pipelines include at least a first pipeline, a second pipeline, and a third pipeline, and the gas pipeline 130 includes a second gas inlet 132 and a third gas inlet 133. The reducing gas is natural gas.
The method comprises the following steps of:
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 introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 7-9 m/h.
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 introduced into the gas pipeline 130 at the flow rate of 7-9 m/h. Preferably, the shielding gas is introduced at a flow rate of 7-9 m/h.
The first pipeline is communicated with the first air inlet part 131 by adjusting the control valve, and natural gas in the first pipeline is introduced into the gas pipeline 130 at the flow rate of 35-45 m/h. Preferably, the natural gas is introduced at a flow rate of 40 m.multid. h.
And (3) placing the mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section 121 of the 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 under the condition that the temperature is 500-700 ℃ and the reducing gas atmosphere is provided by the natural gas in the first pipeline. Preferably, the reduction is carried out for 2 hours at 550 ℃ under conditions where natural gas provides a reducing gas atmosphere.
Under the above conditions, the lithium element in the ternary lithium battery material is thoroughly reduced, so that the subsequent large lithium leaching rate is improved, the energy waste caused by too high reduction temperature and too long 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-ion material reduction device can be controlled by adopting an automatic control system shown in fig. 2.
Alternatively, referring to fig. 3, when the reduction process of the ternary lithium battery material needs to be switched, in the case of reducing the ternary lithium battery material by using the reducing agent to reduce the ternary lithium battery material by using the reducing gas, since the gas pipeline 130 is basically the protective gas, such as nitrogen, at this time, the reducing gas can be directly introduced into the gas pipeline 130 through the first air inlet 131, and after a time delay of 3S, the introduction of the original protective gas is stopped. In the case where the reduction with one reducing gas (the preceding reducing gas) is changed to the reduction with the other reducing gas (the following reducing gas), the shielding gas may be introduced into the gas pipe 130 through the first gas inlet 131 first, and after a delay of 3S, the introduction of the preceding reducing gas may be stopped, and then the following reducing gas may be introduced.
A third aspect of the present application 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 this 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 application, an example will now be described.
Example 1
And reducing the ternary lithium battery material by adopting a ternary lithium battery material reduction device. The gas pipe 130 of the ternary lithium electric 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 gas inlet portion 131, a second gas inlet portion 132, and a third gas inlet portion 133. All air supply lines include a first line, a second line, and a third line.
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 as ternary battery black powder) and 10% (mass fraction) of active carbon powder are uniformly mixed to obtain a mixed material, and the distribution thickness of the mixed material on the conveyor belt 120 is 30mm. In the reduction process, the reduction temperature was 610℃and the reduction time was 2 hours. 12 m/h of nitrogen were introduced from the reaction section 122, and 8 m/h of nitrogen were introduced into the feed section 121 and the discharge section 123, respectively.
After the reduction is finished, the product adopts a water leaching mode, the liquid-solid ratio is 15 (water and the reduced ternary battery material), the leaching time is 120min, and the stirring is carried out every 15 min under the condition of normal temperature.
Example 2
The difference from example 1 is that the thickness of the mixed material in the cloth of the conveyor belt 120 is 50mm.
Example 3
The difference from example 1 is that the conditions for adjusting the control valve and the heating furnace 110 so that the ternary lithium electric material is reduced are:
the thickness of the ternary lithium battery material on the cloth of the conveyor belt 120 is 30mm. In the reduction process, the reduction temperature was 600℃and the reduction time was 2 hours. About 40m of ammonia decomposition gas is introduced from the reaction section 122, so that the hydrogen (75%) in the furnace is ensured to be introduced into the reactor at 25m of m/h, and 8m of nitrogen is respectively introduced into the feeding section 121 and the discharging section 123.
Example 4
The difference from example 3 is that the thickness of the mixed material in the cloth of the conveyor belt 120 is 50mm.
Example 5
The difference from example 1 is that the conditions for adjusting the control valve and the heating furnace 110 so that the ternary lithium electric material is reduced are:
the thickness of the ternary lithium battery material on the cloth of the conveyor belt 120 is 30mm. In the reduction process, the reduction temperature was 550℃and the reduction time was 2 hours. About 40 m/h of natural gas is introduced from the reaction section 122, and 8 m/h of nitrogen is introduced into the feed section 121 and the discharge section 123, respectively.
Example 6
The difference from example 6 is that the thickness of the mix material distributed on the conveyor 120 is 50mm.
The leaching rate of lithium of each example was measured, see table 1.
Table 1 reducing substances, reducing conditions and leaching Rate of examples
| Reducing substances | Reduction conditions | Lithium leaching rate | |
| Example 1 | Carbon (C) | 610 ℃ for 2 hours, the thickness of the cloth is 30mm | 88.06% |
| Example 2 | Carbon (C) | 610 ℃ for 2 hours, the thickness of the cloth is 50mm | 81.01% |
| Example 3 | Hydrogen gas | 600 ℃ for 2 hours, the thickness of cloth is 30mm | 81.95% |
| Example 4 | Hydrogen gas | 600 ℃ for 2 hours, the thickness of the cloth is 50mm | 80.33% |
| Example 5 | Natural gas | 550 ℃ for 2 hours, the thickness of the cloth is 30mm | 92.02% |
| Example 6 | Natural gas | 550 ℃ for 2 hours, the thickness of the cloth is 50mm | 90.12% |
According to the data, the lithium leaching rate of the ternary lithium battery material reduced by the ternary lithium battery material reduction device and the control method is 80% at the minimum, and the leaching rate in the industry is 60% high.
In the above technical solution of the present application, the above is only a preferred embodiment of the present application, and therefore, the patent scope of the present application is not limited thereto, and all the equivalent structural changes made by the description of the present application and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present application.
Claims (10)
1. A ternary lithium battery material reduction device, comprising:
a heating furnace having a heating zone;
the conveyor belt comprises a feeding section, a reaction section and a discharging section which are sequentially arranged along the conveying direction of the conveyor belt, wherein the reaction section passes through a heating zone of the heating furnace;
the gas pipeline is positioned at one side of the conveyor belt, which is close to the heating furnace, and at least passes through the reaction section of the conveyor belt to release working gas required by the reduction of the ternary lithium battery material to the reaction section, and the gas pipeline comprises a first air inlet part for receiving the working gas; the working gas is a reducing gas or a protective gas;
the device comprises at least two air source pipelines and control valves which are arranged corresponding to the air source pipelines, wherein the at least two air source pipelines are respectively connected with the first air inlet part through the corresponding control valves and are used for conveying different working gases to the air pipelines through the first air inlet part.
2. The ternary lithium-ion material reduction apparatus 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 electric material reduction apparatus 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 positioned at the part of the gas 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 pipeline passing through the discharging section, and the third pipeline is connected with the second air inlet part through the corresponding control valve.
4. The ternary lithium-ion material reduction apparatus 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 the position, close to the first air inlet, of the gas pipeline, and the gas flowmeter is arranged at the position, close to at least one of the second air inlet and the third air inlet, of the gas pipeline.
5. The ternary lithium battery material reduction device of any one of claims 1-4, wherein the gas pipeline further comprises a tail gas outlet.
6. A control method of the ternary lithium battery material reduction device according to any one of claims 1 to 5, characterized by comprising the following steps:
one air source pipeline of the at least two air source pipelines is communicated with the first air inlet part through the adjusting control valve, and working gas in the air source pipelines is introduced into the air pipelines;
adding a reducing agent into the ternary lithium battery material, and reducing the ternary lithium battery material in an atmosphere provided by the working gas, wherein the working gas is a protective gas; or (b)
And reducing the ternary lithium battery material in the atmosphere provided by the working gas, wherein the working gas is reducing gas.
7. The control method of the ternary lithium electric material reduction device according to claim 6, wherein at least one of the at least two gas source pipelines comprises a first pipeline, a second pipeline and a third pipeline, and the gas pipeline comprises a second gas inlet part and a third gas inlet part;
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 of:
the control valve is adjusted to enable the third pipeline to be communicated with the second air inlet part, and the protective gas in the third pipeline is led into the gas pipeline at the flow rate of 7-9 m/h;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h;
the control valve is adjusted to enable the third pipeline to be communicated with the first air inlet part, and the protective gas in the third pipeline is led into the gas pipeline at the flow rate of 10-14 m/h;
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 under the condition that the temperature is 500-700 ℃ and the protective gas in a third pipeline provides a protective gas atmosphere; 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 control method of the ternary lithium electric material reduction device according to claim 6, wherein at least one of the at least two gas source pipelines comprises a first pipeline, a second pipeline and a third pipeline, and the gas pipeline comprises a second gas inlet part and a third gas inlet part; 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 control valve is adjusted to enable the third pipeline to be communicated with the second air inlet part, and the protective gas in the third pipeline is led into the gas pipeline at the flow rate of 7-9 m/h;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h;
the control valve is adjusted to enable the second pipeline to be communicated with the first air inlet part, and hydrogen in ammonia decomposition gas in the second pipeline is led into the gas pipeline at a flow rate of 20-30 m/h;
and placing the ternary lithium battery material in a feeding section of the conveyor belt, conveying the ternary lithium battery material to the heating area through the conveyor belt, and reducing the ternary lithium battery material for 1.5-2.5 hours under the condition that ammonia decomposition gas in a third pipeline provides a reducing gas atmosphere at the temperature of 500-700 ℃.
9. The control method of the ternary lithium electric material reduction device according to claim 6, wherein at least one of the at least two gas source pipelines comprises a first pipeline, a second pipeline and a third pipeline, and the gas pipeline comprises a second gas inlet part and a third gas inlet part; 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 following steps:
the control valve is adjusted to enable the third pipeline to be communicated with the second air inlet part, and the protective gas in the third pipeline is led into the gas pipeline at the flow rate of 7-9 m/h;
the third pipeline is communicated with the third air inlet part by adjusting the control valve, and the protective gas in the third pipeline is introduced into the gas pipeline at the flow rate of 7-9 m/h;
the control valve is adjusted to enable the first pipeline to be communicated with the first air inlet part, and natural gas in the first pipeline is led into the gas pipeline at the flow rate of 35-45 m/h;
and (3) placing the mixed material obtained by mixing the ternary lithium battery material and the reducing agent in a feeding section of the conveyor belt, conveying the ternary lithium battery material to the heating area through the conveyor belt, and reducing for 1.5-2.5 hours under the condition that the temperature is 500-700 ℃ and the natural gas in the first pipeline provides a reducing gas atmosphere.
10. A method for recovering lithium, comprising the steps of:
reducing the ternary lithium battery material by the control method of the ternary lithium battery material reduction device according to any one of claims 6-9,
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.
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