CN113405367A - Lithium battery recovery powder reduction equipment and ternary lithium battery recovery powder reduction method - Google Patents
Lithium battery recovery powder reduction equipment and ternary lithium battery recovery powder reduction method Download PDFInfo
- Publication number
- CN113405367A CN113405367A CN202110691019.5A CN202110691019A CN113405367A CN 113405367 A CN113405367 A CN 113405367A CN 202110691019 A CN202110691019 A CN 202110691019A CN 113405367 A CN113405367 A CN 113405367A
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- reduction
- powder
- furnace
- spiral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/08—Screw feeders; Screw dischargers
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium battery recovery, and particularly discloses a lithium battery recovered powder reduction device capable of basically avoiding caking and highly toxic substances generated in a reduction process, and a ternary lithium battery recovered powder reduction method for reducing ternary lithium battery recovered powder by adopting the lithium battery recovered powder reduction device. According to the lithium battery recovery powder reduction equipment, the spiral material scattering device is arranged in the furnace tube of the reduction rotary furnace, so that materials can be prevented from caking in the furnace, and the effect of controlling the retention time of the materials in the furnace is achieved; the material after reduction can be quickly transferred into the discharge spiral from the high-temperature area through the spiral material dispersing device and the spiral discharge sealer, the temperature of the material after reduction in the furnace is effectively prevented from being reduced to be below 300 ℃, and the generation of highly toxic substances of nickel carbonyl and cobalt carbonyl caused by the reaction of carbon monoxide in the cracking gas and metals such as nickel, cobalt and the like in the material after reduction is basically avoided.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to a lithium battery recovery powder reduction device and a ternary lithium battery recovery powder reduction method.
Background
The lithium ion battery has higher working voltage and energy density, stable discharge voltage, no memory effect, light weight and small volume, thereby being widely applied to the fields of mobile electronic equipment, electric automobiles, reserve power supplies and the like. The lithium battery anode material mainly comprises lithium cobaltate, lithium iron phosphate and a ternary composite material, wherein the ternary battery has the advantages of high energy density, high voltage, good cycle performance and safe operation, is particularly suitable for the power requirement of a new energy automobile, is widely applied, and greatly promotes the development of the new energy automobile. With the rapid development of new energy automobiles, on one hand, the use amounts of lithium, nickel, cobalt, manganese and the like are greatly increased, and on the other hand, a large amount of waste lithium ion batteries are eliminated subsequently, so that not only is the resource waste caused, but also the environment is polluted.
The recovery technology of the waste lithium ion battery mainly comprises a liquid phase method and a solid phase method. The liquid phase method requires the use of a large amount of acid and alkali, which not only has high cost, but also causes environmental pollution. For example: the Chinese patent application with publication number CN101871048A discloses a method for recovering cobalt, nickel and manganese from waste lithium batteries, which comprises immersing the positive electrode material of the waste lithium batteries in low-concentration alkali liquor, recovering black powder with low aluminum content, dissolving the recovered black powder with dilute sulfuric acid at low acid, and then adopting Na2SO5、Na2SO3Or reducing and dissolving Fe powder in concentrated sulfuric acid, dissolving in high-concentration acid, performing solid-liquid separation on the obtained substance, and adding P2O4And P5O7The extractant extracts corresponding metals, improves the purity of the recovered metals, but in the whole process, the use of the extractant can generate a large amount of organic waste liquid, which causes great environmental pollutionAnd (4) harming.
The solid phase method can not only discharge a large amount of dust in the recovery process, but also the recovered product has low purity, is not suitable for high-quality recovery and has small profit; in addition, a high-temperature reduction process is often needed in the recovery process of the solid phase method, but the requirements of the high-temperature reduction on the process and equipment are particularly high in the practical production application, and the reduction process of the existing high-temperature reduction process is easy to agglomerate and also easy to generate a highly toxic substance nickel carbonyl.
Disclosure of Invention
The invention aims to provide a lithium battery recycled powder reduction device which can basically avoid caking and highly toxic substances generated in the reduction process.
The technical scheme adopted by the invention for solving the technical problems is as follows: the lithium battery recovery powder reduction equipment comprises a raw material bin, a spiral feeding sealer, a reduction rotary furnace, a spiral discharging sealer, a combustor, a heat exchanger, a bag-type dust collector, a centrifugal fan and an absorption tower;
the reduction rotary furnace comprises a furnace tube, the furnace tube is rotatably arranged on the foundation frame through a furnace tube backing ring and is in transmission connection with the driving device through a rotating gear ring; a spiral material scattering device is arranged in the furnace tube, a fire-resistant insulating layer is covered on the outer wall of the furnace tube, and a heating zone is formed between the fire-resistant insulating layer and the furnace tube;
the bottom of the burner is provided with a combustion-supporting and igniter, an air inlet and a pyrolysis gas inlet, and the air inlet is provided with a gas flow controller;
the raw material bin is arranged at the feed end of the spiral feeding sealer, the discharge end of the spiral feeding sealer is rotatably connected with the front end of the furnace tube through the corrugated tube sealer, the tail end upper part of the furnace tube is provided with a multilayer gas flow divider, the tail end lower part is provided with a dust precipitation collector, the tail end discharge port upper cover of the furnace tube is provided with a furnace tube discharge cover, the discharge end of the furnace tube discharge cover is connected with the feed end of the spiral discharging sealer, the multilayer gas flow divider is connected with the bottom cracking gas inlet of the combustor through a cracking exhaust tube, the top gas outlet of the combustor is connected with the top gas inlet of the heat exchanger, the bottom gas outlet of the heat exchanger is connected with the gas inlet of the bag-type dust collector, and the gas outlet of the bag-type dust collector is connected with the gas inlet of the absorption tower through a centrifugal fan.
Further, still include the second spiral ejection of compact sealer, the feed end of second spiral ejection of compact sealer is connected with the discharge end of spiral ejection of compact sealer.
Further, the spiral discharging sealer and the second spiral discharging sealer are both water-cooling spiral discharging sealers.
Further, a honeycomb type combustion structure is arranged in the combustor.
Further, the heat exchanger is a water-cooling heat exchanger.
The invention also provides a method for reducing the ternary lithium battery recovered powder, and the method adopts the lithium battery recovered powder reduction equipment to reduce the ternary lithium battery recovered powder.
Further, the method comprises the steps of proportioning;
the material preparation step: weighing the ternary lithium battery recovery powder and the reducing agent according to the mass ratio of 1: 2-5, and uniformly mixing the weighed ternary lithium battery recovery powder and the reducing agent to form a mixture.
Furthermore, the reducing agent is battery negative electrode powder, carbon powder or mixed powder, and the mixed powder is formed by mixing the battery negative electrode powder and the carbon powder.
Further, the method also comprises a reduction control step;
reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer to be subjected to carbothermic reduction, the furnace temperature is controlled to be 700-750 ℃, the reduction time is controlled to be 100-130 min, and the pressure in the furnace tube is controlled to be 0-100 Pa.
Further, the method also comprises a pyrolysis gas combustion control step;
and (3) pyrolysis gas combustion control: when pyrolysis gas is pumped into the combustor through the pyrolysis gas extraction pipe for combustion, the oxygen content in the combustor is controlled to be 4-10%, and the combustion temperature is controlled to be 1100-1200 ℃.
The invention has the beneficial effects that: the spiral material scattering device is arranged in the furnace tube of the reduction rotary furnace, so that the materials can be prevented from caking in the furnace, and the effect of controlling the retention time of the materials in the furnace is achieved; the spiral feeding sealer is used for feeding materials, the discharge end of the spiral feeding sealer is connected with the front end of the furnace tube through the bellows sealer, the front end of the reduction rotary furnace can be effectively sealed, air is prevented from entering the reduction rotary furnace, cracking gases such as low molecular alkanes and hydrogen in the furnace can reduce the part of carbon, nickel, cobalt and manganese oxides which cannot be contacted with the cracking gases at high temperature, and the reduction effect is improved; the upper part of the tail end of the furnace tube is provided with the multilayer gas splitter, so that the cracking gas in the furnace can be pumped out, the cracking gas and the reduced materials can be separated, and the external air can be prevented from streaming into the furnace; meanwhile, a furnace tube discharging cover is covered on a discharge port at the tail end of the furnace tube and connected with a feeding end of a spiral discharging sealer, and the reduced material can be quickly transferred into a discharging spiral from a high-temperature area through a spiral material dispersing device and the spiral discharging sealer, so that the temperature of the reduced material in the furnace can be effectively prevented from being reduced to be below 300 ℃, and the generation of highly toxic substances, namely nickel carbonyl and cobalt carbonyl, due to the reaction of carbon monoxide in cracking gas and metals, such as nickel, cobalt and the like, in the reduced material is basically avoided.
Drawings
FIG. 1 is a schematic diagram of an embodiment of a lithium battery recycling powder reduction device according to the present invention;
FIG. 2 is a schematic diagram of an embodiment of a spiral disperser;
FIG. 3 is a partial enlarged view of the end structure of the furnace tube;
FIG. 4 is a flow chart of a process for reducing ternary battery powder by using the lithium battery recovered powder reduction equipment provided by the invention;
labeled as: the device comprises a raw material bin 1, a spiral feeding sealer 2, a corrugated pipe sealer 3, a furnace tube backing ring 4, a rotary gear ring 5, a fireproof heat preservation layer 6, a heating zone 7, a spiral material dispersing device 8, a multilayer gas flow divider 9, a furnace tube discharging cover 10, a dust precipitation collector 11, a spiral discharging sealer 12, a combustion-supporting and igniter 13, a gas flow controller 14, a combustor 15, a heat exchanger 16, a bag-type dust remover 17, a centrifugal fan 18, an absorption tower 19 and a cracking exhaust tube 20.
Detailed Description
The invention is further illustrated by the following figures and examples.
As shown in fig. 1, the lithium battery recycling powder reduction equipment comprises a raw material bin 1, a spiral feeding sealer 2, a reduction rotary furnace, a spiral discharging sealer 12, a burner 15, a heat exchanger 16, a bag-type dust remover 17, a centrifugal fan 18 and an absorption tower 19;
the reduction rotary furnace comprises a furnace tube, the furnace tube is rotatably arranged on the foundation frame through a furnace tube backing ring 4 and is in transmission connection with the driving device through a rotating gear ring 5; a spiral material scattering device 8 is arranged in the furnace tube, a fire-resistant insulating layer 6 is covered on the outer wall of the furnace tube, and a heating zone 7 is formed between the fire-resistant insulating layer 6 and the furnace tube;
the bottom of the burner 15 is provided with a combustion-supporting and igniting device 13, an air inlet and a pyrolysis gas inlet, and the air inlet is provided with a gas flow controller 14;
The raw material bin 1 is mainly used for feeding the lithium battery recovery powder reduction equipment; the spiral feeding sealer 2 can convey the materials loaded in the raw material bin 1 into the reduction rotary furnace through spiral conveying; the bellows sealer 3 is provided with a bellows capable of being extended and compressed, the bellows sealer 3 is mainly used for connecting the discharge end of the spiral feeding sealer 2 with the front end of the furnace tube, the bellows can tightly press the sealing ring on the furnace tube under normal temperature conditions, and the bellows can be compressed to continuously keep sealing action when the furnace tube is heated and expanded so as to effectively seal the front end of the reduction rotary furnace, prevent external air from streaming into the furnace and ensure the reduction effect.
The rotary reduction furnace is mainly used for high-temperature reduction of lithium battery recovered powder, the flow directions of cracked gas and reducing material in a furnace tube of the rotary reduction furnace are the same, the cracked gas is generally low-molecular alkane, hydrogen and the like, the rotary reduction furnace has strong reducibility at high temperature, and the non-contact part of solid carbon and nickel-cobalt-manganese oxide can be reduced.
The furnace tube support rings 4 are mainly used for supporting the furnace tubes and ensuring the furnace tubes to rotate, and two groups of furnace tube support rings 4 are generally arranged at intervals; the rotating gear ring 5 is a transmission part and is mainly used for transmitting the driving action of the driving device to the furnace tube so as to rotate the furnace tube; the fire-resistant insulating layer 6 is made of fire-resistant materials with good insulating performance, such as: the refractory heat-insulating layer 6 is mainly used for heat insulation of a furnace tube so as to ensure the stability of the reduction temperature in the furnace; the heating zone 7 is mainly used for heating the reduction rotary furnace; the spiral material scattering device 8 is mainly used for scattering materials in the furnace pipe, preventing the materials from caking in the furnace, conveying the materials in the furnace pipe and controlling the retention time of the materials in the furnace; as shown in FIG. 2, the spiral material scattering device 8 is generally formed by connecting 5-8 sections of spirals with the diameter of 200mm, the spiral connections are movably connected, the spirals are always positioned at the bottom in the furnace tube and generate sliding friction with the furnace tube when the furnace tube rotates, materials caked on the inner wall of the furnace tube are separated by spiral friction, and simultaneously, large materials can be scattered; the multilayer gas flow divider 9 mainly adopts a multilayer air guide plate structure, and the negative pressure design in an inner exhaust pipe can not only pump away the cracking gas in the furnace, but also prevent external air from streaming to the furnace, thereby solving the problem that the prior reduction rotary furnace can not seal the furnace at high temperature and enter the air; as shown in fig. 3, the multilayer gas splitter 9 generally comprises a plurality of layers of circular rings connected to the discharge end cover of the furnace tube, the width of the inner cavity of each layer of circular ring is 100-200 mm, the height of each layer of circular ring is 100-150 mm, the number of the circular rings is preferably 5, and the top of the circular ring in the middle layer is provided with an exhaust hole; dust-carrying gas in the furnace tube is precipitated to a collecting port after passing through an exhaust pipe and a multilayer gas flow divider 9, then enters a dust precipitation collector 11 from the collecting port, and gas is extracted from an exhaust hole through a cracking extraction pipe 20 under negative pressure; because the negative pressure is pumped out, the multilayer cavity from the exhaust port to the middle part of the furnace body has the function of reducing the air inlet amount and preventing the gas in the furnace from flowing outside the furnace to be dispersed, and the whole multilayer ring can prevent the gas inside and outside the furnace from flowing; the furnace tube discharging cover 10 is mainly used for covering a tail end discharging port of a furnace tube, so that the reduced material can be conveniently led out, and external air can be prevented from streaming into the furnace; the dust precipitation collector 11 is mainly used to collect a large amount of dust generated during the reduction process.
The discharge end of the furnace tube of the reduction rotary furnace is not cooled, and the reduced material can be quickly transferred into the spiral discharge sealer 12 from a high-temperature area by utilizing the spiral material scattering device 8 in the furnace tube, so that the temperature of the reduced material in the furnace can be effectively prevented from being reduced to be below 300 ℃, and the generation of highly toxic substances of nickel carbonyl and cobalt carbonyl caused by the reaction of carbon monoxide and metals such as nickel, cobalt and the like in the reduced material is basically avoided.
The spiral discharging sealer 12 can convey the reduced material led out from the furnace tube discharging cover 10 by spiral conveying and cool the reduced material; a long flight-free shaft section is usually left in front of the feed opening of the spiral discharge sealer 12 to effectively reduce the heat transferred to the bearings. In order to effectively reduce the temperature of the reduced material and avoid agglomeration, the lithium battery recycling powder reduction equipment generally further comprises a second spiral discharging sealer, and the feeding end of the second spiral discharging sealer is connected with the discharging end of the spiral discharging sealer 12. For rapid cooling, the spiral discharging sealer 12 and the second spiral discharging sealer are preferably water-cooled spiral discharging sealers; the water-cooling spiral discharging sealer can quickly reduce the reduced material to below 300 ℃ through indirect water cooling.
The combustor 15 is mainly used for sufficiently combusting the pyrolysis gas so as to convert low molecular alkanes, hydrogen and carbon monoxide in the pyrolysis gas into water and carbon dioxide; the combustor 15 is generally a high-temperature combustor, and a honeycomb type combustion structure is arranged in the combustor 15, so that the combustion temperature in the combustor 15 can be kept at about 1200 ℃, and complete combustion can be guaranteed. The combustion-supporting and ignition device 13 arranged at the bottom of the burner 15 is mainly used for introducing combustion-supporting gas into the burner 15 and igniting, and the air inlet is provided with a gas flow controller 14 which is mainly used for controlling the air inlet amount.
The heat exchanger 16 mainly reduces the temperature of the exhaust gas through heat exchange, and the heat exchanger 16 can be various, preferably a water-cooled heat exchanger; the bag-type dust collector 17 is mainly used for removing dust in the exhaust gas; the centrifugal fan 18 is mainly used for guiding the dedusted emission gas into the absorption tower 19 to remove the acid gas therein, and the centrifugal fan 18 can be various, preferably a medium-pressure centrifugal fan; the absorption tower 19 is mainly used for spraying alkali liquor to remove acid gas in the exhaust gas.
Referring to fig. 1 and 4, the above-mentioned lithium battery recycling powder reduction device is used to reduce the ternary battery powder, and the process is as follows: after uniformly mixing the ternary battery powder and the reducing agent to form a mixture, adding the mixture from a raw material bin 1, conveying the mixture into a reduction rotary furnace through a spiral feeding sealer 2, performing low-temperature cracking and high-temperature anaerobic reduction, and performing sealed discharging and indirect water cooling on the reduced material to below 300 ℃ through a spiral discharging sealer 12; the cracked gas is shunted by the multilayer gas diverter 9 to enter the combustor 15 for high-temperature combustion, the combustion is sent to the heat exchanger 16 for rapid water cooling, then sent to the bag-type dust remover 17 for dust removal treatment, and is sent to the absorption tower 19 by medium-pressure induced air in the centrifugal fan 18 after dust removal, and is sprayed with alkali liquor by the absorption tower 19 for leaching, and finally is discharged.
The invention also provides a method for reducing the ternary lithium battery recovered powder, and the method adopts the lithium battery recovered powder reduction equipment to reduce the ternary lithium battery recovered powder.
The reduction method comprises the steps of material preparation;
the material preparation step: weighing the ternary lithium battery recovery powder and the reducing agent according to the mass ratio of 1: 2-5, and uniformly mixing the weighed ternary lithium battery recovery powder and the reducing agent to form a mixture. The reducing agent can be battery negative electrode powder, carbon powder or mixed powder, and the mixed powder is formed by mixing the battery negative electrode powder and the carbon powder.
The reduction method further comprises a reduction control step;
reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer 2 for carbothermic reduction, the furnace temperature is controlled to be 700-750 ℃, the reduction time is controlled to be 100-130 min, and the pressure in the furnace tube is controlled to be 0-100 Pa.
The above reduction method further comprises a pyrolysis gas combustion control step;
and (3) pyrolysis gas combustion control: when the pyrolysis gas is pumped into the combustor 15 through the pyrolysis gas extraction pipe 20 for combustion, the oxygen content in the combustor 15 is controlled to be 4-10%, and the combustion temperature is controlled to be 1100-1200 ℃.
Example 1
The recovery powder of the ternary battery with the model number of 523 is recovered by adopting the recovery powder reduction equipment for the lithium battery, and the process is as follows:
the material preparation step: weighing and uniformly mixing the weighed ternary lithium battery recovery powder and a reducing agent to form a mixture, wherein the weight of the mixture is 10000 kg; the reducing agent is battery cathode powder, the content of which is 40 percent (mass percentage, the same below);
table 1: table of other ingredients of mixture
| Element(s) | Ni | Co | Mn | Li | Cu | Al | Fe |
| Content (%) | 20.0 | 8.0 | 12.05 | 4.8 | 1.0 | 0.5 | 0.1 |
；
Reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer 2 for carbothermic reduction, the furnace temperature is controlled at 700 ℃, the reduction time is controlled at 120min, and the pressure in the furnace tube is controlled at 0-100 Pa;
and (3) pyrolysis gas combustion control: when the pyrolysis gas is pumped into the combustor 15 through the pyrolysis gas extraction pipe 20 for combustion, the oxygen content in the combustor 15 is controlled at 10%, and the combustion temperature is controlled at 1200 ℃.
During the reduction process, the detection shows that the materials in the reduction rotary furnace are not agglomerated, no smoke or dust overflows from the gas guide plates of the multilayer gas splitter 9, and no highly toxic substances are generated; the product obtained by reduction is powdery.
Example 2
The recovery powder of the ternary battery with the model number of 523 is recovered by adopting the recovery powder reduction equipment for the lithium battery, and the process is as follows:
the material preparation step: weighing and uniformly mixing the weighed ternary lithium battery recovery powder and a reducing agent to form a mixture, wherein the weight of the mixture is 10000 kg; the reducing agent is battery cathode powder, the content of which is 40 percent (mass percentage, the same below);
table 2: table of other ingredients of mixture
| Element(s) | Ni | Co | Mn | Li | Cu | Al | Fe |
| Content (%) | 20.0 | 8.0 | 12.05 | 4.8 | 1.0 | 0.5 | 0.1 |
；
Reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer 2 for carbothermic reduction, the furnace temperature is controlled at 750 ℃, the reduction time is controlled at 130min, and the pressure in the furnace tube is controlled at 0-100 Pa;
and (3) pyrolysis gas combustion control: when the pyrolysis gas is pumped into the combustor 15 through the pyrolysis gas extraction pipe 20 for combustion, the oxygen content in the combustor 15 is controlled at 8%, and the combustion temperature is controlled at 1200 ℃.
During the reduction process, the detection shows that the materials in the reduction rotary furnace are not agglomerated, no smoke or dust overflows from the gas guide plates of the multilayer gas splitter 9, and no highly toxic substances are generated; the product obtained by reduction is powdery.
Example 3
The lithium battery recovered powder reduction equipment provided by the invention is used for reducing the ternary battery recovered powder with the model number of 111, and the process is as follows:
the material preparation step: weighing and uniformly mixing the weighed ternary lithium battery recovery powder and a reducing agent to form a mixture, wherein the weight of the mixture is 10000 kg; the reducing agent is battery cathode powder, the content of which is 40 percent (mass percentage, the same below);
table 3: table of other ingredients of mixture
| Element(s) | Ni | Co | Mn | Li | Cu | Al | Fe |
| Content (%) | 13.33 | 13.33 | 13.33 | 4.9 | 1.0 | 0.5 | 0.1 |
；
Reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer 2 for carbothermic reduction, the furnace temperature is controlled at 700 ℃, the reduction time is controlled at 100min, and the pressure in the furnace tube is controlled at 0-100 Pa;
and (3) pyrolysis gas combustion control: when the pyrolysis gas is pumped into the combustor 15 through the pyrolysis gas extraction pipe 20 for combustion, the oxygen content in the combustor 15 is controlled at 6%, and the combustion temperature is controlled at 1200 ℃.
During the reduction process, the detection shows that the materials in the reduction rotary furnace are not agglomerated, no smoke or dust overflows from the gas guide plates of the multilayer gas splitter 9, and no highly toxic substances are generated; the product obtained by reduction is powdery.
Example 4
The lithium battery recovered powder reduction equipment provided by the invention is used for reducing the ternary battery recovered powder with the model number of 111, and the process is as follows:
the material preparation step: weighing and uniformly mixing the weighed ternary lithium battery recovery powder and a reducing agent to form a mixture, wherein the weight of the mixture is 10000 kg; the reducing agent is carbon powder, and the content of the reducing agent is 40 percent (mass percentage, the same below);
table 4: table of other ingredients of mixture
| Element(s) | Ni | Co | Mn | Li | Cu | Al | Fe |
| Content (%) | 13.33 | 13.33 | 13.33 | 4.9 | 1.0 | 0.5 | 0.1 |
；
Reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer 2 for carbothermic reduction, the furnace temperature is controlled at 720 ℃, the reduction time is controlled at 110min, and the pressure in the furnace tube is controlled at 0-100 Pa;
and (3) pyrolysis gas combustion control: when the pyrolysis gas is pumped into the combustor 15 through the pyrolysis gas extraction pipe 20 for combustion, the oxygen content in the combustor 15 is controlled at 5%, and the combustion temperature is controlled at 1200 ℃.
During the reduction process, the detection shows that the materials in the reduction rotary furnace are not agglomerated, no smoke or dust overflows from the gas guide plates of the multilayer gas splitter 9, and no highly toxic substances are generated; the product obtained by reduction is powdery.
Claims (10)
1. Lithium cell recovery powder reduction equipment, its characterized in that: comprises a raw material bin (1), a spiral feeding sealer (2), a reduction rotary furnace, a spiral discharging sealer (12), a burner (15), a heat exchanger (16), a bag-type dust remover (17), a centrifugal fan (18) and an absorption tower (19);
the reduction rotary furnace comprises a furnace tube, the furnace tube is rotatably arranged on a foundation frame through a furnace tube supporting ring (4) and is in transmission connection with a driving device through a rotating gear ring (5); a spiral material scattering device (8) is arranged in the furnace tube, a fire-resistant insulating layer (6) is covered on the outer wall of the furnace tube, and a heating zone (7) is formed between the fire-resistant insulating layer (6) and the furnace tube;
the bottom of the combustor (15) is provided with a combustion-supporting and igniting device (13), an air inlet and a pyrolysis gas inlet, and the air inlet is provided with a gas flow controller (14);
the raw material bin (1) is arranged at the feed end of the spiral feed sealer (2), the discharge end of the spiral feed sealer (2) is rotatably connected with the front end of the furnace tube through the corrugated pipe sealer (3), the upper part of the tail end of the furnace tube is provided with a plurality of layers of gas diverters (9), the tail end lower part is provided with dust sediment collector (11), the tail end discharge gate upper shield of boiler tube is equipped with boiler tube ejection of compact cover (10), the discharge end of boiler tube ejection of compact cover (10) is connected with the feed end of spiral ejection of compact sealer (12), multilayer gas shunt (9) are connected with the bottom pyrolysis gas access of combustor (15) through schizolysis exhaust tube (20), the top gas outlet of combustor (15) is connected with the top air inlet of heat exchanger (16), the bottom gas outlet of heat exchanger (16) is connected with the air inlet of sack cleaner (17), the gas outlet of sack cleaner (17) is passed through centrifugal fan (18) and is connected with the air inlet of absorption tower (19).
2. The lithium battery recovery powder reducing apparatus as set forth in claim 1, wherein: the spiral discharging sealing device also comprises a second spiral discharging sealing device, and the feeding end of the second spiral discharging sealing device is connected with the discharging end of the spiral discharging sealing device (12).
3. The lithium battery recovery powder reducing apparatus as set forth in claim 2, wherein: the spiral discharging sealer (12) and the second spiral discharging sealer are both water-cooling spiral discharging sealers.
4. The lithium battery recovery powder reducing apparatus as set forth in claim 1, wherein: a honeycomb type combustion structure is arranged in the combustor (15).
5. The lithium battery recovery powder reducing apparatus as set forth in claim 1, wherein: the heat exchanger (16) is a water-cooled heat exchanger.
6. The method for reducing the recovered powder of the ternary lithium battery is characterized by comprising the following steps of: the recovery powder for a ternary lithium battery is reduced by using the recovery powder reduction device for a lithium battery as defined in any one of claims 1 to 5.
7. The method for reducing the ternary lithium battery recycled powder of claim 6, wherein: comprises the steps of proportioning;
the material preparation step: weighing the ternary lithium battery recovery powder and the reducing agent according to the mass ratio of 1: 2-5, and uniformly mixing the weighed ternary lithium battery recovery powder and the reducing agent to form a mixture.
8. The method for reducing a ternary lithium battery recycled powder of claim 7, wherein: the reducing agent is battery negative electrode powder, carbon powder or mixed powder, and the mixed powder is formed by mixing the battery negative electrode powder and the carbon powder.
9. The method for reducing a ternary lithium battery recycled powder of claim 7, wherein: also includes a reduction control step;
reduction control step: when the mixture is conveyed into a reduction rotary furnace through a spiral feeding sealer (2) for carbothermic reduction, the furnace temperature is controlled to be 700-750 ℃, the reduction time is controlled to be 100-130 min, and the pressure in the furnace tube is controlled to be 0-100 Pa.
10. The method for reducing a ternary lithium battery recycled powder of claim 7, wherein: the method also comprises a pyrolysis gas combustion control step;
and (3) pyrolysis gas combustion control: when pyrolysis gas is pumped into the combustor (15) through the pyrolysis gas extraction pipe (20) for combustion, the oxygen content in the combustor (15) is controlled to be 4-10%, and the combustion temperature is controlled to be 1100-1200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110691019.5A CN113405367B (en) | 2021-06-22 | 2021-06-22 | Lithium battery recycling powder reduction equipment and ternary lithium battery recycling powder reduction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110691019.5A CN113405367B (en) | 2021-06-22 | 2021-06-22 | Lithium battery recycling powder reduction equipment and ternary lithium battery recycling powder reduction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113405367A true CN113405367A (en) | 2021-09-17 |
| CN113405367B CN113405367B (en) | 2023-05-23 |
Family
ID=77682365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110691019.5A Active CN113405367B (en) | 2021-06-22 | 2021-06-22 | Lithium battery recycling powder reduction equipment and ternary lithium battery recycling powder reduction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113405367B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117232251A (en) * | 2023-11-14 | 2023-12-15 | 佛山市天禄智能装备科技有限公司 | Exhaust powder return feeding bin of rotary furnace |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE8008426L (en) * | 1980-12-01 | 1982-06-02 | Boliden Ab | PROCEDURE FOR EXTRACTION OF METAL CONTENTS FROM COMPLEX SULFIDIC METAL RAW MATERIALS |
| JP2004238435A (en) * | 2003-02-04 | 2004-08-26 | Toyota Motor Corp | Method of gasifying organic waste and gas conversion apparatus |
| CN200972322Y (en) * | 2006-10-20 | 2007-11-07 | 卢国普 | Rotary metallurgical furnace |
| CN201237429Y (en) * | 2008-07-04 | 2009-05-13 | 杭州赛诺索欧电池有限公司 | Full-sealing continuous rotary kiln with storage bin |
| CN202442584U (en) * | 2012-02-17 | 2012-09-19 | 王长春 | Rotary reduction furnace |
| CN102849801A (en) * | 2012-09-11 | 2013-01-02 | 清华大学 | Device and process for producing manganese monoxide through reduction of low-grade manganese oxide ore by using biomass |
| WO2013152831A1 (en) * | 2012-04-12 | 2013-10-17 | Thyssenkrupp Uhde Gmbh | Method for controlling the temperature in the combustion furnace of a claus unit |
| CN103540753A (en) * | 2013-10-15 | 2014-01-29 | 旻鑫系统股份有限公司 | Refining purifying recycling processing method of heavy metal from collected dust or sludge obtained from processing of heavy metal polluted soil or waste |
| CN103604304A (en) * | 2013-11-22 | 2014-02-26 | 中国矿业大学(北京) | Energy-efficient reduction rotary furnace |
| US20140106287A1 (en) * | 2012-10-08 | 2014-04-17 | Ipsen, Inc. | Industrial Heat Treating Furnace That Uses a Protective Gas |
| CN204151075U (en) * | 2014-10-22 | 2015-02-11 | 天津博尔迈环保科技有限公司 | A kind of sealing cooling discharging device |
| CN205495178U (en) * | 2016-04-14 | 2016-08-24 | 阳新鹏富矿业有限公司 | Smelting furnace vent gas treatment system in |
| CN205940168U (en) * | 2016-07-29 | 2017-02-08 | 北京清新环境技术股份有限公司 | Multistage cooling device suitable for high temperature solid |
| CN111534697A (en) * | 2020-06-09 | 2020-08-14 | 中国恩菲工程技术有限公司 | Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries |
| CN111750664A (en) * | 2020-07-28 | 2020-10-09 | 赣州鼎盛炉业有限公司 | Rotary furnace with heat insulating plate |
| CN111765470A (en) * | 2020-06-19 | 2020-10-13 | 自贡佳源炉业有限公司 | Continuous cracking calcining equipment |
| CN211695824U (en) * | 2019-09-10 | 2020-10-16 | 格林美（无锡）能源材料有限公司 | Lithium battery powder sintering rotary kiln |
| CN112195343A (en) * | 2020-09-11 | 2021-01-08 | 湖南先导新材料科技有限公司 | Lithium battery recycling method and system |
| EP3936631A1 (en) * | 2019-03-04 | 2022-01-12 | Kawasaki Jukogyo Kabushiki Kaisha | Apparatus for roasting lithium ion battery waste |
-
2021
- 2021-06-22 CN CN202110691019.5A patent/CN113405367B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE8008426L (en) * | 1980-12-01 | 1982-06-02 | Boliden Ab | PROCEDURE FOR EXTRACTION OF METAL CONTENTS FROM COMPLEX SULFIDIC METAL RAW MATERIALS |
| JP2004238435A (en) * | 2003-02-04 | 2004-08-26 | Toyota Motor Corp | Method of gasifying organic waste and gas conversion apparatus |
| CN200972322Y (en) * | 2006-10-20 | 2007-11-07 | 卢国普 | Rotary metallurgical furnace |
| CN201237429Y (en) * | 2008-07-04 | 2009-05-13 | 杭州赛诺索欧电池有限公司 | Full-sealing continuous rotary kiln with storage bin |
| CN202442584U (en) * | 2012-02-17 | 2012-09-19 | 王长春 | Rotary reduction furnace |
| WO2013152831A1 (en) * | 2012-04-12 | 2013-10-17 | Thyssenkrupp Uhde Gmbh | Method for controlling the temperature in the combustion furnace of a claus unit |
| CN102849801A (en) * | 2012-09-11 | 2013-01-02 | 清华大学 | Device and process for producing manganese monoxide through reduction of low-grade manganese oxide ore by using biomass |
| US20140106287A1 (en) * | 2012-10-08 | 2014-04-17 | Ipsen, Inc. | Industrial Heat Treating Furnace That Uses a Protective Gas |
| CN103540753A (en) * | 2013-10-15 | 2014-01-29 | 旻鑫系统股份有限公司 | Refining purifying recycling processing method of heavy metal from collected dust or sludge obtained from processing of heavy metal polluted soil or waste |
| CN103604304A (en) * | 2013-11-22 | 2014-02-26 | 中国矿业大学(北京) | Energy-efficient reduction rotary furnace |
| CN204151075U (en) * | 2014-10-22 | 2015-02-11 | 天津博尔迈环保科技有限公司 | A kind of sealing cooling discharging device |
| CN205495178U (en) * | 2016-04-14 | 2016-08-24 | 阳新鹏富矿业有限公司 | Smelting furnace vent gas treatment system in |
| CN205940168U (en) * | 2016-07-29 | 2017-02-08 | 北京清新环境技术股份有限公司 | Multistage cooling device suitable for high temperature solid |
| EP3936631A1 (en) * | 2019-03-04 | 2022-01-12 | Kawasaki Jukogyo Kabushiki Kaisha | Apparatus for roasting lithium ion battery waste |
| CN211695824U (en) * | 2019-09-10 | 2020-10-16 | 格林美（无锡）能源材料有限公司 | Lithium battery powder sintering rotary kiln |
| CN111534697A (en) * | 2020-06-09 | 2020-08-14 | 中国恩菲工程技术有限公司 | Selection-smelting combined comprehensive recovery method and device for waste lithium ion batteries |
| CN111765470A (en) * | 2020-06-19 | 2020-10-13 | 自贡佳源炉业有限公司 | Continuous cracking calcining equipment |
| CN111750664A (en) * | 2020-07-28 | 2020-10-09 | 赣州鼎盛炉业有限公司 | Rotary furnace with heat insulating plate |
| CN112195343A (en) * | 2020-09-11 | 2021-01-08 | 湖南先导新材料科技有限公司 | Lithium battery recycling method and system |
Non-Patent Citations (1)
| Title |
|---|
| 汪琦;: "含碳球团还原反应及其技术" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117232251A (en) * | 2023-11-14 | 2023-12-15 | 佛山市天禄智能装备科技有限公司 | Exhaust powder return feeding bin of rotary furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113405367B (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111271711A (en) | Continuous carbonization pyrolysis treatment method for waste lithium batteries | |
| CN107866437A (en) | A kind of processing method of discarded circuit board pyrolysis recovery | |
| CN206318947U (en) | Continuous waste plastic circulating cracking system | |
| CN110194957A (en) | A kind of waste and old lithium ion battery charing process system | |
| CN111842410A (en) | Waste power battery monomer full-component recovery system | |
| CN212585474U (en) | System for decomposing metal salt through heat storage ball heat storage self-circulation | |
| CN109103538A (en) | A kind of Non-oxygen pyrolytic processing recovery system of waste lithium cell positive plate | |
| CN113405367A (en) | Lithium battery recovery powder reduction equipment and ternary lithium battery recovery powder reduction method | |
| Zhang et al. | Extraction of valuable metals from spent cathode materials by reductive roasting in methane atmosphere | |
| CN115172923A (en) | Method for recovering battery powder through low-temperature pyrolysis desorption | |
| CN206457451U (en) | A kind of carbon black reaction and collection system and carbon black production line | |
| CN112322899B (en) | Method and device for leaching waste lithium ion battery anode | |
| Yang et al. | Mechanism of selective lithium extraction from spent LiFePO4 cathodes in oxidizing alkaline leaching system | |
| CN107022659A (en) | High-temperature slag waste heat gradient recycling system | |
| CN216698489U (en) | Waste ternary power battery treatment system | |
| CN209989443U (en) | Reduction furnace for treating smelting slag containing cobalt and copper | |
| Jiang et al. | An innovative dual-strengthening pretreatment to improve Li and Co leaching in spent lithium-ion batteries: Pyrolysis combined with mechanical grinding | |
| CN113381059A (en) | Device and method for recovering metals in waste ternary lithium batteries based on plasmas | |
| CN106497583A (en) | A kind of cone-type spiral regenerative gas electronic waste pyrolysis system | |
| CN113957238A (en) | Reduction roasting method and reduction roasting system for metal oxide-containing material capable of realizing energy conservation and emission reduction | |
| CN219702976U (en) | High-temperature cyclone decomposition device for solid materials | |
| CN206522777U (en) | A kind of heat accumulating type deflection plate electronic gas refuse pyrolysis system | |
| CN220062627U (en) | Waste battery medium-temperature cracking heat energy recycling device | |
| CN108923093A (en) | Waste lithium cell handles recyclable device | |
| CN220911457U (en) | Treatment system for recycling waste lithium ion batteries based on vertical rotary furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |