CN113479873A - Continuous graphitization and high-temperature carbonization integrated furnace and working method thereof - Google Patents

Continuous graphitization and high-temperature carbonization integrated furnace and working method thereof Download PDF

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CN113479873A
CN113479873A CN202110748023.0A CN202110748023A CN113479873A CN 113479873 A CN113479873 A CN 113479873A CN 202110748023 A CN202110748023 A CN 202110748023A CN 113479873 A CN113479873 A CN 113479873A
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temperature carbonization
graphitization
temperature
continuous
furnace
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孟祥安
王士戈
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Haicheng Shenhe Tech Co ltd
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Haicheng Shenhe Tech Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/205Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30

Abstract

The invention relates to a continuous graphitization and high temperature carbonization integrated furnace and a working method thereof.A furnace body is coaxially provided with a columnar electrode, a tubular electrode and a high temperature carbonization furnace wall from inside to outside, wherein the columnar electrode is an anode electrode, and the tubular electrode is a cathode electrode; the annular space between the columnar electrode and the tubular electrode is a graphitized region; the annular space between the tubular electrode and the high-temperature carbonization furnace wall is a high-temperature carbonization area; the bottom of the graphitization zone is connected with a graphitized material continuous discharging system through a heat preservation section, and the bottom of the high-temperature carbonization zone is connected with a high-temperature carbonization material continuous discharging system. The invention completes the graphitization and high-temperature carbonization processes in the same furnace body, utilizes the heat overflowing in the graphitization process of the graphitized material to heat the high-temperature carbonization material to the high-temperature carbonization temperature, realizes the high-temperature carbonization of the material, and realizes the continuous production of graphitization and high-temperature carbonization; not only reduces the production cost, but also realizes the full utilization of energy.

Description

Continuous graphitization and high-temperature carbonization integrated furnace and working method thereof
Technical Field
The invention relates to the technical field of material carbonization and graphitization, in particular to an integrated furnace for realizing continuous graphitization and high-temperature carbonization of artificial graphite used as a lithium ion battery cathode material and a working method thereof.
Background
The high-purity artificial graphite is widely used as a lithium battery cathode material, and at present, the preparation of the high-purity artificial graphite is mainly realized by adopting an Acheson furnace. The production cycle of the Acheson furnace for preparing the artificial graphite needs about 40 days, a large amount of resistance materials and insulating materials are needed, the thermal efficiency is only 15% -20%, and in addition, other losses result in that the comprehensive thermal efficiency is only about 15%, so that the energy waste is serious, and the production cost is high.
High-temperature carbonization is a new preparation method of lithium ion battery cathode materials, and the materials need to be heated to about 1200 ℃ in the high-temperature carbonization process, so that the current method for preparing the lithium ion battery cathode materials by high-temperature carbonization is widely applied. The temperature difference between graphitization and high temperature carbonization is more than 1500 ℃, if the excessive heat of graphitization can be used for high temperature carbonization, the production cost of the artificial graphite material can be greatly reduced, the full utilization of energy can be realized, and good market benefit and social benefit can be achieved.
Disclosure of Invention
The invention provides a continuous graphitization and high-temperature carbonization integrated furnace and a working method thereof.A graphitization and high-temperature carbonization process is completed in the same furnace body, the heat overflowing in the graphitization process of a graphitization material is utilized to heat the high-temperature carbonization material to a high-temperature carbonization temperature, so that the high-temperature carbonization of the material is realized, and the continuous production of graphitization and high-temperature carbonization is realized; not only reduces the production cost, but also realizes the full utilization of energy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a continuous graphitization and high temperature carbonization integrated furnace comprises a furnace body, a graphitized material continuous discharging system and a high temperature carbonized material continuous discharging system; the furnace body is coaxially provided with a columnar electrode, a tubular electrode and a high-temperature carbonization furnace wall from inside to outside, the columnar electrode and the tubular electrode are respectively connected with an external power supply device, the columnar electrode is an anode electrode, and the tubular electrode is a cathode electrode; the annular space between the columnar electrode and the tubular electrode is a graphitized region; the annular space between the tubular electrode and the high-temperature carbonization furnace wall is a high-temperature carbonization area; a graphitized material inlet is arranged at the top of the furnace body above the corresponding graphitized region, and a high-temperature carbonized material inlet is arranged above the corresponding high-temperature carbonized region; the bottom of the graphitization zone is connected with a graphitized material continuous discharging system through a heat preservation section, and the bottom of the high-temperature carbonization zone is connected with a high-temperature carbonization material continuous discharging system.
The furnace top is provided with a volatile gas outlet.
The furnace top is provided with a temperature thermocouple, and the temperature measuring end of the temperature thermocouple extends into the graphitizing region.
And the outer side of the high-temperature carbonization furnace wall is sequentially provided with a heat-preservation and heat-insulation layer and a furnace outer wall.
The graphitized material continuous discharging system is composed of a graphitized material discharging device, a graphitized material cooling device and a graphitized material outlet bin which are sequentially connected.
The continuous discharging system of the high-temperature carbonized material consists of a high-temperature carbonized material discharging device, a high-temperature carbonized material cooling device and a high-temperature carbonized material outlet bin which are sequentially connected.
And a heat insulation wall is arranged on the outer side of the heat insulation section.
In the working method of the continuous graphitization and high temperature carbonization integrated furnace, in the furnace body, a graphitized material enters a graphitization zone and continuously moves downwards, and a high temperature carbonization material enters a high temperature carbonization zone and continuously moves downwards; heating the graphitized material to 3000-3200 ℃ by a heating device consisting of a columnar electrode and a tubular electrode; heating the external high-temperature carbonized material to 1200-1500 ℃ by the overflow heat of the graphitization process; the graphitized material after graphitization is discharged through a graphitized material continuous discharging system, and the high-temperature carbonized material after high-temperature carbonization is discharged through a high-temperature carbonized material continuous discharging system.
Compared with the prior art, the invention has the beneficial effects that:
1) the continuous graphitization process is adopted, and the materials are preheated, heated, insulated and cooled in the continuous downward moving process of the materials, so that the continuous production is realized, the process is effectively controlled, the full utilization of energy is realized, and the thermal efficiency reaches more than 80%;
2) resistance materials and heat insulation materials are not needed, and the cost of auxiliary materials is greatly reduced;
3) utilizing the heat overflowing in the continuous graphitization process to heat the graphitized material moving downwards to the high-temperature carbonization material outside the channel and moving downwards to the material in the channel to the high-temperature carbonization temperature, so that the material is carbonized at high temperature; the high-temperature carbonization process is also a continuous heating, discharging and discharging process, namely the continuous high-temperature carbonization process is realized;
4) after heat in the graphitization process overflows, the heat is absorbed and separated by the outer high-temperature carbonized material, so that the material is carbonized at high temperature by utilizing the overflowing heat, the furnace body is effectively protected from being damaged by high temperature, the service life of the furnace body is prolonged, and the safety operation of the furnace body is guaranteed.
Drawings
FIG. 1 is a schematic structural diagram of a continuous graphitization and high temperature carbonization integrated furnace according to the present invention.
In the figure: 1. graphitized material inlet 2, high-temperature carbonized material inlet 3, columnar electrode 4, tubular electrode 5, high-temperature carbonized furnace wall 6, heat-preservation and heat-insulation layer 7, volatile gas outlet 8, furnace outer wall 9, power supply device 10, heat-preservation section 11, graphitized material discharging device 12, graphitized material cooling device 13, graphitized material outlet bin 14, high-temperature carbonized material discharging device 15, high-temperature carbonized material cooling device 16, high-temperature carbonized material outlet bin 17, temperature-measuring thermocouple I, graphitizing zone II and high-temperature carbonized zone
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
as shown in fig. 1, the continuous graphitization and high temperature carbonization integrated furnace provided by the invention comprises a furnace body, a graphitized material continuous discharging system and a high temperature carbonization material continuous discharging system; the furnace body is coaxially provided with a columnar electrode 3, a tubular electrode 4 and a high-temperature carbonization furnace wall 5 from inside to outside, the columnar electrode 3 and the tubular electrode 4 are respectively connected with an external power supply device 9, the columnar electrode 3 is an anode electrode, and the tubular electrode 4 is a cathode electrode; the annular space between the columnar electrode 3 and the tubular electrode 4 is a graphitized region I; the annular space between the tubular electrode 4 and the high-temperature carbonization furnace wall 5 is a high-temperature carbonization area II; a graphitized material inlet 1 is arranged at the top of the furnace body above the corresponding graphitized zone I, and a high-temperature carbonized material inlet 2 is arranged above the corresponding high-temperature carbonized zone II; the bottom of the graphitization zone I is connected with a graphitized material continuous discharging system through a heat preservation section 10, and the bottom of the high-temperature carbonization zone II is connected with a high-temperature carbonization material continuous discharging system.
The furnace top is provided with a volatile gas outlet 7.
The furnace top is provided with a temperature thermocouple 17, and the temperature measuring end of the temperature thermocouple 17 extends into the graphitization zone I.
And a heat-preservation and heat-insulation layer 6 and an outer furnace wall 8 are sequentially arranged on the outer side of the high-temperature carbonization furnace wall 5.
The continuous discharging system for the graphitized materials is composed of a graphitized material discharging device 11, a graphitized material cooling device 12 and a graphitized material outlet bin 13 which are connected in sequence.
The continuous discharging system of the high-temperature carbonized material consists of a high-temperature carbonized material discharging device 14, a high-temperature carbonized material cooling device 15 and a high-temperature carbonized material outlet bin 16 which are connected in sequence.
And a heat insulation wall is arranged on the outer side of the heat insulation section 10.
A working method of the continuous graphitization and high temperature carbonization integrated furnace is characterized in that in a furnace body, a graphitization material enters a graphitization zone I and continuously moves downwards, and a high temperature carbonization material enters a high temperature carbonization zone II and continuously moves downwards; heating the graphitized material to 3000-3200 ℃ by a heating device consisting of a columnar electrode 3 and a tubular electrode 4; heating the external high-temperature carbonized material to 1200-1500 ℃ by the overflow heat of the graphitization process; the graphitized material after graphitization is discharged through a graphitized material continuous discharging system, and the high-temperature carbonized material after high-temperature carbonization is discharged through a high-temperature carbonized material continuous discharging system.
The graphitization and high-temperature carbonization integrated furnace is a continuous and efficient device capable of simultaneously performing graphitization and high-temperature carbonization, and the graphitization and the high-temperature carbonization processes are completed in the same furnace body. The furnace body is divided into a graphitization zone I and a high-temperature carbonization zone II, wherein the graphitization zone I is positioned in the middle of the furnace body and consists of a columnar electrode 3 and a tubular electrode 4, an annular space between the graphitization zone I and the tubular electrode is the graphitization zone I, and a graphitization material is heated and graphitized in the zone. The periphery of the tubular electrode 4 is provided with a high-temperature carbonization zone II which is an annular space formed between the tubular electrode 4 and the high-temperature carbonization outer furnace wall 5; when the graphitization and high temperature carbonization integrated furnace works, the high temperature carbonization material is heated to the high temperature carbonization temperature by utilizing the heat overflowing in the graphitization process.
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
[ examples ] A method for producing a compound
As shown in fig. 1, in this embodiment, the continuous graphitization and high temperature carbonization integrated furnace includes a furnace body, a graphitized material continuous discharging system, and a high temperature carbonization material continuous discharging system.
The upper part of the top of the furnace body is provided with a sealing cover body. The top of the sealing cover body is provided with a graphitized material inlet 1 and a high-temperature carbonized material inlet 2; graphitized materials and high-temperature carbonized materials enter the corresponding graphitized area I and the high-temperature carbonized area II from corresponding inlets; the top of the sealing cover body is also provided with a volatile gas outlet 7, and volatile gas discharged in the graphitization process and the high-temperature carbonization process is discharged out of the furnace body from the volatile gas outlet 7 and enters a subsequent processing device after being condensed for environmental protection processing.
In the embodiment, the columnar electrode 3 adopts a cylindrical graphite rod, the tubular electrode 4 adopts a graphite circular tube, the graphite rod is positioned at the center of the graphite circular tube, and the graphite rod and the graphite circular tube jointly form a graphitization zone I; the heat preservation section 10 is established to the bottom in graphitization district I, accomplishes the graphitization material of graphitization process through the heat preservation process after, gets into graphitization material cooling device 12 through graphitization material eduction gear 11, discharges into graphitization material export storehouse 13 after the cooling. In this embodiment, the graphitized material discharging device 11 is a star discharger made of a graphite material resistant to 2000 ℃, and has the advantages of sealing performance, high temperature resistance, controllable discharge amount, and capability of blocking gas and preventing external gas from flowing into the furnace body. The graphite cooling device 12 adopts a water cooling jacket structure to cool the graphitized material, the water cooling jacket is arranged at the outer side of the graphitized material channel, and the cooling water quantity is controllable.
The periphery of the graphitization area I is a high-temperature carbonization area II, the high-temperature carbonization area II is an annular space formed by a graphite round tube and a high-temperature carbonization furnace wall 5 together, a high-temperature carbonized material which finishes the high-temperature carbonization process enters a high-temperature carbonized material cooling device 15 from a high-temperature carbonized material discharge device 14, and is discharged into a high-temperature carbonized material outlet bin 16 after being cooled. In this embodiment, the high-temperature carbonized material discharge device 14 is a star-shaped discharger made of heat-resistant alloy material, which can resist temperature up to 900 ℃, has sealing property and controllable discharge amount, and can block gas to prevent external gas from flowing into the furnace body. The high-temperature carbonized material cooling device 15 adopts a water cooling jacket structure to cool the high-temperature carbonized material, the water cooling jacket is arranged on the outer side of the high-temperature carbonized material channel, and the amount of cooling water is controllable.
The outer side of the high-temperature carbonization furnace wall 5 is provided with a heat-preservation and heat-insulation layer which is made of composite material with 1800 ℃ high temperature resistance and insulating property.
And the top of the sealing cover body is also provided with a temperature thermocouple 17 for measuring the temperature of the graphitization zone I. The upper parts of the graphitization zone I and the high-temperature carbonization zone II are respectively provided with a material level measuring device.
Through 1 cloth in to graphitization district I of graphitization material entry, through high temperature carbonization material entry 2 cloth II in to the high temperature carbonization district, link to each other columnar electrode 3 with the positive pole of outside power supply unit 9, link to each other tubular electrode 4 with the negative pole of outside power supply unit 9, the circular telegram back, I heating heaies up in graphitization district, heats the graphitization material to the required temperature of graphitization. And then, starting the graphitized material continuous discharge system, allowing the graphitized material after graphitization to enter a graphitized material cooling device 12 through a heat preservation section 10 and a graphitized material discharge device 11, and allowing the graphitized material after cooling to enter a graphitized material outlet bin 13.
The heat overflowing after the temperature of the graphitization zone I is raised is conducted to the high-temperature carbonized material in the high-temperature carbonization zone II through the outer wall of the tubular electrode 4 to carry out high-temperature carbonization on the high-temperature carbonized material. The graphitization temperature of the graphitization material is 3000-3200 ℃, and the high temperature carbonization temperature of the high temperature carbonization material is only 1200-1500 ℃, namely the temperature difference between the graphitization zone I and the high temperature carbonization zone II is more than 1500 ℃, so that the temperature requirement of high temperature carbonization can be met by utilizing the heat overflowing from the graphitization zone I. The high-temperature carbonized material after the high-temperature carbonization process enters a high-temperature carbonized material cooling device 15 through a high-temperature carbonized material discharge device 14, and is discharged into a high-temperature carbonized material outlet bin 16 after being cooled.
Volatile gas generated in the temperature rising process of the graphitized material is converged with volatile gas generated in the temperature rising process of the high-temperature carbonized material, discharged through a volatile gas outlet 7, condensed and then enters a subsequent processing device for environment-friendly processing.
Before the temperature of the graphitization zone I is raised, the material is distributed into the graphitization zone I, and the material is filled to the required height according to the process requirement. In general, most of the materials to be graphitized are carbon materials, which are non-conductive or have low conductivity, so that at the initial temperature-raising stage, a graphite conductive material with a proper height needs to be filled in the lower section of the graphitization region between the columnar electrode 3 and the tubular electrode 4. After the anode and the cathode are electrified, resistance heat is generated after current is conducted through the graphite conductive material, the current flows among the conductive materials filled among the 2 electrodes in an initial temperature rise state, the graphitized material positioned at the corresponding part is heated under the action of the resistance heat, and the temperature is continuously raised to reach 3000-3200 ℃. Due to the conduction of the temperature, the temperature of the graphitized material at the upper part is increased from bottom to top according to a certain temperature gradient. The conductivity of the graphitized material between the anode and the cathode changes along with the increase of the temperature, the conductivity of the graphitized material forms a conductivity gradient which gradually decreases from bottom to top, and the conductivity of the graphitized material is optimal when the graphitized material reaches the graphitization temperature. After the initial temperature rise process, when stable temperature distribution, current and resistance gradient are formed between the anode and the cathode, continuous material distribution and material discharge are started, otherwise, the resistivity between 2 electrodes is further reduced, and the current is continuously increased, so that over-temperature and over-current are generated.
By controlling the discharge speed of the graphitized material, the resistance gradient formed by the temperature rise between the 2 electrodes can be constant, and the current is further kept constant. Under a normal working state, the graphitization zone I forms three temperature rising sections, namely, the lower section (within 600mm from the bottom) of the graphitization zone is a conductor temperature rising section, the graphitization material in the section is heated quickly, the resistance is low, the section is in a full conduction state, and the temperature can rise to 3000-3200 ℃; the middle section (the lower section of the graphitized zone is upward within 600 mm) of the graphitized zone is a semiconductor temperature rise section, the temperature of the section is about 3000-2000 ℃, the graphitization degree of the graphitized material is not high, the graphitized material is mostly in a semiconductor state, and the electric conductivity is poor. The upper section of the graphitizing zone (the area above the middle section of the graphitizing zone) is a preheating section, and the temperature of the section is raised mainly through the heat uploaded by the conductor temperature raising section and the semiconductor temperature raising section. The graphitized material is continuously heated and the graphitized material is continuously discharged, so that the constant temperature rise parameter in the furnace is kept, and further the continuous graphitizing production is realized.
The high-temperature carbonization material enters a high-temperature carbonization zone II after being distributed, the overflow heat is transmitted to the high-temperature carbonization zone II through the outer wall of the tubular electrode along with the temperature rise of the graphitization zone I, so that the high-temperature carbonization material is heated, the high-temperature carbonization temperature is generally 1200-1500 ℃, the overflow heat can meet the requirement of high-temperature carbonization, and after the temperature rise of the high-temperature carbonization material reaches the process requirement, continuous distribution and continuous discharge are started, so that the high-temperature carbonization process and the graphitization process are synchronously carried out.
In this embodiment, the outer side of the high-temperature carbonization furnace wall of the continuous graphitization and high-temperature carbonization integrated furnace is provided with a heat preservation and insulation layer. Because the periphery of the graphitization zone I is provided with the high-temperature carbonization zone II, the heat overflowing in the graphitization process is firstly absorbed and blocked by the high-temperature carbonization material, and the heat conducted to the high-temperature carbonization furnace wall 5 and the heat-preservation and heat-insulation insulating layer 6 is greatly reduced, generally not more than 1200-1500 ℃, only by selecting proper heat-preservation and heat-insulation materials, the safety of the furnace body can be ensured, the maintenance cost is reduced, and the service life of the whole furnace is greatly prolonged.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (8)

1. A continuous graphitization and high temperature carbonization integrated furnace is characterized by comprising a furnace body, a graphitized material continuous discharging system and a high temperature carbonized material continuous discharging system; the furnace body is coaxially provided with a columnar electrode, a tubular electrode and a high-temperature carbonization furnace wall from inside to outside, the columnar electrode and the tubular electrode are respectively connected with an external power supply device, the columnar electrode is an anode electrode, and the tubular electrode is a cathode electrode; the annular space between the columnar electrode and the tubular electrode is a graphitized region; the annular space between the tubular electrode and the high-temperature carbonization furnace wall is a high-temperature carbonization area; a graphitized material inlet is arranged at the top of the furnace body above the corresponding graphitized region, and a high-temperature carbonized material inlet is arranged above the corresponding high-temperature carbonized region; the bottom of the graphitization zone is connected with a graphitized material continuous discharging system through a heat preservation section, and the bottom of the high-temperature carbonization zone is connected with a high-temperature carbonization material continuous discharging system.
2. A continuous graphitization, high temperature carbonization integrated furnace as claimed in claim 1, wherein the furnace top is provided with a volatile gas outlet.
3. The continuous graphitization and high temperature carbonization integrated furnace as claimed in claim 1, wherein the furnace top is provided with a temperature thermocouple, and the temperature measuring end of the temperature thermocouple extends into the graphitization zone.
4. The continuous graphitization and high temperature carbonization integrated furnace as claimed in claim 1, wherein the outer side of the high temperature carbonization furnace wall is provided with a heat insulation layer and a furnace outer wall in sequence.
5. The continuous graphitization and high temperature carbonization integrated furnace as claimed in claim 1, wherein the graphitized material continuous discharging system comprises a graphitized material discharging device, a graphitized material cooling device and a graphitized material outlet bin which are connected in sequence.
6. The continuous graphitization and high temperature carbonization integrated furnace as claimed in claim 1, wherein the continuous high temperature carbonization material discharging system comprises a high temperature carbonization material discharging device, a high temperature carbonization material cooling device and a high temperature carbonization material outlet bin which are connected in sequence.
7. The continuous graphitization and high temperature carbonization integrated furnace as claimed in claim 1, wherein the heat preservation section is provided with a heat preservation and heat insulation wall on the outer side.
8. The working method of the continuous graphitization and high temperature carbonization integrated furnace as claimed in any one of claims 1 to 7, wherein in the furnace body, a graphitized material enters the graphitization zone and continuously moves downwards, and a high temperature carbonized material enters the high temperature carbonization zone and continuously moves downwards; heating the graphitized material to 3000-3200 ℃ by a heating device consisting of a columnar electrode and a tubular electrode; heating the external high-temperature carbonized material to 1200-1500 ℃ by the overflow heat of the graphitization process; the graphitized material after graphitization is discharged through a graphitized material continuous discharging system, and the high-temperature carbonized material after high-temperature carbonization is discharged through a high-temperature carbonized material continuous discharging system.
CN202110748023.0A 2021-07-01 2021-07-01 Continuous graphitization and high-temperature carbonization integrated furnace and working method thereof Pending CN113479873A (en)

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