CN110451486B - Device and method for preparing carbon nanotubes in batches - Google Patents
Device and method for preparing carbon nanotubes in batches Download PDFInfo
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- CN110451486B CN110451486B CN201910730497.5A CN201910730497A CN110451486B CN 110451486 B CN110451486 B CN 110451486B CN 201910730497 A CN201910730497 A CN 201910730497A CN 110451486 B CN110451486 B CN 110451486B
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Abstract
The invention discloses a device and a method for preparing carbon nano tubes in batches. Based on the technology of preparing carbon nano tubes by floating catalytic chemical vapor deposition, inorganic ceramic beads are used as a collecting carrier and are placed in a high-temperature zone of an inclinable tubular rotary furnace, and a carbon source and a catalyst are introduced for growing the carbon nano tubes. After the growth is finished, the furnace body is inclined and simultaneously rotates, the carbon nano tubes deposited on the wall of the rotary furnace are scraped by using ceramic beads, the carbon nano tubes enter a solid powder separator for separation, and carbon nano tube powder is brought into a powder collector by inert gas flow to be collected, so that the carbon nano tubes are finally obtained. The invention can realize the continuous batch preparation of the carbon nano tube, solves the problem that the carbon nano tube product is easy to deposit on the tube wall in the furnace under the reaction condition of obtaining stable airflow field distribution, obtains the high-quality carbon nano tube, is easy to enlarge and realize industrialization, and has important economic value.
Description
Technical Field
The invention belongs to the technical field of new materials, relates to a nano carbon material, and particularly relates to a device and a method for preparing carbon nanotubes in batches.
Background
The special nanotube tubular structure of the carbon nanotube endows the carbon nanotube with excellent comprehensive performance, and has important application in the fields of mechanical enhancement, conductive filling, heat conduction modification and the like. The multi-walled carbon nanotube is industrialized, is applied to the field of lithium battery conductive additives on a large scale, and new application fields are continuously mature, so that a huge market space is gradually shown. Therefore, the scale-controllable preparation of carbon nanotubes, and the realization of continuous mass production, are important requirements for the further development of the current carbon nanotube preparation technology. The mainstream preparation method in the field of carbon nanotubes at present is a chemical vapor deposition method, and a crystalline sp2 hybrid carbon material is deposited and grown on the surface of a catalyst by cracking an organic carbon source at high temperature. The invention Chinese patent CN200710098478.2 discloses a method and a device for continuously producing carbon nanotubes, which adopts a fluidized bed process and utilizes a catalyst to be in a fluidized suspension state in a reaction cavity to prepare carbon nanotube powder. The Chinese invention patent CN201610378632.0 discloses a self-cleaning fluidized bed reactor for carbon nanotube production, which uses a stirring scraper device in a reaction cavity to scrape off carbon nanotubes which may be adhered to the inner wall of the fluidized bed reactor, and does not need intermittent shutdown for cleaning, thereby obtaining higher production efficiency. The invention patent CN201610772335.4 discloses a continuous carbon nanotube generation device, which solves the problem that the carbon nanotubes are easy to adhere to the inner wall of a cavity in the production process through a layer plate device, and improves the production efficiency. Most of the existing preparation technologies can not well solve the problem of carbon nanotube collection, and especially when the floating chemical vapor deposition technology is adopted to prepare the carbon nanotubes, a large amount of the carbon nanotubes are deposited in the reaction cavity and cannot be effectively collected, so that the preparation efficiency and the production cost are greatly influenced.
Disclosure of Invention
It is a primary objective of the embodiments of the present disclosure to provide an apparatus and method for batch preparation of carbon nanotubes, so as to overcome the disadvantages in the prior art.
In order to achieve the purpose of the invention, the technical scheme of the embodiment of the disclosure is as follows: a method for preparing carbon nanotubes in batches specifically comprises the following steps:
s1) loading the collected carrier into a solid feeder, and introducing inert gas to empty air;
s2) adjusting the tiltable tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce inert gas;
s3) starting a solid feeder, and loading the collected carrier into the tiltable tubular rotary furnace;
s4) starting a temperature rise program of the tubular rotary furnace, raising the temperature to a specified temperature, and switching and introducing a carbon source, a catalyst and a mixed carrier gas;
s5) after the reaction is finished, stopping introducing the mixed gas, switching to introduce the inert gas, starting a furnace tube rotating device to rotate the furnace tube for a certain time at a certain rotating speed, then starting a furnace body tilting mechanism to enable the furnace body to tilt downwards towards a discharge port, starting a solid powder separator valve, and pouring the obtained product into a solid powder separator filled with the inert gas;
and S6) after a linkage valve of the tubular furnace and the solid powder separator is closed, opening a rotary disc of the solid powder separator, introducing inert gas, separating the collected carrier from the powder product, feeding the powder product into a powder collector, and separating to obtain a final product.
And S7) repeating the steps S3-S6 to realize the continuous batch preparation of the carbon nano tubes.
And S7), repeating the process, wherein the furnace body can not be cooled, and continuous production is realized.
According to the embodiment of the disclosure, the inorganic ceramic beads of the collecting carrier in S1) are zirconia, alumina, silicon nitride, mullite or quartz, and the diameter is 0.1 mm-5 mm; the inert gas may be nitrogen, argon, and helium.
According to the embodiment of the disclosure, the specified temperature in the S4) is 600-1200 ℃, and the reaction time is 10 minutes-5 hours; the mass ratio among the carbon source, the catalyst and the mixed carrier gas is as follows: 5-30:0.05-5:50-200.
According to an embodiment of the present disclosure, the carbon source is methane, ethane, propane, n-hexane, heptane, ethylene, propylene, acetylene, methanol, ethanol, isopropanol, n-butanol, methyl ether, diethyl ether, benzene, toluene, or xylene; the catalyst is ferrocene; the mixed carrier gas is a mixed gas of inert gas and hydrogen, and the volume ratio of the inert gas to the hydrogen is (20): 90.
according to the embodiment of the disclosure, in the step S5), the furnace tube rotates at 10-200 r/min for 2-30 min, and the inclination angle is 10-45 degrees.
According to the embodiment of the disclosure, the rotating speed of the solid powder separator rotating disc in S6) is 50-200 r/min, and the time is 2-30 min.
According to the embodiment of the disclosure, a growth promoter can be further added in the S4), wherein the growth promoter is thiophene, and the mass ratio of the growth promoter to the thiophene is 0.01-0.5.
It is another object of an embodiment of the present disclosure to provide an apparatus for mass production of carbon nanotubes according to the above method, the apparatus comprising a solid feeder, a tiltable tube type rotary kiln, a solid powder separator, a powder collector, a collecting carrier and an auxiliary system;
the solid feeder is used for adding materials into the tiltable tube type rotary furnace;
the tiltable tube type rotary furnace is used for synthesizing carbon nanotubes;
the collecting carrier is used for collecting the materials stuck on the side wall of the tiltable tubular rotary furnace;
the solid powder separator is used for separating the carbon nano tubes bonded on the surface of the collecting carrier;
the powder collector is used for collecting the separated carbon nano tubes;
the auxiliary system is used for supplying power to the tiltable tubular rotary furnace, the solid powder separator and the powder collector and providing raw material gas, reaction atmosphere and reaction environment required by the reaction;
wherein the solid feeder, the tiltable tubular rotary furnace, the solid powder separator and the powder collector are sequentially connected in series in a sealing way and are controlled to be opened and closed by a valve,
the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system, and the vacuum system is connected with the tiltable tubular rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed inside the solids feeder.
According to the embodiment of the disclosure, the furnace tube of the tiltable tube type rotary furnace is made of quartz tube materials, the diameter of the middle part is larger than the diameters of the two ends, and the diameters of the two ends are as follows: the middle diameter = 1.1-1:5, and the furnace tube can rotate continuously, and the whole furnace body can incline downwards 0-45 degrees towards the tail part of the furnace tube.
According to the embodiment of the disclosure, the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, inert gas can be introduced from the bottom, the solid material and the powder are separated in the stirring process, and the solid material and the powder are brought into the powder collector by air flow.
The solid feeder is a screw feeding mechanism and is protected by inert gas.
The powder collector can be any one of centrifugal separation, cyclone separation and filtering separation modes.
Compared with the prior art, the invention has the advantages that:
(1) The ceramic beads are simultaneously used as a collecting carrier for preparing the carbon nano tubes by a floating catalysis method and also used as a grinding medium in the subsequent grinding process to grind and scrape the carbon nano tubes from the inside of the reaction cavity, so that carbon nano tube products on the surfaces of the ceramic beads and the inner wall of the reaction cavity can be completely collected;
(2) The device simultaneously realizes the functions of ceramic ball feeding, chemical vapor deposition preparation, powder separation and collection, can continuously enter the next batch of secondary production under the condition that the furnace body is not cooled, realizes batch preparation, reduces energy consumption and improves efficiency;
(3) The furnace tube rotating process after the reaction is adopted, the problem that a large number of carbon nanotubes are deposited inside a reaction cavity in the process of preparing the carbon nanotubes by floating catalytic chemical deposition is solved, the process stability of the preparation method can be effectively maintained, unstable airflow caused by turbulence is avoided, and quick collection is realized.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for batch production of carbon nanotubes according to the present invention.
FIG. 2 scanning electron micrograph of the product deposited directly on the surface of the ceramic beads of example 1.
FIG. 3A further enlarged scanning electron micrograph of the product deposited directly on the surface of the ceramic beads of example 1.
Fig. 4 scanning electron micrograph of carbon nanotube product after final separation of example 1.
Fig. 5 scanning electron micrograph of carbon nanotube product prepared in example 2.
Fig. 6 a scanning electron microscope photograph of the carbon nanotube product prepared in example 3.
In the drawings
1. A furnace body tilting device; 2. a solid feed device; 3. a furnace tube rotating device; 4. a quartz furnace chamber; 5. a reaction furnace; 6. a solid powder separator; 7. powder collector
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, an apparatus for mass production of carbon nanotubes according to the present invention comprises a solid feeder, a tiltable tube type rotary kiln, a solid powder separator, a powder collector, a collecting carrier and an auxiliary system;
the solid feeder is used for adding materials into the tiltable tube type rotary furnace;
the tiltable tube type rotary furnace is used for synthesizing carbon nanotubes;
the collecting carrier is used for collecting the adhesive on the side wall of the tiltable tubular rotary furnace;
the solid powder separator is used for separating the carbon nano tubes bonded on the surface of the collecting carrier;
the powder collector is used for collecting the separated carbon nano tubes;
the auxiliary system is used for supplying power to the tiltable tubular rotary furnace, the solid powder separator and the powder collector and providing raw material gas, reaction atmosphere and reaction environment required by the reaction;
wherein the solid feeder, the tiltable tubular rotary furnace, the solid powder separator and the powder collector are sequentially connected in series in a sealing manner and are controlled to be opened and closed by a valve,
the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system, and the vacuum system is connected with the tiltable tubular rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed inside the solids feeder.
According to the embodiment of the disclosure, the tiltable tube type rotary furnace comprises a furnace body tilting device and a furnace body, wherein the furnace body is arranged on the furnace body tilting device, the furnace body comprises a reaction furnace and a furnace tube, the diameter of the middle part of the furnace tube is larger than the diameters of the two ends of the furnace tube, and the reaction furnace is arranged at the middle position of the furnace tube;
the diameters of the two ends of the furnace tube are as follows: the middle diameter = 1.1-1:5, and the furnace tube can rotate continuously, and the whole furnace body can incline downwards 0-45 degrees towards the tail part of the furnace tube.
According to the embodiment of the disclosure, the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, inert gas can be introduced from the bottom, the solid material and the powder are separated in the stirring process, and the solid material and the powder are brought into the powder collector by air flow.
The solid feeder is a screw feeding mechanism and is protected by inert gas.
The powder collector adopts any one of centrifugal separation, cyclone separation and filtering separation modes
Another object of an embodiment of the present disclosure is to provide a method for preparing carbon nanotubes in batch, the method specifically includes the following steps:
s1) putting the collected carrier into a solid feeder, and introducing inert gas to empty air;
s2) adjusting the tiltable tube type rotary furnace to be in a horizontal state, vacuumizing, and switching to introduce inert gas;
s3) starting a solid feeder, and loading the collecting carrier into a tiltable tubular rotary furnace;
s4) starting a temperature rise program of the tubular rotary furnace, raising the temperature to a specified temperature, and switching and introducing a carbon source, a catalyst and mixed carrier gas;
s5) after the reaction is finished, stopping introducing the mixed gas, switching to introduce the inert gas, starting a furnace tube rotating device to rotate the furnace tube for a certain time at a certain rotating speed, then starting a furnace body tilting mechanism to enable the furnace body to tilt downwards towards a discharge port, starting a solid powder separator valve, and pouring the obtained product into a solid powder separator filled with the inert gas;
and S6) after the linking valves of the tubular furnace and the solid powder separator are closed, opening a turntable of the solid powder separator, simultaneously introducing inert gas, separating the collected carrier from the powder product, feeding the separated powder product into a powder collector, and obtaining a final product after separation.
And S7) repeating the steps S3-S6 to realize continuous batch preparation of the carbon nanotubes.
And S7), repeating the process, wherein the furnace body can not be cooled, and continuous production is realized.
Example 1
The device for preparing the carbon nano tubes in batches is formed by sequentially connecting a tiltable tubular rotary furnace, a solid feeder, a solid powder separator and a powder collector in series in a sealing way, and is controlled to be opened and closed by a valve. The solid feeder is a screw feeding mechanism and is protected by inert gas; the furnace tube material of the tiltable tubular rotary furnace is quartz tube material, the diameter of the middle part of the furnace tube material is larger than the diameters of two ends, the diameters of two ends: the middle diameter = 1.5, the furnace tube can rotate continuously, the whole furnace body can incline downwards to the tail part of the furnace tube by 0-45 degrees; the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom; the powder collector adopts a filtration separation mode; in addition, the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system; the vacuum system is connected with the tiltable tube type rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed within a double jacket of the solid feeder.
The preparation process of the carbon nano tube comprises the following steps: putting mullite ceramic beads with the diameter of 2mm into a solid feeder, and introducing argon gas to empty air; adjusting the tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce argon gas; starting a solid feeder, and loading the ceramic beads into a tubular rotary furnace; and starting a temperature rise program of the tubular rotary furnace, and raising the temperature to 800 ℃. Introducing a pre-dissolved catalyst solution (ferrocene toluene solution) and a mixed carrier gas (argon and hydrogen mixed gas with the mass ratio of 9:1) into a reaction furnace, wherein the carbon source: catalyst: the mass ratio of mixed carrier gas is 10. After the reaction is finished, argon gas is introduced in a switching mode, a furnace tube rotating device is started, the furnace tube rotates for 30 minutes at the rotating speed of 50 revolutions per minute, then a furnace body tilting mechanism is started, the furnace body tilts downwards towards a discharge port by an angle of 30 degrees, a solid powder separator valve is started, and ceramic beads and the obtained product are poured into a solid powder separator filled with inert gas argon gas in the rotating process. After a linking valve of the tubular furnace and the solid powder separator is closed, a solid powder separator turntable is opened, meanwhile, inert gas argon is introduced into the atmosphere, the rotating speed of the separator turntable is increased to 100 revolutions per minute, stirring is carried out for 30 minutes, ceramic beads are separated from powder products, the ceramic beads and the powder products enter a powder collector, and the final products are obtained after separation. The separated ceramic beads can be reused continuously, and the furnace body can enter the next batch of production without cooling.
FIG. 2 is a photograph showing the appearance of the ceramic beads used in example 1 and the collected product obtained by the preparation. FIG. 3 is a scanning electron microscope photograph of the ceramic beads of example 1 after carbon nanotubes have been deposited on the surface. FIG. 4 is a scanning electron microscope photograph of the product collected in the powder collection bag after separation by the solid powder separator of the example.
Example 2
The device for preparing the carbon nano tubes in batches is formed by sequentially connecting the tiltable tubular rotary furnace, the solid feeder, the solid powder separator and the powder collector in series in a sealing way, and is controlled to be opened and closed by a valve. The solid feeder is a screw feeding mechanism and is protected by inert gas; the furnace tube material of the tiltable tubular rotary furnace is quartz tube material, the diameter of the middle part of the furnace tube material is larger than the diameters of two ends, the diameters of two ends: the middle diameter = 1.1, the furnace tube can rotate continuously, the whole furnace body can incline downwards to the tail part of the furnace tube by 0-45 degrees; the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom; the powder collector adopts a cyclone separation mode; in addition, the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system; the vacuum system is connected with the tiltable tube type rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed within a double-layered jacket of the solids feeder.
The preparation process of the carbon nano tube comprises the following steps: loading zirconia ceramic beads with the diameter of 0.1mm into a solid feeder, and introducing nitrogen gas to empty air; adjusting the tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce nitrogen gas; starting a solid feeder, and loading the ceramic beads into a tubular rotary furnace; and opening the tubular rotary furnace to heat up to 600 ℃. Introducing a pre-dissolved catalyst solution (ferrocene normal hexane solution) and a mixed carrier gas (nitrogen and hydrogen mixed gas with the mass ratio of 20): catalyst: mixing the carrier gas at a mass ratio of 10. After the reaction is finished, nitrogen is introduced in a switching mode, a furnace tube rotating device is started, the furnace tube is made to rotate for 30 minutes at the rotating speed of 10 revolutions per minute, then a furnace body inclining mechanism is started, the furnace body inclines downwards towards a discharge port by an angle of 30 degrees, a solid powder separator valve is started, and ceramic beads and obtained products are poured into a solid powder separator filled with inert gas nitrogen in the rotating process. After the linking valves of the tubular furnace and the solid powder separator are closed, the rotating disc of the solid powder separator is opened, meanwhile, the inert gas nitrogen of the atmospheric flow is introduced, the rotating speed of the rotating disc of the separator is increased to 50 revolutions per minute, the stirring is carried out for 30 minutes, the ceramic beads and the powder product are separated, the ceramic beads and the powder product enter a powder collector, and the final product is obtained after the separation.
Example 3
The device for preparing the carbon nano tubes in batches is formed by sequentially connecting a tiltable tubular rotary furnace, a solid feeder, a solid powder separator and a powder collector in series in a sealing way, and is controlled to be opened and closed by a valve. The solid feeder is a screw feeding mechanism and is protected by inert gas; the furnace tube material of the tiltable tubular rotary furnace is quartz tube material, the diameter of the middle part of the furnace tube material is larger than the diameters of two ends, the diameters of two ends: the middle diameter =1:5, the furnace tube can rotate continuously, and the whole furnace body can incline downwards to the tail part of the furnace tube by 0-45 degrees; the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom; the powder collector adopts a filtering separation mode; in addition, the auxiliary system comprises a vacuum system, a gas path system, a power supply system and a cooling system; the vacuum system is connected with the tiltable tube type rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed within a double jacket of the solid feeder.
The preparation process of the carbon nano tube comprises the following steps: putting alumina ceramic beads with the diameter of 5mm into a solid feeder, and introducing helium gas to empty air; adjusting the tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce helium gas; starting a solid feeder, and loading the ceramic beads into a tubular rotary furnace; starting a tubular rotary furnace temperature rise program, and rising the temperature to 1200 ℃. Introducing a catalyst solution (ferrocene ethanol solution) dissolved in advance, a growth promoter thiophene and a mixed carrier gas (helium and hydrogen mixed gas with the mass ratio of 1: catalyst: growth promoter: the mass ratio of mixed carrier gas is 30: 200, reaction time 1 hour. After the reaction is finished, introducing helium, starting a furnace tube rotating device to rotate the furnace tube for 2 minutes at the rotating speed of 200 revolutions per minute, then starting a furnace body tilting mechanism to enable the furnace body to tilt downwards at an angle of 30 degrees towards a discharge port, starting a solid powder separator valve, and pouring ceramic beads and the obtained product into a solid powder separator filled with inert gas helium in the rotating process. And after a linkage valve of the tubular furnace and the solid powder separator is closed, opening a solid powder separator turntable, introducing an atmospheric inert gas helium, increasing the rotating speed of the separator turntable to 200 revolutions per minute, stirring for 2 minutes, separating the ceramic beads from the powder product, feeding the ceramic beads into a powder collector, and separating to obtain a final product.
Example 4
The device for preparing the carbon nano tubes in batches is formed by sequentially connecting a tiltable tubular rotary furnace, a solid feeder, a solid powder separator and a powder collector in series in a sealing way, and is controlled to be opened and closed by a valve. The solid feeder is a screw feeding mechanism and is protected by inert gas; the furnace tube material of the tiltable tubular rotary furnace is quartz tube material, the diameter of the middle part of the furnace tube material is larger than the diameters of two ends, the diameters of two ends: the middle diameter = 1.5, the furnace tube can rotate continuously, the whole furnace body can incline downwards to the tail part of the furnace tube by 0-45 degrees; the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom; the powder collector adopts a filtration separation mode; in addition, the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system; the vacuum system is connected with the tiltable tube type rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed within a double jacket of the solid feeder.
The preparation process of the carbon nano tube comprises the following steps: filling quartz ceramic beads with the diameter of 2mm into a solid feeder, and introducing argon gas to empty air; adjusting the tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce argon gas; starting a solid feeder, and loading the ceramic beads into a tubular rotary furnace; starting a tubular rotary furnace temperature rise program, and raising the temperature to 850 ℃. Introducing a catalyst solution (ferrocene ether solution) dissolved in advance, a carbon source gas (methane) and a mixed carrier gas (argon and hydrogen mixed gas with the mass ratio of 9:1) into a reaction furnace, wherein the carbon source (ether and methane): catalyst (ferrocene): mixing the carrier gases (argon and hydrogen) at a mass ratio of 10. After the reaction is finished, argon gas is introduced in a switching mode, a furnace tube rotating device is started, the furnace tube rotates for 30 minutes at the rotating speed of 100 revolutions per minute, then a furnace body tilting mechanism is started, the furnace body tilts downwards towards a discharge port by an angle of 30 degrees, a solid powder separator valve is started, and ceramic beads and the obtained product are poured into a solid powder separator filled with inert gas argon gas in the rotating process. And after a linkage valve of the tubular furnace and the solid powder separator is closed, opening a solid powder separator turntable, introducing an atmospheric inert gas argon gas, increasing the rotating speed of the separator turntable to 200 revolutions per minute, stirring for 30 minutes, separating the ceramic beads from the powder product, feeding the ceramic beads into a powder collector, and separating to obtain a final product.
Example 5
The device for preparing the carbon nano tubes in batches is formed by sequentially connecting a tiltable tubular rotary furnace, a solid feeder, a solid powder separator and a powder collector in series in a sealing way, and is controlled to be opened and closed by a valve. The solid feeder is a screw feeding mechanism and is protected by inert gas; the furnace tube material of the tiltable tube type rotary furnace is quartz tube material, the diameter of the middle part of the furnace tube material is larger than the diameters of the two ends, the diameters of the two ends are as follows: the middle diameter = 1.5, the furnace tube can rotate continuously, the whole furnace body can incline downwards to the tail part of the furnace tube by 0-45 degrees; the solid powder separator is a double-layer water-cooling stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom; the powder collector adopts a filtration separation mode; in addition, the auxiliary system comprises a vacuum system, a gas circuit system, a power supply system and a cooling system; the vacuum system is connected with the tiltable tube type rotary furnace; the gas path system is respectively connected with the air inlets of the tiltable tubular rotary furnace, the solid feeder and the solid powder separator; the cooling system is disposed within a double jacket of the solid feeder.
The preparation process of the carbon nano tube comprises the following steps: loading silicon nitride ceramic beads with the diameter of 0.8mm into a solid feeder, and introducing argon gas to empty air; adjusting the tubular rotary furnace to be in a horizontal state, vacuumizing, and then switching to introduce argon gas; starting a solid feeder, and loading the ceramic beads into a tubular rotary furnace; starting a tubular rotary furnace temperature rise program, and raising the temperature to 950 ℃. Introducing a catalyst solution (ethanol solution of ferrocene) dissolved in advance, a carbon source gas (ethylene), a growth promoter (thiophene) and a mixed carrier gas (mixed gas of argon and hydrogen in a mass ratio of 1:1) into a reaction furnace, wherein the carbon source (ethanol and ethylene): catalyst (ferrocene): growth promoter (thiophene): mixing the carrier gas (argon and hydrogen) at a mass ratio of 10. After the reaction is finished, argon is introduced in a switching mode, a furnace tube rotating device is started, the furnace tube is made to rotate for 30 minutes at the rotating speed of 50 revolutions per minute, then a furnace body inclining mechanism is started, the furnace body inclines downwards towards a discharge hole by an angle of 30 degrees, a solid powder separator valve is started, and ceramic beads and the obtained product are poured into a solid powder separator filled with inert gas argon in the rotating process. And after a linkage valve of the tubular furnace and the solid powder separator is closed, opening a solid powder separator turntable, introducing an atmospheric inert gas argon gas, increasing the rotating speed of the separator turntable to 100 revolutions per minute, stirring for 30 minutes, separating the ceramic beads from the powder product, feeding the ceramic beads into a powder collector, and separating to obtain a final product.
While several embodiments of the present invention have been presented herein, it will be appreciated by those skilled in the art that changes may be made to the embodiments herein without departing from the spirit of the invention. The above examples are merely illustrative and should not be taken as limiting the scope of the invention.
Claims (7)
1. The method for preparing the carbon nano tubes in batches is characterized in that a device adopted by the method comprises a solid feeder, a tiltable tube type rotary furnace, a solid powder separator, a powder collector, a collecting carrier and an auxiliary system;
the solid feeder is used for adding materials into the tiltable tube type rotary furnace;
the tiltable tube type rotary furnace is used for synthesizing carbon nanotubes;
the collecting carrier is used for collecting the carbon nano tubes stuck on the side wall of the tiltable tube type rotary furnace;
the solid powder separator is used for separating the carbon nano tubes bonded on the surface of the collecting carrier;
the powder collector is used for collecting the separated carbon nano tubes;
the auxiliary system is used for supplying power to the tiltable tubular rotary furnace, the solid powder separator and the powder collector and providing raw material gas, reaction atmosphere and reaction environment required by the reaction;
the auxiliary system comprises a vacuum system, a gas path system, a power supply system and a cooling system, wherein the vacuum system is connected with the tiltable tubular rotary furnace; the gas path system is respectively connected with the tiltable tubular rotary furnace, the solid feeder and the gas inlet of the solid powder separator; the cooling system is disposed inside the solids feeder; the preparation method adopting the device specifically comprises the following steps:
s1) loading a collected carrier into a solid feeder, and introducing inert gas to empty air; the inert gas is nitrogen, argon or helium; s2) adjusting the tiltable tube type rotary furnace to be in a horizontal state, vacuumizing, and switching to introduce inert gas; s3) starting a solid feeder, and loading the collected carrier into the tiltable tubular rotary furnace; s4) starting a temperature rise program of the tubular rotary furnace, raising the temperature to a specified temperature, and switching and introducing a carbon source, a catalyst and mixed carrier gas;
the specified temperature is 600-1200 ℃, and the reaction time is 10 minutes-5 hours; the mass ratio of the carbon source to the catalyst to the mixed carrier gas is as follows: 5-30:0.05-5:50-200 parts of;
s5) after the reaction is finished, stopping introducing the mixed gas, switching to introduce the inert gas, starting a furnace tube rotating device to rotate the furnace tube for a certain time at a certain rotating speed, then starting a furnace body tilting mechanism to enable the furnace body to tilt downwards towards a discharge port, starting a solid powder separator valve, and pouring the obtained product into a solid powder separator filled with the inert gas;
the rotating speed of the furnace tube is 10-200 r/min, the time is 2-30 min, and the inclination angle is 0-45 degrees;
s6) after closing a linkage valve of the tubular furnace and the solid powder separator, opening a solid powder separator turntable, simultaneously introducing inert gas, separating a collected carrier from a powder product, feeding the separated powder product into a powder collector, and separating to obtain a final product, namely a carbon nano tube; and S7) repeating the steps S3-S6 to realize continuous batch preparation of the carbon nanotubes.
2. The method according to claim 1, wherein the furnace tube of the tiltable tube type rotary furnace is made of a quartz tube material, the diameter of the middle part is larger than that of the two ends, and the diameters of the two ends are as follows: the middle diameter = 1.1-1:5, and the furnace tube can rotate continuously, and the whole furnace body can incline downwards 10-45 degrees towards the tail part of the furnace tube.
3. The method of claim 1, wherein the solid powder separator is a double-layer water-cooled stainless steel barrel with stirring blades at the bottom, and inert gas can be introduced from the bottom to separate the solid material from the powder during stirring and be carried into the powder collector by the gas flow.
4. The method of claim 1, wherein the collection support inorganic ceramic beads are zirconia, alumina, silicon nitride, mullite, or quartz; the diameter is 0.1 mm-5 mm.
5. The method according to claim 1, wherein the carbon source is methane, ethane, propane, n-hexane, heptane, ethylene, propylene, acetylene, methanol, ethanol, isopropanol, n-butanol, methyl ether, ethyl ether, benzene, toluene, or xylene; the catalyst is ferrocene; the mixed carrier gas is a mixed gas of inert gas and hydrogen, and the volume ratio of the inert gas to the hydrogen is (20): 90.
6. the method of claim 1, wherein: the rotating speed of the rotating disc of the solid powder separator in the S6) is 50-200 r/min, and the time is 2-30 min.
7. The method of claim 1, wherein: and S4) adding a growth promoter, wherein the growth promoter is thiophene, and the mass ratio of the growth promoter to the thiophene is 0.01-0.5.
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