CN119040852A - Preparation device and method for producing carbon nano tube by floating chemical vapor deposition method - Google Patents
Preparation device and method for producing carbon nano tube by floating chemical vapor deposition method Download PDFInfo
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- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
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- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation device and a preparation method for producing carbon nanotubes by a floating chemical vapor deposition method. The device comprises a feeding unit, a reaction tube and a collecting unit, wherein the reaction tube is divided into a first section and a second section, the feeding unit is arranged at an inlet, the collecting unit is arranged at an outlet, a rod-shaped heating body is arranged in an inner cavity of the first section, the length direction of the rod-shaped heating body is forward to the central axis of the reaction tube, and the rod-shaped heating body can generate heat to heat nearby reaction media. The device and the method provided by the invention are beneficial to reducing the vortex phenomenon of the first section, avoiding the agglomeration and deactivation of catalyst particles at the inlet, solving the problem that buoyancy becomes more prominent due to the increase of temperature gradient, and the reduction of convection vortex also leads to the remarkable reduction of amorphous carbon and ferric oxide in the synthesized CNT aerogel, thereby improving the yield and purity of the carbon nano tube, and further realizing the continuous preparation of the carbon nano tube with high yield, high yield and high purity.
Description
Technical Field
The invention relates to the technical field of carbon nanotube preparation, in particular to a preparation device and a preparation method for producing carbon nanotubes by a floating chemical vapor deposition method.
Background
The single-wall carbon nano tube has wide application prospect in the fields of electrons, photoelectricity and materials due to the unique structure and excellent performance.
The currently prevailing single-walled carbon nanotube fabrication techniques include arc discharge methods [ s.ijima, helical microtubules of graphitic carbon, nature 354 (6348) (1991) -58], laser ablation methods [Bethune D S,Kiang C H,De VriesM S,et al.Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls[J].Nature,1993,363：605]、 chemical vapor deposition (CVD method )[Y.-L.Li,A.Kinloch Ian,H.Windle Alan,DirectSpinning of Carbon Nanotube Fibers from Chemical Vapor Deposition Synthesis,Science 304(5668)(2004)276-278.]. wherein FCCVD techniques allow ultra-long one-dimensional carbon nanotube materials to be synthesized in a single step and assembled into the desired form.
In contrast to substrate-based CVD processes that use a fixed catalyst surface in a constant temperature environment, the FCCVD process involves moving gas phase catalyst particles that float by a temperature differential regime in a buffer gas environment. These active particles form carbon nanotube products on their surfaces at a rapid growth rate to form ultra-long nanotubes that are bundled together to form a cohesive aerogel network that facilitates their collection into the desired microscopic entity [I.G′omez-Palos,et al.,Gas-to-nanotextile：high-performance materials from floating 1D nanoparticles,Nanoscale 15(13)(2023)6052-6074.].
Not only single-walled carbon nanotubes, but also double-walled and even multi-walled carbon nanotubes can be prepared in batches by FCCVD process.
At present, FCCVD for preparing the carbon nano tube mainly faces two problems, namely, 1, how to improve the conversion rate of a carbon source, and 2, how to realize the effective amplified production and realize the macroscopic preparation of the high-quality carbon nano tube. In theory, gaseous hydrocarbons decompose on semi-liquid catalyst aerosol particles to form solid carbon nanotubes suspended in the gas, and finally form continuously produced carbon nanotubes, and the FCCVD process is usually performed in one or more through lumens, such as reaction tubes made of high temperature resistant materials, and expanding the tube diameter is one of the main ways to increase the productivity.
However, in the prior art, the inner diameter of the reaction tube is still smaller and is mostly less than 100mm, and research and development personnel in the field have made many attempts, but find that blindly directly enlarging the tube diameter generally causes difficulty in stably outputting products, but is unfavorable for mass production, and according to the discovery and understanding of the inventor of the invention, the discovery and understanding should relate to the vortex phenomenon of the first section (the initial section of injection), under the condition that the inner diameter is larger, the temperature gradient of the first section of the reaction tube in the axial direction and the radial direction is larger, and the gas buoyancy caused by the larger temperature gradient is uneven, so that the vortex phenomenon is caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation device and a preparation method for producing carbon nano tubes by a floating chemical vapor deposition method. Mainly solves the problem that the preparation of carbon nano tubes with high quality is difficult to be stably carried out on large-diameter reaction tubes when the FCCVD process is used for preparing the carbon nano tubes in batches.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
In a first aspect, the present invention provides a preparation apparatus for producing carbon nanotubes by a floating chemical vapor deposition method, including a feeding unit, a reaction tube, and a collecting unit, wherein the reaction tube is divided into a first section and a second section, the feeding unit is disposed at an inlet of the first section for injecting a reaction medium into the reaction tube, and the collecting unit is disposed at an outlet of the second section for collecting formed carbon nanotubes;
At least the inner diameter of the first section of the reaction tube is more than 200mm, and a rod-shaped heating body is arranged in the inner cavity of the first section, and the length direction of the rod-shaped heating body is along the central axis of the reaction tube;
In the floating chemical vapor deposition process for producing carbon nanotubes, the rod-shaped heater can generate heat to heat the reaction medium in the vicinity.
In a second aspect, the present invention also provides a method for producing carbon nanotubes using the above-described production apparatus, comprising:
the temperature of the reaction tube is generally the temperature reached by the heated region of the reaction tube, and can be the temperature of the whole section of the reaction tube or the temperature reached by the middle part, or the temperature of the two ends of the reaction tube is slightly lower due to natural cooling, so long as the conditions of growing the carbon nano tube by the floating catalysis method are met.
Injecting a reaction medium into the reaction tube from an inlet, wherein the reaction medium comprises a catalyst, a cocatalyst, a carbon source and a reaction gas;
collecting the carbon nanotubes from the outlet.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
The device and the method provided by the invention are beneficial to reducing the vortex phenomenon of at least the first section, avoiding the agglomeration and deactivation of catalyst particles at the inlet, solving the problem that buoyancy becomes more prominent due to the increase of temperature gradient, and the reduction of convection vortex also leads to the remarkable reduction of amorphous carbon and ferric oxide in the synthesized CNT aerogel, thereby improving the yield and purity of the carbon nano tube, and further realizing the continuous preparation of the carbon nano tube with high yield, high yield and high purity.
In summary, the device and the method provided by the invention are more beneficial to eliminating convection vortex in the large-diameter reactor tube in the process amplification process, wherein the buoyancy becomes more prominent due to the increase of the temperature gradient, realizing the continuous preparation of the single-walled carbon nanotube with large yield, high yield and high purity, and the device is hopeful to promote the wider application of the single-walled carbon nanotube in various fields and promote the commercialized development of the domestic carbon nanotube technology.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
FIG. 1 is a schematic view of a manufacturing apparatus according to an exemplary embodiment of the present invention;
fig. 2 is a schematic diagram showing a distribution state of a plurality of rod-shaped heaters according to an exemplary embodiment of the present invention;
FIG. 3 is an electron micrograph of single wall carbon nanotubes prepared according to an exemplary embodiment of the present invention;
FIG. 4 is a graph showing Raman spectrum measurements of single-walled carbon nanotubes prepared according to an exemplary embodiment of the present invention
FIG. 5 is a thermogravimetric analysis test chart of single-walled carbon nanotubes prepared according to an exemplary embodiment of the present invention.
The reference numerals indicate that 1, a carbon source feeding pipeline, 2, an inert gas feeding pipeline, 3, a reducing gas feeding pipeline, 4, a catalyst feeding pipeline, 5, a rod-shaped heating body, 6, a carbon tube collecting chamber air inlet, 7, a gas-solid separation chamber, 8, a gas outlet, 9 and a product outlet.
Detailed Description
As shown in the background art, the prior art for FCCVD to grow carbon nanotubes has paid attention to the regulation of the gas flow field in the first stage, for example, many prior arts have proposed the use of a mechanical structure to perform the first stage rectification, including but not limited to providing a porous rectifier in the first stage, the direction of the porous rectifier being parallel to the axial direction of the reaction tube so that the gas flow forms a laminar flow along the axial direction, and others involving a secondary reaction tube, also called "liner tube", which is a tube with a smaller diameter so that the reaction medium moves along the direction of the liner tube, thereby achieving mechanical rectification.
However, in the above prior art, the phenomenon of thermally induced buoyancy vortex which is peculiar to the large diameter reaction tube is not broken through yet, and becomes very remarkable in the large diameter reaction tube, which directly results in a decrease in the growth efficiency and quality of the carbon tube, whereas in the smaller diameter reaction tube which is generally used, the internal temperature distribution and flow field variation are not complicated due to the size limitation and the closer heat exchange distance, and the influence thereof is not so remarkable that most researchers ignore the influence thereof.
Therefore, referring to the ideas in the above-mentioned prior arts, when the structural rectifying structure is disposed in the large-diameter reaction tube, the rectifying structure cannot perform its effective rectifying function in the small-size reaction tube, and the problem needs to be solved in a targeted manner for the thermal field and flow field characteristics of the large-size reaction tube.
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one from another component or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such components or method steps.
The invention aims to provide equipment for continuously producing single-walled carbon nanotubes by a chemical vapor deposition method, which is based on the discovery and understanding of the inventor of the invention, and carries out the first section of rectification in a large-size reaction tube from the aspect of adjusting heat distribution so as to realize the stable and high-quality preparation of the carbon nanotubes in the large-size reaction tube.
Based on the above object, the embodiment of the invention provides a preparation device for producing carbon nanotubes by a floating chemical vapor deposition method, which comprises a feeding unit, a reaction tube and a collecting unit, wherein the reaction tube is divided into a first section and a second section, the feeding unit is arranged at an inlet of the first section and is used for injecting a reaction medium into the reaction tube, the collecting unit is arranged at an outlet of the second section and is used for collecting formed carbon nanotubes, at least the inner diameter of the first section of the reaction tube is more than 200mm, a rod-shaped heating body is arranged in an inner cavity of the first section, the length direction of the rod-shaped heating body is along the central axis of the reaction tube, and when the carbon nanotubes are produced by the floating chemical vapor deposition method, the rod-shaped heating body can generate heat to heat the nearby reaction medium.
In the above technical solution, the cross section of the reaction tube is generally circular or quasi-circular, but other shapes, such as polygons, are not excluded, and when the reaction tube is non-circular, the inner diameter is the average value of the radial inner widths of the reaction tube in all directions, and the reaction tube is generally equal in diameter, namely the inner diameters of the first section, the growth section and the tail section are equal, but may not be equal, at least the diameter of the first section is large in diameter, such as the buoyancy vortex phenomenon of the first section is very obvious when the diameter is more than 200mm and even more than 300mm, and the feeding unit can adopt a specific structure in the following embodiment, or can adopt a new injection structure which is common in the field or self-developed in the self-development, and the functional unit can be used for injecting the reaction medium for growing the carbon nanotubes without being limited by the specific structure, and similarly, the collecting unit is also a large functional unit, and the specific structure is not limited, and can realize the collecting function.
As can be seen from the above technical solution, the present invention provides a rectifying method which is completely different from the mechanical rectifying method in the prior art, but realizes the rectifying by introducing an additional heat source, and the heat source is used to readjust the temperature field of the first section, and the direction of the constructed heat field is from inside to outside, which is essentially a thermally induced rectifying method, specifically, the heat source solves the problem of eliminating convection and eddy current phenomena in the large diameter reactor tube during the process amplification by weakening the temperature gradient, while in general understanding, the plurality of rod-shaped heating bodies have certain rectifying shapes, however, in a plurality of experiments, the rectifying of the first section can be effectively realized in the small diameter reactor tube by simply relying on the shape of the rod-shaped substances, but in the large diameter reactor tube, the mechanical rectifying effect caused by the rod-shaped substances is almost not present.
In addition, the addition of the rod-shaped heating body ensures that the catalyst can enter the growth section from the first section with consistent residence time while rectification, so that the phenomenon that part of the catalyst flows back due to vortex flow (even part of the catalyst enters the growth section after flowing back for many times in the first section, the activity or the size of the catalyst is obviously changed due to the fact that the residence time is too long) is avoided, the phenomenon that the catalyst entering the growth section is inconsistent, the activity and the size are different, and finally the purity problem of the product is brought.
According to the experimental results of some embodiments of the present invention, when a rod-shaped heating body is not added, in the preparation test of a large-sized reaction tube, the calculated carbon conversion rate is only 25%, and after a heating rod is added at the inlet of the reactor, the calculated carbon conversion rate can reach 49% according to the experimental results, so that the yield improvement rate can be close to 100%. In addition, according to experimental results and calculated carbon I G/ID, the crystallinity and quality of the produced single-wall carbon nano tube can reach 60-100, which is improved by 58 percent.
Regarding the temperature of the thermally induced rectification proposed in the above-described scheme, in some embodiments, the heat generation temperature of the rod-shaped heating body can reach 300 to 700 ℃.
With regard to more specific constructional features, in some embodiments the rod-shaped heating body extends from the inlet to the end of the first section along the central axis.
Typically, in some embodiments, the length of the first section is 10-33% of the total length of the reaction tube.
Further, it is preferable that the rod-shaped heating body is disposed on the central axis when the number of the rod-shaped heating bodies is one, and a plurality of the rod-shaped heating bodies are uniformly distributed around the central axis when the number of the rod-shaped heating bodies is a plurality. For example, when two rod-shaped heating bodies exist, the two rod-shaped heating bodies are symmetrical by taking the central axis as a symmetry axis, when a plurality of rod-shaped heating bodies exist, the rod-shaped heating bodies are arranged into a plurality of corner points of a regular polygon, and the center of the polygon is the central axis.
In terms of dimensional characteristics, in some embodiments, a circle is constructed with the central points of the plurality of rod-shaped heating bodies as construction points (i.e., the central points of the plurality of rod-shaped heating bodies are all located on the circle as shown with reference to fig. 2), the center of the circle coincides with the central axis, and the diameter of the circle is 30-50% of the inner diameter of the first section.
In order to regulate the thermal field of the first section more precisely, in some embodiments, the provided preparation device may further comprise a temperature detection unit comprising a temperature detector, at least one of which is arranged on or near the rod-shaped heating body, capable of detecting the heating state of the rod-shaped heating body.
Specifically, for example, there may be a plurality of temperature detectors such as thermocouples or infrared sensing probes, etc., for detecting the temperature of the reaction tube and the temperature of the rod-shaped heating body, respectively.
As some typical examples of the above technical solutions, the present invention provides a preparation apparatus for preparing single-walled carbon nanotubes using FCCVD, which includes a feeding unit, a temperature adjusting unit, a reaction tube, a detecting unit, and a collecting unit.
The feeding unit can comprise a plurality of groups of air supply pipelines, liquid feed pumps, solid powder feeders, atomizers and the like, and comprises a plurality of groups of air supply pipelines, liquid feed pumps, solid powder feeders and atomizers, wherein the air inlets of the air supply pipelines are all positioned at the top of the reactor, the atomizers are positioned at the liquid discharge ports, and the outlets of the solid powder feeders are positioned at the top of the reactor. The temperature regulating unit comprises a plurality of groups of electric heating rods, the heating rods are connected with the top of the reactor and extend downwards, and the temperature gradient distribution is changed by heating surrounding gas, so that the adjustment of the whole gas flow field is realized, the purpose of reducing vortex is achieved, and the yield and purity of the single-walled carbon nanotubes are improved; the detection unit comprises a pressure detector and a temperature detector, wherein the pressure detector is arranged at the upstream of the reaction pipeline and the collecting device and is used for detecting gas pressure in the reaction pipeline and the collecting device, the temperature detector is positioned at different positions of the reactor and is used for detecting the temperature of different positions of the reactor, the product collecting unit comprises a carbon nano tube collecting chamber, a vacuum pump and cyclone separation equipment, the carbon nano tube collecting chamber is a hollow closed cavity, and the carbon nano tube collecting chamber comprises a gas-solid separation device, a tail gas outlet and a product discharge port.
The inner diameter of the reaction tube can be 100-500 mm, the length of the reaction tube is generally 1500-3000 mm, the number of the electric heating rods can be 1-4, the electric heating rods are uniformly distributed in the inlet of the reaction tube, and the length of the heating rods is 100-1000mm.
Corresponding to the above preparation device, the second aspect of the embodiment of the present invention also provides a preparation method for producing carbon nanotubes by using the above device, which includes the following steps:
Bringing at least the growth section of the reaction tube to a first set temperature, and bringing the rod-like heating body in the reaction tube to a second set temperature, the first set temperature being higher than the second set temperature;
Injecting a reaction medium into the reaction tube from an inlet, wherein the reaction medium comprises a catalyst, a cocatalyst, a carbon source and a reaction gas;
collecting the carbon nanotubes from the outlet.
And with respect to specific reaction conditions and material selections, in some embodiments, the second set temperature is 300-700 ℃.
In some embodiments, the first set temperature is 800-1500 ℃.
In some embodiments, the catalyst comprises any one or a combination of two or more of ferrocene, nickel-dicyclopentadienyl, cobalt-dicyclopentadienyl, ferric chloride.
In some embodiments, the promoter comprises any one or a combination of two or more of sulfur powder, selenium powder, thiophene, carbon disulfide.
In some embodiments, the carbon source comprises a gaseous carbon source comprising any one or a combination of two or more of ethanol, propanol, toluene, and/or a liquid carbon source comprising any one or a combination of two or more of methane, ethane, propane, carbon monoxide, carbon dioxide.
In some embodiments, the reactive gas comprises at least one of a reducing gas comprising any one or a combination of two or more of hydrogen, water vapor, ammonia, and an inert gas comprising any one or a combination of two or more of argon, nitrogen, helium.
In some embodiments, the molar ratio of carbon source to catalyst is from 1:1 to 100 and the molar ratio of catalyst to cocatalyst is from 1:1 to 10.
In some embodiments, the total flow of the reactant gas is 20000-100000sccm.
As some typical examples of the above technical solutions, the preparation method specifically may include the following steps:
s1) raising the temperature of the vertical furnace to a specified temperature, introducing carrier gas, turning on a power supply of the rod-shaped heating body to enable the power supply to reach the specified temperature,
S2) feeding the solid catalyst and the auxiliary agent into a reaction zone through a powder feeder, and then feeding a carbon source and a reaction gas into a reaction furnace to react in a high-temperature zone;
s3) at the outlet end of the vertical furnace, the grown carbon nanotube product enters a product collecting chamber under the action of air flow, single-walled carbon nanotubes are discharged into a collecting tank from the bottom after being subjected to gas-solid separation, and tail gas is discharged through a tail gas outlet of the collecting chamber, so that the effect of continuous discharging is achieved;
further, the designated temperature in the step S1) is 800-1500 ℃, the carrier gas is at least one of nitrogen, argon and helium, the flow is 50-10000sccm, and the designated temperature of the rod-shaped heating body is 300-700 ℃. Further, the catalyst in S2) is at least one of ferrocene, nickel-dicyclopentadienyl, cobaltous oxide and ferric chloride, the cocatalyst is at least one of sulfur powder, selenium powder, thiophene and carbon disulfide, and preferably, the carbon source is at least one of ethanol, propanol and toluene, the liquid carbon source is at least one of methane, ethane, propane, carbon monoxide and carbon dioxide, the reaction gas is at least one of a reducing gas and an inert gas, the reducing gas comprises hydrogen, water vapor and ammonia, and the inert gas comprises argon, nitrogen and helium. The molar ratio of the carbon source to the catalyst is 1-100, the molar ratio of the catalyst to the sulfur source is 1-10, the ratio of the flow rate of the reducing gas to the flow rate of the inert gas is 1-10, the feeding amount of the carbon source is 20ml/min, the feeding amount of the catalyst is 0.1g/min, and the reaction gas comprises 8000sccm of hydrogen and 8000sccm of argon.
Of course, the above reaction conditions are only typical conditions for batch preparation of single-walled carbon nanotubes by using large-diameter reaction tubes, and do not mean that the preparation can be performed only by using the above conditions under the technical concept of the present invention, for example, when preparing carbon nanotubes with different wall numbers, a specific preparation process can be adaptively adjusted, but all embodiments that utilize the technical means of thermal rectification provided by the present invention and have the related effect of thermal rectification fall within the feasible scope of the present invention.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The present embodiment first exemplifies a carbon nanotube production apparatus whose structure is shown in fig. 1, the main components comprising a carbon source feed pipe 1, an inert gas feed pipe 2, a reducing gas feed pipe 3, a catalyst feed pipe 4, a rod-like heating body 5, a carbon tube collecting chamber gas inlet 6, a gas-solid separation chamber 7, a gas outlet 8, and a product outlet 9.
The carbon source feeding pipeline 1, the inert gas feeding pipeline 2, the reducing gas feeding pipeline 3 and the catalyst feeding pipeline 4 form a feeding unit, and preferably, the embodiment adopts liquid carbon source alcohol, after fully mixing a carbon source and a sulfur source (serving as a cocatalyst), the mixture enters the carbon source feeding pipeline 1 through a feeding pump, an outlet of the carbon source feeding pipeline 1 is connected with a sprayer, and the sprayer is used for providing a carbon source for a reactor, so that the carbon source supplied by a carbon source feeding port can be gasified rapidly and uniformly. The catalyst adopts the solid feeding mode, and catalyst feed pipe 4 import links to each other with the powder feeder export, and the catalyst can evenly get into catalyst feed pipe 4 under the drive of carrier gas to ensure the effective utilization of catalyst, other reactant materials, like carrier gas, reducing gas hydrogen gets into from reducing gas feed pipe 3, and inert gas gets into from inert gas feed pipe 2.
The rod-shaped heating bodies 5 are arranged along the direction of the reaction tube from the inlet of the reaction tube, 4 rod-shaped heating bodies 5 are arranged, the diameter of a circle surrounded by the four rod-shaped heating bodies 5 is 150mm, the diameter of the concentrically arranged reaction tube is 300mm, and the length of the heating rod accounts for 33% of the total length of the reactor.
The catalyst is a mixture of ferrocene and sulfur powder (wherein the mass ratio of ferrocene to sulfur is 1:0.5), the carbon source is ethanol (water with the mass fraction of 1% is used as an etching agent), the mass ratio of the catalyst to the carbon source is 1:99, the reducing gas is hydrogen, and the inert gas is argon.
The specific method comprises the following steps:
Heating the whole temperature of the reactor to 1250 ℃ by using electric heating, setting an electric heating rod to 600 ℃ and specifically distributing the electric heating rod into 4 uniform reactors as shown in figure 3;
Step two, mixing a carbon source and a sulfur source, then introducing the mixture into a sprayer through a feed pump, introducing reaction gas into a gas supply pipeline, introducing a catalyst into a pipeline 4 through a powder feeder, and then converging the carbon source, the catalyst and the reaction gas into a reaction pipeline heated by a heating ring, wherein the carbon source feed amount is 20ml/min, the catalyst feed amount is 0.2g/min, and the reaction gas comprises 8000sccm of hydrogen and 12000sccm of argon;
the single-wall carbon nano tube is discharged into a collecting tank from the bottom after gas-solid separation, and tail gas is discharged through a tail gas outlet of the collecting chamber, so that the effect of continuous discharging is achieved;
The SEM of the obtained product is shown in fig. 3, the raman diagram is shown in fig. 4, and the thermogravimetric analysis is shown in fig. 5, and it can be seen from these diagrams that the carbon nanotubes prepared by the embodiment of the invention have the advantages of high quality and high purity.
Example 2
This example is substantially identical to example 1, except that the heating rod selected is a single one, located at the center of the reaction tube, in the same manner as example 1.
The IG/ID of the prepared product is about 35, and the heat weight residue is 30.56%.
Comparative example 1
This comparative example is substantially the same as example 1, except that the heating rod is directly removed.
The prepared product I G/ID is about 20, the thermal weight residue is close to 50%, and the product quality is obviously lower than that of the example 1.
Comparative example 2
This comparative example is substantially the same as example 3, except that the heating rod is maintained but not heated.
The prepared product I G/ID is about 20, the thermal weight residue is close to 50%, and the experimental result is close to that of comparative example 1.
This means that, although the shape of the heating rod itself is a rod-like body along the direction of the gas flow, it should have a certain rectifying action, but this action is not critical to achieve primary rectification in large diameter reaction tubes, and can only be achieved depending on the way of rectifying the reconstructed thermal field proposed by the present invention.
Comparative example 3
In this comparative example, a honeycomb rectifier was used as the mechanical rectifying means in the prior art, and the rectifier was inserted into the first stage to mechanically rectify the current.
The prepared product I G/ID is about 25, the thermal weight residue is close to 45%, and the product quality is obviously lower than that of the example 1.
Comparative example 4
The comparative example adopts a peripheral heating manner, and the heating sheet is wrapped around the periphery of the first stage so that the temperature of the heating sheet coincides with the temperature set by the thermal heating in example 3.
The prepared product I G/ID is about 20, the thermal weight residue is close to 50%, and the experimental result is close to that of comparative example 1.
This is because, in order to adjust the thermal field in the large-diameter reaction tube and to avoid turbulence due to buoyancy, it is necessary to form a temperature gradient from inside to outside by using a rod-shaped heating body, and even if the temperatures are the same, the equivalent function cannot be obtained by using only the wrap-around heating method.
Based on the above examples and comparative examples, it is clear that the apparatus and method provided in the embodiments of the present invention are advantageous for reducing the vortex phenomenon of at least the first stage, avoiding agglomeration and deactivation of catalyst particles at the inlet, solving the problem that buoyancy becomes more prominent due to an increase in temperature gradient, and reducing convection vortex also results in a significant reduction in amorphous carbon and iron oxide in the synthesized CNT aerogel, thereby improving the yield and purity of carbon nanotubes, and thus realizing continuous preparation of carbon nanotubes with high yield, and high purity.
In summary, the device and the method provided by the invention are more beneficial to eliminating convection vortex in the large-diameter reactor tube in the process amplification process, wherein the buoyancy becomes more prominent due to the increase of the temperature gradient, realizing the continuous preparation of the single-walled carbon nanotube with large yield, high yield and high purity, and the device is hopeful to promote the wider application of the single-walled carbon nanotube in various fields and promote the commercialized development of the domestic carbon nanotube technology.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The preparation device for producing the carbon nano tube by the floating chemical vapor deposition method comprises a feeding unit, a reaction tube and a collecting unit, wherein the reaction tube is divided into a first section and a second section, the feeding unit is arranged at an inlet of the first section and is used for injecting a reaction medium into the reaction tube, and the collecting unit is arranged at an outlet of the second section and is used for collecting the formed carbon nano tube;
The method is characterized in that at least the inner diameter of a first section of the reaction tube is more than 200mm, a rod-shaped heating body is arranged in an inner cavity of the first section, and the length direction of the rod-shaped heating body is forward to the central axis of the reaction tube;
In the floating chemical vapor deposition process for producing carbon nanotubes, the rod-shaped heater can generate heat to heat the reaction medium in the vicinity.
2. The apparatus according to claim 1, wherein the heating temperature of the rod-shaped heating body can reach 300 to 700 ℃.
3. Preparation device according to claim 1, characterized in that the rod-shaped heating body extends from the inlet in the direction of the central axis to the end of the first section;
preferably, the length of the first section is 10-33% of the total length of the reaction tube.
4. The manufacturing apparatus according to claim 1, wherein when the number of the rod-shaped heating bodies is one, the rod-shaped heating bodies are disposed on the central axis;
When the number of the rod-shaped heating bodies is multiple, the rod-shaped heating bodies are uniformly distributed around the central axis.
5. The apparatus according to claim 4, wherein the number of the rod-shaped heating bodies is set to be plural, a circle is constructed with a center point of the plural rod-shaped heating bodies as a construction point as viewed on a cross section of the reaction tube, a center of the circle coincides with the central axis;
the diameter of the circle is 30-50% of the inner diameter of the first section.
6. The manufacturing apparatus according to claim 1, further comprising a temperature detection unit including a temperature detector, at least one of the temperature detectors being provided on or near the rod-shaped heating body, capable of detecting a heating state of the rod-shaped heating body.
7. A production method for producing carbon nanotubes using the production apparatus according to any one of claims 1 to 6, comprising:
Bringing the reaction tube to a first set temperature, and bringing the rod-shaped heating body in the reaction tube to a second set temperature, the first set temperature being higher than the second set temperature;
Injecting a reaction medium into the reaction tube from an inlet, wherein the reaction medium comprises a catalyst, a cocatalyst, a carbon source and a reaction gas;
collecting the carbon nanotubes from the outlet.
8. The method of claim 7, wherein the second set temperature is 300-700 ℃;
and/or the first set temperature is 800-1500 ℃.
9. The preparation method according to claim 7, wherein the catalyst comprises any one or a combination of more than two of ferrocene, nickel-dicyclopentadienyl, cobalt-dicyclopentadienyl and ferric chloride;
and/or the cocatalyst comprises any one or more than two of sulfur powder, selenium powder, thiophene and carbon disulfide;
And/or the carbon source comprises a gaseous carbon source and/or a liquid carbon source, wherein the liquid carbon source comprises any one or more than two of ethanol, propanol and toluene, and the gaseous carbon source comprises any one or more than two of methane, ethane, propane, carbon monoxide and carbon dioxide;
And/or the reaction gas comprises at least one of a reducing gas and an inert gas, wherein the reducing gas comprises any one or more than two of hydrogen, water vapor and ammonia, and the inert gas comprises any one or more than two of argon, nitrogen and helium.
10. The method of claim 7, wherein the molar ratio of carbon source to catalyst is 1:1-100 and the molar ratio of catalyst to cocatalyst is 1:1-10;
and/or the total flow rate of the reaction gas is 20000-1 00000sccm.
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| US20100260650A1 (en) * | 2008-01-31 | 2010-10-14 | Shuichi Shiraki | Apparatus for Carbon Nanotube Synthesis |
| CN114053985A (en) * | 2021-11-09 | 2022-02-18 | 江西铜业技术研究院有限公司 | Preparation device and method of single-walled carbon nanotube |
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| JP2005041752A (en) * | 2003-07-25 | 2005-02-17 | Nikkiso Co Ltd | Reaction tube equipment with internal heating element |
| US20100260650A1 (en) * | 2008-01-31 | 2010-10-14 | Shuichi Shiraki | Apparatus for Carbon Nanotube Synthesis |
| CN114053985A (en) * | 2021-11-09 | 2022-02-18 | 江西铜业技术研究院有限公司 | Preparation device and method of single-walled carbon nanotube |
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