CN114808196A - Carbon nanotube preparation device, injection assembly thereof and carbon nanotube preparation method - Google Patents
Carbon nanotube preparation device, injection assembly thereof and carbon nanotube preparation method Download PDFInfo
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- CN114808196A CN114808196A CN202210408791.6A CN202210408791A CN114808196A CN 114808196 A CN114808196 A CN 114808196A CN 202210408791 A CN202210408791 A CN 202210408791A CN 114808196 A CN114808196 A CN 114808196A
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
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Abstract
The invention discloses a carbon nanotube preparation device, an injection assembly thereof and a method for preparing carbon nanotubes by using the same. The preparation device comprises: the reaction furnace tube for providing the carbon nano tube growth environment comprises a first end, a middle section and a second end; an injection assembly sealingly connected to the first end; the temperature control assembly is arranged on the periphery of the reaction furnace tube and is used for controlling the process temperature of at least the middle section of the reaction furnace tube; the injection assembly comprises: the device comprises an injection flange connected to the first end in a sealing manner, a first raw material passage and a second raw material passage which penetrate through the injection flange, and a sublimation tank; the sublimation tank is communicated with the first raw material passage and used for accommodating and sublimating the catalytic source so that the gaseous catalytic source enters the reaction furnace tube through the first raw material passage, and the second raw material passage is used for at least injecting a carbon source into the reaction furnace tube. The preparation device, the components and the method thereof greatly improve the yield of the carbon nano tube preparation and the stability of the preparation process.
Description
Technical Field
The invention relates to the technical field of inorganic carbon materials, in particular to a carbon nanotube preparation device, an injection assembly thereof and a carbon nanotube preparation method.
Background
The carbon nano tube has excellent physical and chemical properties, and the assembly of the carbon nano tube into a macroscopic body, such as a fiber, is one of important ways for realizing the macroscopic application of the carbon nano tube, and has important significance for the fields of national economy, national defense, aerospace and the like.
The preparation method of the carbon nano tube fiber mainly comprises a wet spinning method, an array spinning method and a floating catalysis direct spinning method. The floating catalytic carbon nanotube fiber has the advantages of high mechanical property, easiness in large-scale continuous preparation and the like, and is considered to be the carbon nanotube fiber preparation method with the most potential and application prospect.
The efficiency of the preparation of floating carbon nanotube fibers is one of the major issues of concern to researchers in this field. The typical preparation method of the floating catalytic carbon nanotube fiber comprises the steps of continuously injecting a ferrocene (as a catalytic source)/thiophene (as a sulfur source)/ethanol (as a carbon source) solution into a high-temperature reaction cavity under the action of a carrier gas, decomposing ferrocene at high temperature under a high-temperature gas phase environment to form iron catalytic source nano particles, further saturating and separating out carbon atoms generated by high-temperature pyrolysis of an ethanol carbon source on the surfaces of the catalytic source nano particles to grow carbon nanotubes and further aggregating to form a sleeve-shaped aerogel structure, and densifying a carbon nanotube fiber aerogel precursor to obtain the carbon nanotube fiber. The existing preparation of carbon nanotube fibers or other forms of floating carbon nanotube materials has the phenomena of low preparation efficiency and unstable preparation process.
For example, in most of the prior art, in the process of preparing carbon nanotube fiber by the floating catalytic direct spinning method, the catalytic source and the carbon source solvent are mainly supplied in the following ways: (1) in patent CN1005407764C, a solution is prepared from a catalytic source and a carbon source solvent, and the solution is injected into a high-temperature reaction furnace through a nozzle to prepare the carbon nanotube continuous fiber. (2) The patent CN103435029A prepares a solution by a catalytic source and a carbon source solvent, and injects the solution into a high-temperature reaction furnace under the action of carrier gas by an ultrasonic atomization mode, so that the solution gasification efficiency and the fiber preparation efficiency can be improved to a certain extent. (3) In patent CN111020747A, a solution is prepared by a catalytic source and a carbon source solvent, and is injected into a high-temperature reaction furnace by carrier gas after being pre-gasified by a gasification tank, so that the continuity and stability of a fiber process can be improved. However, with the above-mentioned prior art solutions, no matter how the raw material ratio and the process parameters are adjusted, a larger yield and a stable preparation process cannot be obtained at the same time.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention is directed to a carbon nanotube manufacturing apparatus, an injection module thereof, and a carbon nanotube manufacturing method.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides an injection assembly applied to an apparatus for manufacturing a carbon nanotube, including:
the device comprises an injection flange, a first raw material passage and a second raw material passage which penetrate through the injection flange, and a sublimation tank;
the sublimation tank is communicated with the first raw material passage and used for accommodating and sublimating the catalytic source so that the gaseous catalytic source enters the reaction furnace tube through the first raw material passage, and the second raw material passage is used for at least injecting a carbon source into the reaction furnace tube.
In a second aspect, the present invention also provides an apparatus for efficiently preparing carbon nanotubes, comprising: the reaction furnace tube is used for providing a carbon nano tube growth environment and comprises a first end, a middle section and a second end which are sequentially connected; an injection assembly sealingly connected to the first end; the temperature control assembly is arranged on the periphery of the reaction furnace tube and is used for at least controlling the process temperature of the middle section of the reaction furnace tube;
the injection assembly is the above injection assembly, and includes: the device comprises an injection flange connected to the first end in a sealing manner, a first raw material passage and a second raw material passage which penetrate through the injection flange, and a sublimation tank;
the sublimation tank is communicated with the first raw material passage and used for accommodating and sublimating the catalytic source so that the gaseous catalytic source enters the reaction furnace tube through the first raw material passage, and the second raw material passage is used for at least injecting a carbon source into the reaction furnace tube.
In a third aspect, the present invention further provides a method for efficiently preparing carbon nanotubes, which is applied to the efficient preparation system, and includes:
controlling the temperature of the middle section of the reaction furnace tube to reach the process temperature, and introducing process gas into the reaction furnace tube;
sublimating the catalytic source into a gaseous state in the sublimation tank, and carrying the gaseous catalytic source by carrier gas to enter a reaction furnace pipe through a first raw material passage;
a carbon source is led into the reaction furnace pipe through a second raw material passage;
and the carbon source and the catalytic source generate a carbon nano tube precursor in the reaction furnace tube, the carbon nano tube precursor is output from the second end of the reaction furnace tube, and the carbon nano tube precursor is collected by using a collecting assembly.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
the high-efficiency preparation device, the components and the method thereof provided by the invention inject the catalytic source in a gaseous state through the sublimation tank, can avoid the limitation of the solubility of the catalytic source in a carbon source, greatly increase the concentration of catalytic particles, provide more carbon nanotube growing points, avoid the local precipitation phenomenon of the catalytic source in a reaction furnace tube caused by the heat absorption of the carbon source, and greatly improve the yield of the carbon nanotube preparation and the stability of the preparation process.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the detailed drawings.
Drawings
FIG. 1 is a schematic structural diagram of a system for efficiently preparing carbon nanotubes according to an exemplary embodiment of the present invention;
FIG. 2 is a photomicrograph of a carbon nanotube fiber provided in accordance with an exemplary embodiment of the present invention;
FIG. 3 is an electron micrograph of the surface topography of a carbon nanotube fiber provided in accordance with an exemplary embodiment of the present invention;
description of reference numerals: 1. a housing; 2. a raw material pipe; 3. heating a jacket; 4. a support table; 5. sealing the flange; 6. a carrier gas inlet; 7. a base; 8. a first feedstock passage; 9. a first gas flow controller; 10. an injector; 11. a second gas flow controller; 12. injecting a flange; 13. a reaction furnace tube; 14. a temperature control assembly; 15. a carbon nanotube precursor; 16. a liquid seal tank chamber; 17. a tail gas outlet; 18. a water tank; 19. sealing the liquid; 20. a fiber winding device; 21. carbon nanotube fibers.
Detailed Description
The inventors have long studied and practiced to find that, based on the existing preparation method of floating catalytic carbon nanotubes, a large yield and a stable preparation process cannot be obtained at the same time, and those skilled in the art may tend to increase the injection amount of the reaction raw material to obtain a large yield, however, the inventors found that the injection amount of the carbon source increases with the solution injection manner of the catalytic source and the carbon source in the prior art, which is limited by the solubility of the catalytic source in the carbon source, and in order to increase the injection amount of the catalytic source, the quality of the generated carbon nanotube precursor becomes poor, and there is an upper limit of the yield, above which a larger yield cannot be obtained even if the injection amount of the liquid material is increased, and the opposite effect is easily achieved. Thus, the present inventors found that in order to increase the yield of carbon nanotubes, the injection ratio of the catalytic source to the carbon source should be focused primarily, rather than simply increasing the number of catalytic sources and/or carbon sources.
In short, the present inventors have found that in the prior art method of preparing a floating carbon nanotube fiber, ferrocene (one of the catalytic sources) is pyrolyzed to form iron atoms, and the iron atoms are agglomerated in a gas phase environment to form nanoparticles and serve as catalytic source particles for carbon nanotube growth. The content of ferrocene is increased in the reaction system, so that the number of iron catalytic source particles in the system can be increased, and the yield of carbon tubes and carbon nanotube fibers is improved. The method of dissolving ferrocene in liquid ethanol or acetone to provide ferrocene to the reaction system is limited by the solubility of ferrocene in the above solvents, the injection amount of ferrocene is limited, and the number of iron catalytic source nanoparticles and the yield of the final carbon nanotube are further limited.
In addition, the inventor also finds that in the floating catalytic chemical reaction process, the liquid carbon source needs to be completely gasified to perform the subsequent catalytic reaction, and the gasification and cracking of the carbon source need to absorb heat. However, because the sublimation temperature of ferrocene is higher than the gasification temperature of solvents such as ethanol and acetone, ethanol and acetone are likely to volatilize at the injection port of the liquid carbon source during the reaction process, and ferrocene is not completely volatilized or is re-condensed due to heat absorption of the carbon source after volatilization and is continuously accumulated locally, so that the supply ratio of the carbon source and the catalytic source is unstable, and the stability and the continuity of the subsequent reaction process are affected.
Moreover, the present inventors found in long-term practice that in the prior art, by increasing the injection amount of the liquid mixed carbon source or by using other methods such as introducing a large amount of sulfur-containing auxiliary agent, the yield is increased, and at the same time, the stability of the preparation process is reduced, that is: the prior art can not achieve high yield and high stability at the same time.
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be 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, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second," and the like, may be used solely to distinguish one element or method step from another element or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such elements or method steps.
Referring to fig. 1, an embodiment of the present invention provides an apparatus for efficiently preparing carbon nanotubes, including: the reaction furnace tube 13 is used for providing a carbon nanotube growth environment, the reaction furnace tube 13 comprises a first end, a middle section and a second end which are connected in sequence, an injection assembly which is connected with the first end of the reaction furnace tube 13 in a sealing way, and a temperature control assembly 14 which is arranged on the periphery of the reaction furnace tube 13, and the temperature control assembly 14 is used for at least controlling the process temperature of the middle section of the reaction furnace tube 13.
In some embodiments, the injection assembly comprises: an injection flange 12 hermetically connected to the first end, a first raw material passage 8 and a second raw material passage penetrating the injection flange 12, and a sublimation tank; the sublimation tank is communicated with the first raw material passage 8 and is used for accommodating and sublimating a catalytic source so that the gaseous catalytic source enters the reaction furnace tube 13 through the first raw material passage 8, and the second raw material passage is used for at least injecting a carbon source into the reaction furnace tube 13.
In some embodiments, the first feedstock passage 8 is provided with a thermal insulation structure.
In some embodiments, the insulating structure is capable of maintaining the temperature of the first raw material passage 8 above 150 ℃ while performing carbon nanotube production.
In some embodiments, the insulating structure comprises an insulating layer and/or an active heating structure. The active heating structure may be, for example, an electric heating wire or an electric heating winding belt, which may be wrapped around the first material passage 8 alone, or may be matched with an insulating layer to achieve a better insulating effect, and for the insulation of the first material passage 8, those skilled in the art may make modifications or substitutions according to the existing technical teaching, but all of them fall within the protection scope of the present invention.
In some embodiments, the sublimation tank includes a sealed tank body, a feedstock tube 2 disposed within the tank body, and a heating jacket 3 surrounding the feedstock tube 2. The tank body is provided with a carrier gas inlet 6 and a catalytic source outlet, and the catalytic source outlet is communicated with the first raw material passage 8; the two ends of the raw material pipe 2 are provided with openings for accommodating the catalytic source, and the heating jacket 3 is used for controlling at least the temperature in the raw material pipe 2.
In some embodiments, the material of the raw material tube 2 includes one or a combination of quartz and corundum.
In some embodiments, the material of the body of the heating jacket 3 is a heat conducting material, and the heat conducting material includes metal and/or graphite, and in some further embodiments, the material of the body of the heating jacket 3 is preferably copper. The copper material generally refers to copper-containing metals having high thermal conductivity, such as pure copper and copper alloys. Of course, the heating jacket 3 may be a heating structure such as an electric heating wire or an electric heating rod fixed outside or inside the copper main body.
In some embodiments, the heating jacket 3 is capable of controlling the temperature within the feedstock tube 2 to 100300 ℃.
In some embodiments, the tank comprises a casing 1 and a sealing flange 5 which can be assembled or disassembled, and the raw material pipe 2 and the heating jacket 3 are thermally isolated from the sealing flange 5. The main purpose of the thermal insulation is to prevent the high-temperature aging failure of the sealing material caused by the heat of the raw material pipe 2 and the heating jacket 3 being conducted to the sealing flange 5.
In some embodiments, the feedstock pipe 2 and the heating jacket 3 are connected to the sealing flange 5 by a support table 4.
In some embodiments, the opening of the feedstock pipe 2 is disposed adjacent to the catalytic source outlet.
In some embodiments, the first feed passage 8 extends into the reaction furnace tube 13 after passing through the injection flange 12 such that the temperature at the end of the first feed passage 8 is above 300 ℃ when the middle section of the reaction furnace tube 13 reaches the process temperature. The present inventors have found that when the temperature of the end of the first raw material passage 8 reaches 300 ℃ or higher, the re-precipitation phenomenon that may occur when the catalytic source is influenced by the carbon source endotherm can be avoided to the maximum extent.
In some embodiments, the high efficiency manufacturing apparatus further comprises a first gas flow controller 9 and a second gas flow controller 11 in communication with the interior of the reactor furnace tube 13, wherein the first gas flow controller 9 is configured to control the flow of the carrier gas, and the second gas flow controller 11 is configured to pump a desired flow of the process gas into the reactor furnace tube 13. The carrier gas is, for example, argon, nitrogen or other process gas, and may even be a gaseous second carbon source, and the like, and the second gas may be, for example, hydrogen, argon, nitrogen, and the like, and those skilled in the art can adaptively adjust the pumping type and flow rate of the setting gas, and may even add more gas flow controllers, and various modifications made by those skilled in the art according to the main technical concept of the present invention and their practical requirements are within the scope of the present invention.
Based on the above technical solutions, as some typical application examples, the main structure of one exemplary apparatus provided by the present invention includes: ferrocene sublimation tank, control sample injection module, fiber growth module and fiber collection module.
Ferrocene sublimation jar includes stainless steel sublimation jar shell 1, the quartz raw material pipe 2 of splendid attire ferrocene, copper even hot heating jacket 3 and corresponding temperature regulating device, brace table 4, sealing flange 5, carrier gas entry 6, base 7. The sample control module comprises a sublimation gas heat preservation pipeline (namely the first raw material passage 8), a first gas flow controller 9, a carbon source solution injection pump, a second gas flow controller 11 and a reaction furnace sealing flange 5 (namely the injection flange 12). The fiber growth module comprises a high-temperature reaction furnace tube 13 and an electric heating furnace (namely the temperature control assembly 14). The fiber collecting module comprises a liquid seal box chamber 16, a tail gas outlet 17, a water tank 18, sealing liquid 19 and a fiber winding device 20.
In the above exemplary apparatus, the ferrocene sublimation tank is used to allow the ferrocene as the catalyst to be directly added in a gaseous form to the carbon nanotube reaction growth system, for example, 5-10g of solid ferrocene may be first charged into the quartz raw material tube 2, the quartz raw material tube 2 may be placed on the support table 4, and then the stainless steel sealed housing 1 may be covered and sealed by the sublimation tank sealing flange 5. The raw material pipe 2 is heated to a preset temperature through the copper even heating jacket 3, the temperature of the copper even heating jacket 3 can be accurately controlled through a thermocouple, the highest temperature can reach 350 ℃, and the raw material pipe 2 can be uniformly distributed due to the fact that copper with good heat conduction is adopted as a heat transfer medium, and the phenomenon of nonuniform heating is avoided. The sublimation temperature of the ferrocene is higher than 100 ℃, and the temperature of the copper uniform heating jacket 33 can be set to be 100-300 ℃ according to the required sublimation amount when in use. Because the design service temperature is higher, if the heating jacket 3 and the sealing flange 5 directly contact, the sealing gasket can not bear, so the heating jacket 3 and the sealing flange 5 need to be separated by the support table 4. Then, argon is introduced through the carrier gas inlet 6, and the ferrocene sublimated into the gaseous state in the sublimation tank is taken out of the sublimation tank. The opening part of quartz raw material pipe 2 is close with the catalytic source exit position of sublimation jar, can take the most ferrocene that sublimates out of the sublimation jar, avoids the sublimation gas to pile up after other position condensations in the sublimation jar.
The sample injection control module is mainly used for adjusting the gas flow through a gas flow controller. The ferrocene vapor sublimed in the sublimation tank is brought into the reaction furnace system for reaction through the heat-insulating first raw material passage 8, the heat preservation of the pipeline is to prevent the sublimation gas from being re-solidified due to temperature reduction in the pipeline conveying process, and the temperature of the heat-insulating pipeline can be set to 150 ℃ for example. The flow of argon can be adjusted by the first gas flow controller 9 according to the amount of ferrocene sublimation gas required. The carbon source solution on the other side can be injected through an injector 10, the injection rate can be 25-30ml/h, the flow of argon and hydrogen can be regulated and controlled through a second gas flow controller 11, and the gasified carbon source solution is driven to enter the reaction chamber. The flow rates of hydrogen and argon may range, for example, from 1 to 5 SLM.
The above is an exemplary illustration of the efficient manufacturing apparatus provided by the present invention, which can produce a large amount of carbon nanotubes stably, and at this time, the carbon nanotubes produced by the apparatus are still in a precursor state, and are a fluffy aerogel, and if a carbon nanotube material capable of being used macroscopically, such as carbon nanotube fibers or films, is to be obtained, the carbon nanotube material still needs to be matched with a collecting assembly to form an overall system. Therefore, the embodiments of the present invention continue to provide a system based on the above-mentioned apparatus.
With continued reference to fig. 1, in some embodiments, the above-mentioned manufacturing apparatus further includes a collecting assembly, which is connected to the second end of the reaction furnace 13 and is used for collecting the carbon nanotube precursor 15 output from the second end of the reaction furnace 13.
In some embodiments, the collection assembly comprises a carbon nanotube fiber collection assembly or a carbon nanotube film collection assembly.
As an example, the carbon nanotube fiber collecting assembly may be obtained by taking the carbon nanotube aerogel precursor generated in the reaction furnace tube 13 out of the chamber by the carrier gas, drawing the carbon nanotube aerogel precursor into water in the liquid seal chamber 16 for densification, then drawing the carbon nanotube aerogel precursor out of the water, and performing roller winding collection by the fiber winding device 20 to obtain a carbon nanotube fiber finished product, wherein the winding rate may be, for example, 5 to 30 m/min.
Of course, the manner of collecting the carbon nanotube film is not critical, and those skilled in the art can easily replace various carbon nanotube collecting devices disclosed in other prior arts, such as film collecting, aerogel collecting, or even collecting carbon nanotube dispersion or composite material, etc., or design other collecting devices and collecting methods different from those disclosed in the prior arts. Any collection mode change and replacement based on the core concept of the invention still belong to the protection scope of the invention.
The embodiment of the invention also provides an efficient preparation method of the carbon nano tube, which is applied to the efficient preparation device and comprises the following steps:
controlling the temperature of the middle section of the reaction furnace tube 13 to reach the process temperature, and introducing process gas into the reaction furnace tube 13.
The catalytic source is sublimated into gas in the sublimation tank and enters the reaction furnace tube 13 through the first raw material passage 8 by being carried by the carrier gas.
A carbon source is introduced into the reaction furnace tube 13 through the second raw material passage.
The carbon source and the catalytic source generate a carbon nanotube precursor 15 in the reaction furnace tube 13 and output at the second end of the reaction furnace tube 13, and the carbon nanotube precursor 15 is collected by a collecting assembly.
In some embodiments, the process temperature is 1000-.
In some embodiments, the yield of carbon nanotubes is above 3 g/h.
As an example, in the high temperature reaction furnace tube 13, the vaporized ferrocene decomposes to an iron catalyst, catalyzing the carbon source to form the carbon nanotube precursor 15. The high temperature reaction furnace tube 13 may have a diameter of 50250mm and a length of 50200cm, for example. The furnace body is heated by means of an electric heating rod, and the furnace temperature of the electric heating furnace can be set to be 1000-1500 ℃ for example.
The embodiment of the invention also provides the carbon nano tube prepared by the high-efficiency preparation method.
In some embodiments, the macroscopic morphology of the carbon nanotubes is carbon nanotube fibers.
In some embodiments, the carbon nanotube fibers have a continuity of greater than 1000 m.
As some typical application examples, the device of the invention introduces a catalyst precursor (ferrocene) gasification tank on the basis of a device for preparing carbon nanotube fibers by a floating catalytic CVD method, the supply of ferrocene is changed into the supply of sublimation gas, and the supply amount is not limited by solubility any more, thereby enabling the growth of the carbon nanotube fibers to be more efficient. And after the ferrocene is dissolved in the carbon source solution, a local precipitation phenomenon can occur when the ferrocene enters a high-temperature reaction furnace chamber. The device for introducing the catalyst precursor (ferrocene) gasification tank can separate ferrocene from a carbon source, and the ferrocene and the carbon source are independently introduced into the reaction furnace tube 13 after sublimation gasification, so that the phenomenon of local precipitation of the ferrocene is avoided, the supply of the carbon source/catalyst in the growth process is more uniform, and the uniformity and the continuity of the growth of the carbon nanotube fiber are enhanced.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
This example provides an example of a specific carbon nanotube fiber, which is prepared as follows:
this example employs a carbon nanotube production system as shown in fig. 1, in which a sublimation tank includes a stainless steel casing 1 in which a raw material tube 2 of quartz is provided, a heating jacket 3 made of copper is fitted around the raw material tube 2, both the raw material tube 2 and the heating jacket 3 are placed on a support table 4, and the support table 4 is fixed to a sealing flange 5; the reaction furnace tube 13 is a corundum tube, the inner diameter of the corundum tube is 100mm, and the length of the corundum tube is 1350 mm;
the outlet of the sublimation tank is connected with a first raw material passage 8, the first raw material passage 8 extends all the way and penetrates through an injection flange 12 hermetically arranged at the first end of a reaction furnace tube 13, and then the first raw material passage continues to extend a certain distance into the reaction furnace tube 13, so that the temperature of the tail end of the reaction furnace tube is over 300 ℃ during preparation;
the second raw material passage is communicated with a carbon source injector 10, liquid alcohol is contained in the carbon source injector 10, and 1% of thiophene is dissolved in the alcohol to be used as a sulfur source;
the collection end adopts a component as shown in figure 1, and comprises a liquid seal box chamber 16 connected with the second end of the reaction furnace tube 13, the opening section of the liquid seal box chamber 16 is immersed in a sealing liquid 19 in a water tank 18, a tail gas outlet 17 is arranged on one side of the liquid seal box chamber, and a fiber winding device 20 is arranged on one side of the water tank 18;
when the preparation system is adopted to prepare the carbon nanotube fiber 21, the heating jacket 3 in the sublimation tank is set to be 200 ℃, the flow rate of carrier gas (argon) entering the sublimation tank is controlled to be 1SLM through the first gas flow controller 9, the alcohol carbon source is injected at the injection rate of 30ml/h on the other side, hydrogen and argon mixed gas with the volume ratio of 1: 1 is introduced into the sublimation tank through the second gas flow controller 11, the reaction furnace tube 13 is controlled to be 1350 ℃ through the temperature control component 14, and the winding speed of the fiber winding device 20 is 20 m/min.
The carbon nanotube fiber 21 prepared in this example has a very high yield of 3.5g/h and a continuity of 1000m, the macroscopic state of the fiber is shown in fig. 2, the microscopic surface morphology is shown in fig. 3, and it should be noted that the continuity is limited by the capacity limitation of the carbon source injector 10, and if an injection pump capable of continuously and stably providing a liquid carbon source is used, the continuity is still higher theoretically, which indicates that the carbon nanotube preparation of this example has both a very high yield and a very high stability.
Example 2
This example provides a specific example of a carbon nanotube fiber manufacturing process, which is substantially similar to example 1 except that:
the temperature of the heating jacket 3 was controlled to 250 ℃.
The yield of the prepared carbon nano tube fiber 21 is 3g/h, and the continuity reaches 1000 m.
Example 3
This example provides a specific example of a carbon nanotube fiber manufacturing process, which is substantially similar to example 1 except that:
the liquid carbon source is acetone.
The yield of the prepared carbon nano tube fiber 21 is 3g/h, and the continuity reaches 1000 m.
Example 4
This example provides a specific example of a carbon nanotube fiber manufacturing process, which is substantially similar to example 1 except that:
the reaction furnace tube 13 is a quartz tube.
The yield of the prepared carbon nano tube fiber 21 is 2g/h, and the continuity reaches 600 m.
Comparative example 1
This comparative example provides an example of a specific carbon nanotube fiber preparation, the procedure of which is shown below:
by adopting the sample introduction mode of the invention, the temperature of the extending position of the ferrocene injection pipe is 150 ℃, the ferrocene injection pipe does not enter the high-temperature reaction chamber (300 ℃), and the rest structure and material size are the same as those of the embodiment 1.
The carbon nanotube fiber 21 prepared in this comparative example has a yield of only 1g/h, and the continuity (stability) is significantly weaker than that of example 1, the continuity being 300 m. Ferrocene segregation was observed at the outlet of the injection tube.
Comparative example 2
This comparative example provides an example of a specific carbon nanotube fiber preparation, the procedure of which is shown below:
adopting the existing solution injection method, the prepared liquid carbon source is a saturated ferrocene ethanol solution, and the concentration of thiophene is the same as that in the embodiment 1;
and the structure and material dimensions were the same as those of example 1 except that the sublimation tank and the corresponding first raw material passage 8 and first gas flow controller 9 were not provided.
The carbon nanotube fiber 21 prepared in this comparative example had a yield of only 1.5g/h, and had a continuity (stability) significantly weaker than that of example 1, the continuity being 400 m.
Based on the above embodiments and the comparative example, it is clear that the efficient preparation apparatus, the components thereof and the method provided by the present invention inject the catalytic source in a gaseous state through the sublimation tank, so that the limitation of the solubility of the catalytic source in the carbon source can be avoided, the concentration of the catalytic particles is greatly increased, more carbon nanotube growth points are provided, the local precipitation phenomenon caused by the catalytic source being affected by the heat absorption of the carbon source in the reaction furnace tube 13 is avoided, and the yield of the carbon nanotube preparation and the stability of the preparation process are greatly improved.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. An injection assembly applied to a carbon nanotube manufacturing apparatus, comprising:
the device comprises an injection flange, a first raw material passage and a second raw material passage which penetrate through the injection flange, and a sublimation tank;
the sublimation tank is communicated with the first raw material passage and is used for accommodating and sublimating the catalytic source so that the gaseous catalytic source enters the reaction furnace tube through the first raw material passage, and the second raw material passage is used for at least injecting a carbon source into the reaction furnace tube.
2. The infusion assembly of claim 1, wherein the first feedstock passage is provided with a thermal insulation structure;
preferably, the heat-insulating structure can maintain the temperature of the first raw material passage at 150 ℃ or higher when the carbon nanotube is produced;
preferably, the heat insulation structure comprises an insulation layer and/or an active heating structure.
3. The inject assembly of claim 1, wherein the sublimation canister includes a sealed canister body, a feedstock tube disposed within the canister body, and a heating jacket surrounding the feedstock tube;
the tank body is provided with a carrier gas inlet and a catalytic source outlet, and the catalytic source outlet is communicated with the first raw material passage; the two ends of the raw material pipe are provided with openings for accommodating the catalytic source, and the heating sleeve is used for at least controlling the temperature in the raw material pipe.
4. The inject assembly of claim 3, wherein the material of the feedstock pipe comprises one or a combination of quartz and corundum;
preferably, the material of the main body of the heating jacket is a heat conducting material, and the heat conducting material comprises metal and/or graphite, and is further preferably copper;
preferably, the heating jacket can control the temperature in the raw material pipe to be 100-300 ℃.
5. The infusion assembly of claim 3, wherein the tank comprises a sectional or separable outer shell and a sealing flange, the feedstock tube and heating jacket being thermally isolated from the sealing flange;
preferably, the raw material pipe and the heating jacket are connected with the sealing flange through a support table;
preferably, the opening of the feedstock pipe is adjacent to the catalytic source outlet.
6. An apparatus for producing carbon nanotubes, comprising:
the reaction furnace tube is used for providing a carbon nano tube growth environment and comprises a first end, a middle section and a second end which are sequentially connected; the inject assembly of any one of claims 1-5, the inject assembly is sealingly connected to the first end; and the temperature control assembly is arranged on the periphery of the reaction furnace tube and is used for at least controlling the process temperature of the middle section of the reaction furnace tube.
7. The production apparatus according to claim 6, wherein the first raw material passage of the injection assembly extends into the reaction furnace tube after penetrating the injection flange so that a temperature of an end of the first raw material passage is 300 ℃ or higher when the intermediate stage reaches the process temperature.
8. The apparatus of claim 6, further comprising a first gas flow controller and a second gas flow controller in communication with the interior of the reactor furnace tube, the first gas flow controller configured to control a flow of a carrier gas and the second gas flow controller configured to pump a desired flow of process gas into the reactor furnace tube.
9. The apparatus of claim 6, further comprising a collecting assembly coupled to the second end of the reaction furnace tube for collecting the carbon nanotube precursor output from the second end of the reaction furnace tube;
preferably, the collecting member comprises a carbon nanotube fiber collecting member or a carbon nanotube film collecting member.
10. A method for producing a carbon nanotube, which is applied to the production apparatus according to any one of claims 6 to 9, comprising:
controlling the temperature of the middle section of the reaction furnace tube to reach the process temperature, and introducing process gas into the reaction furnace tube;
sublimating the catalytic source into a gaseous state in the sublimation tank, and carrying the gaseous catalytic source by carrier gas to enter a reaction furnace pipe through a first raw material passage;
a carbon source is led into the reaction furnace pipe through a second raw material passage;
the carbon source and the catalytic source generate a carbon nanotube precursor in the reaction furnace tube and output the carbon nanotube precursor at the second end of the reaction furnace tube, a collection assembly is used for collecting the carbon nanotube precursor, and the carbon nanotube precursor can be selectively converted into a carbon nanotube macroscopic body;
preferably, the process temperature is 1000-1500 ℃, and the process gas comprises hydrogen and argon;
preferably, the yield of the carbon nano tube is more than 3 g/h;
preferably, the carbon nanotube macroscopic body comprises carbon nanotube fibers or carbon nanotube films, and the continuity of the carbon nanotube fibers is more than 1000 m.
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