CN114933296A - Carbon nanotube and method for producing the same - Google Patents
Carbon nanotube and method for producing the same Download PDFInfo
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- CN114933296A CN114933296A CN202210697365.9A CN202210697365A CN114933296A CN 114933296 A CN114933296 A CN 114933296A CN 202210697365 A CN202210697365 A CN 202210697365A CN 114933296 A CN114933296 A CN 114933296A
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- sealable container
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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
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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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
- C01B2202/04—Nanotubes with a specific amount of walls
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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
- C01B2202/36—Diameter
Abstract
The invention discloses a carbon nano tube and a preparation method thereof. The preparation method of the carbon nano tube comprises the following steps: introducing natural gas and inert gas into a sealed sealable container containing molten metallic copper, such that the natural gas and inert gas enter the molten metallic copper to form carbon nanotubes; wherein the sealable container is disposed in a heating device; the volume ratio of the natural gas to the inert gas is (0.5-5): 1, and the sealed sealable container has an inert atmosphere. The method of the invention can successfully prepare the carbon nano tube.
Description
Technical Field
The invention relates to a carbon nano tube and a preparation method thereof.
Background
The carbon nano tube is a coaxial circular tube formed by hexagonally arranged carbon atoms, and has the characteristics of light weight, high hardness, high strength and high flexibility; and have some unusual electrical and chemical properties. With the intensive research of the carbon nano tube, the wide application prospect of the carbon nano tube is continuously shown. At present, the catalyst is mainly prepared by an arc discharge method, a chemical deposition method, a laser ablation method, a solid-phase pyrolysis method, an ion or laser sputtering method, a polymerization synthesis method or a catalytic cracking method.
CN101195482A discloses a method for growing semiconducting single-walled carbon nanotubes. Placing a catalyst on a substrate; and placing the substrate between the two electrode plates, and growing the semiconductor single-walled carbon nanotube on the substrate by adopting a chemical vapor deposition method in a chemical vapor deposition system. The method requires that the catalyst be placed on a substrate.
CN107128904A discloses a method for preparing graphene by metal catalysis. Heating the metal material to be completely melted under the protection of inert gas, then introducing mixed gas consisting of inert gas and carbon source growth gas into molten metal, reducing the carbon source growth gas in the molten metal to obtain graphene, leaving with gas flow, and separating from the gas to obtain the graphene. The method can only obtain micron-sized sheet graphene, but cannot obtain carbon nanotubes.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a novel method for preparing carbon nanotubes, which can obtain carbon nanotubes. Another object of the present invention is to provide a carbon nanotube.
In one aspect, the present invention provides a method for preparing a carbon nanotube, comprising the steps of:
introducing natural gas and inert gas into a sealed sealable container containing molten metallic copper, such that the natural gas and inert gas enter the molten metallic copper to form carbon nanotubes;
wherein the sealable container is disposed in a heating device;
the volume ratio of the natural gas to the inert gas is (0.5-5): 1, and the sealed sealable container is filled with inert atmosphere.
According to the preparation method, preferably, the flow rate of the natural gas introduced into the sealed and sealable container is 1-6L/min, and the flow rate of the inert gas introduced into the sealed and sealable container is 0.5-4L/min.
According to the production method of the present invention, preferably, the inert gas is argon gas.
According to the preparation method of the invention, the temperature of the molten metal copper is preferably 1000-1500 ℃.
According to the preparation method of the invention, preferably, the pressure in the sealed and sealable container is 0.08-0.15 MPa.
The preparation method according to the present invention preferably further comprises the steps of:
the metallic copper is heated to form molten metallic copper, the sealable container is sealed, and an inert atmosphere is then formed in the sealable container.
According to the production method of the present invention, preferably, the sealable container is a ceramic crucible.
According to the production method of the present invention, preferably, the inert atmosphere is an argon atmosphere.
In another aspect, the present invention provides a carbon nanotube prepared by the above preparation method.
According to the carbon nanotube of the present invention, preferably, the diameter of the carbon nanotube is 50 to 80nm, and the number of layers is 3 to 4.
The invention leads natural gas and inert gas with specific volume ratio into molten metal copper, and successfully synthesizes the carbon nano tube.
Drawings
FIG. 1 is a scanning electron microscope image of a tunnel of the carbon nanotube obtained in example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< method for producing carbon nanotubes >
The preparation method of the carbon nano tube comprises the following steps: natural gas and inert gas are passed into a sealed sealable container containing molten metallic copper, and the natural gas and inert gas are allowed to enter the molten metallic copper to form carbon nanotubes. The sealable container is disposed in a heating device. For example by providing the sealable container in the lower part of the heating device. The heating device may be a high temperature furnace.
The present invention provides for the introduction of natural gas and inert gas together into a sealed, sealable container. Natural gas and inert gas can be fed separately as two streams into sealed sealable containers; alternatively, the natural gas stream may be mixed with the inert gas stream prior to introduction into the sealed sealable container. Natural gas and inert gas are introduced from the upper part of the molten metal copper. According to one embodiment of the invention, the natural gas and inert gas may be passed into the sealed sealable container in a direction perpendicular to the level of the molten metallic copper. According to another embodiment of the invention, the natural gas and inert gas may be introduced into the sealed sealable container at an angle to the level of the molten metallic copper.
The natural gas is mainly formed by mixing gaseous low molecular hydrocarbon and non-hydrocarbon gas, the main component of the natural gas is methane, and the natural gas also contains a small amount of ethane, propane, nitrogen, butane and the like, and the content of the methane can reach more than 80 wt%. The present inventors have surprisingly found that carbon nanotubes can be successfully formed by passing natural gas and an inert gas into a sealed sealable container at a volume ratio.
In the invention, the volume ratio of the natural gas to the inert gas is (0.5-5): 1; preferably (1-3): 1; more preferably (1.2-2): 1. According to one embodiment of the invention, the volume ratio of natural gas to inert gas is 1.5: 1. The volume ratio of natural gas to inert gas may represent the volume ratio of natural gas to inert gas introduced into the sealed sealable container per unit time, or may represent the volume ratio of natural gas to inert gas in the sealable container. When the amount of the natural gas is too small, the flaky graphene is easy to form; when the amount of natural gas is too much, carbon spheres are easily formed. Carbon nanotubes can be successfully formed using the above volume ratio of natural gas to inert gas.
In the invention, the flow rate of natural gas introduced into the sealed container can be 1-6L/min; preferably, 2-5L/min; more preferably 2.5 to 4L/min. According to one embodiment of the invention, the flow rate of natural gas into the sealed and sealable container is 3L/min. Thus, not only can the efficiency be ensured, but also the carbon nano tube can be successfully formed.
In the present invention, the inert gas may be argon gas. This aids in the formation of carbon nanotubes. The flow rate of the inert gas introduced into the sealed container can be 0.5-4L/min; preferably 1-3L/min; more preferably 1.5 to 2.5L/min. According to one embodiment of the invention, the inert gas is introduced into the sealed sealable container at a flow rate of 2L/min. Thus, not only can the efficiency be ensured, but also the carbon nano tube can be successfully formed.
In the invention, the temperature of the molten metal copper is 1000-1500 ℃; preferably 1050-1200 ℃; more preferably 1080 to 1100 ℃.
According to one embodiment of the invention, natural gas and inert gas are introduced under the condition that the temperature of molten metal copper is 1000-1500 ℃. Preferably, natural gas and inert gas are introduced under the condition that the temperature of molten metal copper is 1050-1200 ℃. More preferably, natural gas and inert gas are introduced at 1080-1100 ℃. Therefore, not only can energy be saved, but also the metal copper can exist in a molten state, and simultaneously, the carbon source in the natural gas can be fully cracked.
The pressure in the sealed sealable container can be 0.08-0.15 MPa; preferably 0.09-0.13 MPa; more preferably 0.10 to 0.12 MPa. The sealable container has an inert atmosphere therein; preferably, the inert atmosphere is an argon atmosphere. And introducing gas for forming an inert atmosphere into the sealable container, exhausting the air in the sealable container, and enabling the sealable container to reach the required pressure. This aids in the formation of carbon nanotubes. The gas forming the inert atmosphere may be argon.
The sealable container of the present invention may be a crucible capable of being sealed. For example, the crucible is sealed with a lid to form a sealed crucible. According to one embodiment of the invention, the crucible is a ceramic crucible.
Natural gas and inert gas introduced into the sealable container form bubbles in the molten copper metal. The bubbles serve as a vessel for the natural gas cracking reaction. The molten copper metal forming the bubbles produces a smooth inner surface of the metal wall due to the surface tension of the liquid, such inner surface of the metal wall acting as a deposition bed. The natural gas is cracked to generate carbon and hydrogen, and the carbon is deposited on the bubble wall under the catalytic action of the hydrogen and molten metal copper to form the carbon nano tube. The bubbles rise and break in the molten metal copper, and the carbon nanotubes in the bubbles are released, so that the carbon nanotubes are enriched and recovered.
In certain embodiments, the method further comprises the steps of: the metallic copper is heated to form molten metallic copper, the sealable container is sealed, and an inert atmosphere is then formed in the sealable container. The heating may be performed in an air atmosphere.
< carbon nanotubes >
The carbon nano tube is prepared by the method. The diameter of the carbon nano tube is 50-80 nm. The number of carbon nanotube layers is 3-4.
Example 1
(1) The metallic copper is heated in a ceramic crucible to form molten metallic copper at a temperature of 1080 ℃. Covering and sealing the ceramic crucible; then argon gas is introduced into the ceramic crucible, and the air in the sealed ceramic crucible is discharged, so that the pressure in the ceramic crucible is 0.1 MPa.
(2) The molten metallic copper was maintained at 1080 ℃ by the heating action of the heating device. Simultaneously introducing natural gas and argon gas from the top of the ceramic crucible, wherein the flow rate of the natural gas is 3L/min, and the flow rate of the argon gas is 2L/min, so as to form the carbon nano tube.
Fig. 1 is a tunnel scanning electron microscope image of the carbon nanotube obtained in the present example. The diameter of the carbon nanotube of this embodiment is 50-80 nm, and the number of layers is 3-4.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may occur to those skilled in the art may fall within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A method for preparing carbon nanotubes is characterized by comprising the following steps:
introducing natural gas and inert gas into a sealed sealable container containing molten metallic copper, such that the natural gas and inert gas enter the molten metallic copper to form carbon nanotubes;
wherein the sealable container is disposed in the heating device;
wherein the volume ratio of the natural gas to the inert gas is (0.5-5): 1, and the sealed sealable container has an inert atmosphere therein.
2. The method of claim 1, wherein the natural gas is introduced into the sealed and sealable container at a flow rate of 1 to 6L/min and the inert gas is introduced into the sealed and sealable container at a flow rate of 0.5 to 4L/min.
3. The method of claim 1, wherein the inert gas is argon.
4. The method according to claim 1, wherein the temperature of the molten metal copper is 1000 to 1500 ℃.
5. The method of claim 1, wherein the pressure within the sealed and sealable container is between 0.08 Mpa and 0.15 Mpa.
6. The method of claim 1, further comprising the steps of:
the metallic copper is heated to form molten metallic copper, the sealable container is sealed, and then an inert atmosphere is formed in the sealable container.
7. The method of claim 6, wherein the sealable container is a ceramic crucible.
8. The method of claim 1, wherein the inert atmosphere is an argon atmosphere.
9. A carbon nanotube produced by the production method according to any one of claims 1 to 8.
10. The carbon nanotube according to claim 9, wherein the carbon nanotube has a diameter of 50 to 80nm and a number of layers of 3 to 4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210697365.9A CN114933296A (en) | 2022-06-20 | 2022-06-20 | Carbon nanotube and method for producing the same |
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| CN202210697365.9A CN114933296A (en) | 2022-06-20 | 2022-06-20 | Carbon nanotube and method for producing the same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060141153A1 (en) * | 2002-06-24 | 2006-06-29 | Honda Giken Kogyo Kabushiki Kaisha | Method for making carbon nanotubes |
| JP2007153694A (en) * | 2005-12-06 | 2007-06-21 | Toray Ind Inc | Method and apparatus for producing carbon nanotube |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN107128904A (en) * | 2017-05-11 | 2017-09-05 | 张丽慧 | A kind of method that metal catalytic prepares graphene |
| CN111977635A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Carbon nano tube and preparation method thereof |
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- 2022-06-20 CN CN202210697365.9A patent/CN114933296A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060141153A1 (en) * | 2002-06-24 | 2006-06-29 | Honda Giken Kogyo Kabushiki Kaisha | Method for making carbon nanotubes |
| JP2007153694A (en) * | 2005-12-06 | 2007-06-21 | Toray Ind Inc | Method and apparatus for producing carbon nanotube |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN107128904A (en) * | 2017-05-11 | 2017-09-05 | 张丽慧 | A kind of method that metal catalytic prepares graphene |
| CN111977635A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Carbon nano tube and preparation method thereof |
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