Reaction apparatus for catalyzing the production of single-walled carbon nanotubes and its applications

Abstract

The present invention discloses a reaction device for catalyzing the formation of single-walled carbon nanotubes. The reaction device for catalyzing the formation of single-walled carbon nanotubes includes a reaction vessel, which has a reaction space inside. At least a catalyst input channel and a first water-cooled pipe are provided on the reaction vessel. A first channel is formed inside the first water-cooled pipe. The catalyst input channel and the first channel are respectively communicated with the reaction space. The catalyst input channel is used to input a catalyst precursor into the reaction space, and the first water-cooled pipe is at least used to input an inert gas into the reaction space through the first channel. The reaction device for catalyzing the formation of single-walled carbon nanotubes of the present invention can achieve the effects of facilitating the growth of single-walled carbon nanotubes, saving the catalytic cost, and improving the catalytic efficiency.

Description

Technical Field

[0001] The present invention relates to a reaction device for catalyzing the generation of single-walled nanotubes, belonging to the technical field of nanotubes. Background Art

[0002] Single-walled carbon nanotubes (SWCNTs) are rolled structures of single-layer graphene, with excellent mechanical, electrical and other properties, and have a wide range of application scenarios in the fields of nanoelectronics, electrochemical energy storage materials, catalysis, hydrogen storage, etc. The main preparation methods of single-walled carbon nanotubes include laser ablation method, arc discharge method, chemical vapor deposition method, etc. The carbon nanotubes prepared by the laser ablation method have good quality, but the yield is low and the required equipment is expensive. The arc discharge method has a high reaction temperature, and there are more graphitized carbon and iron particles wrapped by carbon in the prepared carbon nanotubes, and it is difficult to remove them. In the chemical vapor deposition method, at 800 - 1200 °C, gaseous hydrocarbons are adsorbed on catalyst particles and decomposed to generate carbon nanotubes. This method has controllable conditions, and the obtained carbon nanotubes have a very high purity and are easy to be applied to industrial scale production of single-walled carbon nanotubes; ferrocene, as a precursor of an iron catalyst, has stable chemical properties and can dissolve in organic solvents such as ethanol, benzene, toluene, etc., and is widely used in the preparation of single-walled carbon nanotubes by floating chemical vapor deposition method. Ferrocene begins to decompose at 650 °C, and the generated iron particles will vaporize in the high-temperature zone. As the temperature decreases, the iron vapor will re-nucleate to form iron particles.

[0003] However, the prior art cannot make good use of the property of ferrocene to transform between gaseous, liquid and solid states with temperature change to catalyze the growth of single-walled nanotubes and prepare single-walled nanotubes, resulting in a low preparation efficiency of single-sided nanotubes during the preparation process. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a reaction device for catalyzing the generation of single-walled nanotubes.

[0005] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include:

[0006] An embodiment of the present invention provides a reaction device for catalyzing the generation of single-walled nanotubes, including:

[0007] A reaction vessel, the interior of the reaction vessel has a reaction space, and at least a catalyst input channel and a cooling medium channel are provided on the reaction vessel. The catalyst input channel is at least used to input a catalyst precursor into the reaction space, and the cooling medium channel is at least used to transport a cooling medium to the input port of the catalyst input channel.

[0008] Furthermore, the cooling medium channel includes a first water-cooled pipe with a first channel formed inside. The catalyst input channel and the first channel are respectively in communication with the reaction space. The catalyst input channel is used to input a catalyst precursor into the reaction space, and the first water-cooled pipe is at least used to input an inert gas into the reaction space through the first channel.

[0009] Furthermore, a plurality of air holes are formed in the side wall of the first water-cooled pipe, and both ends of the air holes are respectively in communication with the first channel and the reaction space.

[0010] Furthermore, a second water-cooled pipe is further provided on the reaction vessel, with a second channel formed inside. The second channel is in communication with the reaction space, and the second water-cooled pipe is at least used to input a gaseous carbon source into the reaction space through the second channel.

[0011] Furthermore, the first water-cooled pipe and the second water-cooled pipe are both provided with water-cooling channels which are respectively arranged outside the first channel and the second channel.

[0012] Furthermore, the first water-cooled pipe and the second water-cooled pipe are made of a metal material.

[0013] Furthermore, the gas flow direction at the outlet of the second water-cooled pipe is biased towards the center of the reaction space.

[0014] Furthermore, the axial length of the pipe wall of the second water-cooled pipe close to the side wall of the reaction vessel is greater than the axial length of the pipe wall of the second water-cooled pipe away from the inner wall of the reaction vessel.

[0015] Furthermore, define the end of the first channel in the reaction space as the first position, and define the end of the second channel in the reaction space as the second position. The first position and the second position are used to ensure that the catalyst precursor is input into the reaction space to form catalyst particles first and then contact the gaseous carbon source.

[0016] Furthermore, the second position is downstream of the first position, and the distance between the first position and the second position is 10 - 30 cm.

[0017] An embodiment of the present invention further provides a device for preparing single-walled carbon nanotubes. Having the reaction device for catalyzing the generation of single-walled nanotubes, it further includes:

[0018] A catalyst injection module which is at least used to supply a catalyst precursor and a carrier gas carrying the catalyst precursor to the catalyst input channel.

[0019] Further, the catalyst injection module includes: a catalyst precursor feeding device for providing a catalyst precursor;

[0020] a liquid feeding device for providing a catalyst and an etchant;

[0021] an evaporation device respectively connected to the catalyst precursor feeding device and the liquid feeding device, for evaporating the catalyst precursor, the promoter, and the etchant into gases, and the catalyst input channel is connected to the evaporation device;

[0022] a gas preheating device connected to the catalyst input channel, for mixing, preheating and inputting a reducing gas and an inert gas into the catalyst input channel in sequence.

[0023] Further, the reaction device further includes a collection device connected to the reaction vessel for collecting the carbon nanotubes generated in the reaction vessel.

[0024] Further, an ultrasonic spraying device is provided between the liquid feeding device and the evaporation device for atomizing the promoter and the etchant.

[0025] Further, a ball valve is provided between the collection device and the reaction vessel.

[0026] Further, a negative pressure is formed inside the collection device relative to the reaction space.

[0027] An embodiment of the present invention further provides a method for preparing single-walled carbon nanotubes, including:

[0028] providing the device for preparing single-walled carbon nanotubes, inputting a catalyst precursor into the reaction space, forming atomic vapor of the catalyst precursor, then introducing a cold inert gas into the reaction space to make the atomic vapor react with the inert gas to form catalyst particles, and then introducing a gaseous carbon source into the reaction space to make the catalyst particles meet the gaseous carbon source to form carbon nanotubes.

[0029] Further, while introducing the catalyst precursor, a gaseous promoter and an etchant are introduced.

[0030] Further, the catalyst precursor, the promoter, and the etchant are carried by an inert gas and input into the reaction space.

[0031] Further, in the reaction space, the position where the inert gas is introduced is above the position where the gaseous carbon source is introduced in the vertical direction, and is at least used to ensure that the catalyst precursor is input into the reaction space to form catalyst particles first and then contact the gaseous carbon source.

[0032] Compared with the prior art, the advantages of the present invention include:

[0033] 1. In the present invention, by introducing a part of inert gas to cool the gaseous catalyst, the catalyst is transformed from gaseous state to solid state or liquid state to form catalyst particles, and the sulfur-containing species generated by the decomposition of the cocatalyst can be adsorbed on the surface of the catalyst particles, which is convenient for the subsequent growth of single-walled carbon nanotubes;

[0034] 2. In the present invention, small pores are opened on the side wall of the first water-cooled tube, and all the inert gas enters the reaction space from the side wall pores, so as to cool the gaseous catalyst and make it nucleate and grow into liquid or solid catalyst particles;

[0035] 3. In the present invention, the second position is arranged downstream of the first position, that is, it can ensure that the catalyst reacts with the inert gas first and then contacts the gaseous carbon source, avoiding a large amount of ineffective thermal decomposition of the carbon source caused by premature introduction of the gaseous carbon source, thereby saving the catalytic cost and improving the catalytic efficiency. Description of the Drawings

[0036] Figure 1 is a schematic structural diagram of a device for preparing single-walled carbon nanotubes provided in a typical embodiment of the present invention;

[0037] Figure 2 is a schematic structural diagram of the first water-cooled tube of a device for preparing single-walled carbon nanotubes provided in a typical embodiment of the present invention;

[0038] Figure 3 is a schematic structural diagram of the second water-cooled tube of a device for preparing single-walled carbon nanotubes provided in a typical embodiment of the present invention;

[0039] Figure 4 is a scanning electron microscope image of a method for preparing single-walled carbon nanotubes provided in another typical embodiment of the present invention;

[0040] Figure 5 is a Raman spectrum diagram of a method for preparing single-walled carbon nanotubes provided in another typical embodiment of the present invention;

[0041] Figure 6 is a thermogravimetric curve of a method for preparing single-walled carbon nanotubes provided in another typical embodiment of the present invention;

[0042] Figure 7It is a transmission electron microscope image of a method for preparing single-walled carbon nanotubes provided in another typical embodiment of the present invention.

[0043] Explanation of reference numerals:

[0044] 1. Reaction vessel; 2. Reaction space; 3. Catalyst input channel; 4. First water-cooling tube; 5. First channel; 6. Air hole; 7. Second water-cooling tube; 8. Second channel; 9. Water-cooling channel; 10. Catalyst precursor feeding device; 11. Liquid feeding device; 12. Evaporation device; 13. Gas preheating device; 14. Collection device; 15. Ultrasonic spraying device; 16. Ball valve. Detailed implementation manners

[0045] In view of the deficiencies in the prior art, the inventors of this case have proposed the technical solution of the present invention through long-term research and a large number of practices. The following will further explain the technical solution, its implementation process, principles, etc.

[0046] Example 1

[0047] As Figure 1 shown, it is a device for preparing single-walled carbon nanotubes according to the first embodiment of the present invention, which includes a reaction device for catalyzing the generation of single-walled nanotubes. The reaction device for catalyzing the generation of single-walled nanotubes includes a reaction vessel 1. The reaction vessel 1 has a reaction space 2 inside. A catalyst input channel 3, a pair of first water-cooling tubes 4 and a pair of second water-cooling tubes 7 are provided on the reaction vessel 1. First channels 5 and second channels 8 are respectively opened inside the first water-cooling tube 4 and the second water-cooling tube 7. The catalyst input channel 3, the first channel 5 and the second channel 8 are respectively communicated with the reaction space 2. The catalyst input channel 3 is used to input the catalyst precursor into the reaction space 2. The first water-cooling tube 4 is used to input the inert gas into the reaction space 2 through the first channel 5. The temperature at the outlet of the first water-cooling tube 4 is 20 - 40 °C. Part of the inert gas is sent into the reaction vessel 1 by the first water-cooling tube 4 to cool the gaseous catalyst, make it nucleate and form catalyst particles, which is convenient for the subsequent growth of carbon nanotubes. The second water-cooling tube 7 is used to input the gaseous carbon source into the reaction space 2 through the second channel 8. However, if the catalyst contacts the gaseous carbon source before the formation of particles, it will cause some amorphous carbon to wrap the catalyst particles and deactivate the catalyst, thus reducing the utilization rate of the gaseous carbon source and the catalyst. Therefore, the gaseous carbon source is sent to the vicinity of the catalyst nucleation region by the second water-cooling tube 7. When the catalyst enters the reaction space 2, it first undergoes catalysis by the inert gas to form catalyst particles, and then reacts with the gaseous carbon source, avoiding premature introduction of the gaseous carbon source and causing a large amount of ineffective thermal decomposition of the carbon source to generate amorphous carbon, thereby ensuring the utilization rate of the gaseous carbon source and the catalyst.

[0048] Preferably, as Figure 2As shown, a plurality of air holes 6 are formed in the side wall of the first water-cooling pipe 4. Both ends of the air holes 6 are respectively communicated with the first channel 5 and the reaction space 2, so that all the inert gas enters the reaction vessel 1 from the side wall air holes 6, cools the gaseous catalyst, and nucleates and grows liquid or solid catalyst particles.

[0049] Specifically, both the first water-cooling pipe 4 and the second water-cooling pipe 7 are provided with water-cooling channels 9. The water-cooling channels 9 are respectively arranged outside the first channel 5 and the second channel 8. The flowing cooling water in the water-cooling channels 9 takes away the heat of the inert gas or the gaseous carbon source, so that the inert gas or the gaseous carbon source remains in a low-temperature state when entering the reaction vessel 1 from the injection pipe. It should be noted that the first water-cooling pipe 4 and the second water-cooling pipe 7 are made of metal.

[0050] That is to say, the first water-cooling pipe 4 and the second water-cooling pipe 7 are a kind of cooling device, which has a double-layer metal shell structure. The inner layer passes gas and the outer layer passes cooling water to achieve the effect of cooling the gas.

[0051] Preferably, as Figure 3 shown, the axial length of the side wall of the second water-cooling pipe 7 close to the side wall of the reaction vessel 1 is greater than the axial length of the side wall of the second water-cooling pipe 7 far from the inner wall of the reaction vessel 1, reducing the contact between the gaseous carbon source and the furnace wall when the gaseous carbon source is input into the reaction space 2.

[0052] Define the end of the first channel 5 in the reaction space 2 as the first position, and define the end of the second channel 8 in the reaction space 2 as the second position. Specifically, the second position is located downstream of the first position. The distance between the first position and the second position is 10-30 cm. The first position and the second position are used to ensure that after the catalyst precursor is input into the reaction space 2, catalyst particles are first formed and then contacted with the gaseous carbon source, avoiding a large amount of thermal decomposition of the gaseous carbon source when the gaseous carbon source and the catalyst precursor enter the reaction vessel 1 from the top together, and at the same time, it can improve the quality of the carbon tube and increase the utilization efficiency of the gaseous carbon source.

[0053] The device for preparing single-walled carbon nanotubes provided by the present invention further includes: a catalyst precursor feeding device 10, a liquid feeding device 11, an evaporation device 12, a gas preheating device 13, and a collection device 14. The function of the catalyst precursor feeding device 10 is to precisely control the feeding amount of the catalyst precursor. The catalyst precursor feeding device 10 includes, but is not limited to, a powder feeder, a loss-in-weight feeder, an injection pump, and a peristaltic pump. Any device that can accurately control the feeding of solids and liquids can be used as the catalyst precursor feeding device 10; the function of the liquid feeding device 11 is to precisely control the liquid promoter and etchant to enter the evaporation device 12. The liquid feeding device 11 includes, but is not limited to, a loss-in-weight feeder, an injection pump, and a peristaltic pump. Any device that can accurately control the feeding of liquids can be used as the liquid feeding device 11; the function of the evaporation device 12 is to evaporate the solid or liquid catalyst precursor, promoter, and etchant into gases so that the gaseous catalyst precursor, promoter, and etchant can enter the reaction vessel 1 under the carrier of an inert gas. At the same time, it can also preheat the catalyst precursor, promoter, etchant, and the inert gas used to carry other components; the gas preheating device 13 is connected to the catalyst input channel 3. The gas preheating device 13 is used to mix, preheat, and input the reducing gas and the inert gas into the catalyst input channel 3 in sequence; the number of the collection devices 14 is two. The collection devices 14 are connected to the reaction vessel 1. The collection devices 14 are used to collect the carbon nanotubes generated in the reaction vessel 1.

[0054] It should be noted that the catalyst precursor is one or more of inorganic compounds and organic compounds formed by iron, cobalt, and nickel that are easily decomposed or volatilized, such as ferrocene, cobaltocene, nickelocene, ferrous chloride, etc., and its feeding rate is 3 - 80 ml / h.

[0055] It should be noted that the reducing gas passing through the gas preheating device 13 is hydrogen, and its flow rate is 2 - 10 L / min.

[0056] It should be noted that the inert gas passing through the gas preheating device 13 is one or more of nitrogen, argon, and helium, and its flow rate is 1 - 8 L / min.

[0057] It should be noted that a part of the cold inert gas is introduced into the reaction space 2 through the first water-cooled tube 4 at the first position, and its gas volume is 0.2 - 2 L / min.

[0058] It should be noted that the promoter is one or more of thiophene, elemental sulfur, sulfur, thiourea, methanethiol, butanethiol, dimethyl disulfide, 2-chlorothiophene, polythiophene, and methylamine thiocyanate. Among them, the amount of the solid promoter is 0.3 - 20 ml / h, and the amount of the liquid promoter is 0.02 - 4 ml / min.

[0059] It should be noted that the etchant is one or more of water, carbon dioxide, and hydrogen. The amount of the liquid etchant is 0.01 - 4 ml / min, and the amount of the gaseous etchant is 10 - 200 ml / min. If a gaseous etchant is selected, a gas mass flowmeter or a rotameter can be used for precise feeding of the etchant.

[0060] It should be noted that the gaseous carbon source in the second water-cooled tube 7 can be one or more of methane, ethylene, carbon monoxide, propylene, propane, acetylene, natural gas, etc., and its flow rate is 20 - 500 ml / min.

[0061] It should be noted that the cold gaseous carbon source introduced into the reaction space 2 through the second water-cooled tube 7 at the second position has a gas volume of 20 - 500 ml / min.

[0062] Preferably, an ultrasonic spraying device 15 is provided between the liquid feeding device 11 and the evaporation device 12. The ultrasonic spraying device 15 is used to atomize the cocatalyst and the etchant.

[0063] Preferably, a ball valve 16 is provided between the collection device 14 and the reaction vessel 1. The ball valve 16 is used to control the connection between the collection device 14 and the reaction vessel 1.

[0064] Preferably, a negative pressure is formed inside the collection device 14 relative to the reaction space 2.

[0065] The collection device 14 includes a filter bag, and a hard porous material is installed on one side of the collection device 14 to support the filter bag. The porous material includes but is not limited to a sand core, sintered metal, porous plastic, and honeycomb ceramics. When the collection device 14 is working properly, the ball valve 16 connecting the reaction device and the collection device 14 is opened, and the vacuum system is turned on. The generated single-walled carbon nanotubes move from the reaction device to the collection device 14 under the action of the negative pressure in the collection device 14 and are enriched in the collection device 14. When the number of single-walled carbon nanotubes in the collection device 14 is too large, another collection device 14 is enabled, the current collection device 14 is closed, and the single-walled carbon nanotubes in the collection device 14 are cleaned. By alternately using the two collection devices 14, continuous collection of single-walled carbon nanotubes can be achieved.

[0066] The operation of the device for preparing single-walled carbon nanotubes provided by the present invention is described below: the catalyst precursor feeding device 10 accurately controls the feeding amount of the catalyst precursor and feeds the catalyst precursor into the evaporation device 12; the liquid feeding device 11 is used to accurately control the amount of the liquid co-catalyst and the etchant, and the catalyst and the etchant are fed into the ultrasonic spray device, and then fed into the evaporation device 12 after being atomized; the catalyst precursor, the co-catalyst and the etchant are vaporized into steam in the evaporation device 12, and enter the reaction vessel 1 through the catalyst input channel 3 under the carrier of a small amount of inert atmosphere; the mixed gas of the reducing gas and the inert gas is heated to a certain temperature by the gas preheater and fed into the reaction vessel 1 through the catalyst input channel 3, thereby reducing the heating load of the reaction vessel 1; the gaseous catalyst precursor is decomposed into catalyst particles at the appropriate position of the reaction vessel 1, and the catalyst particles with small particle size are decomposed into catalyst particles; The catalytic agent particles continue to vaporize into steam; a portion of cold inert gas is introduced into the first position of the reaction vessel 1 through the first water-cooling tube 4 to cool the gaseous catalyst, so that it is cooled to form nuclei to form catalyst particles, and adsorbs sulfur-containing substances produced by the decomposition of the catalyst to form catalyst particles that are beneficial to the growth of carbon tubes; at the second position of the reaction vessel 1, a cold gaseous carbon source is introduced by means of the second water-cooling tube 7 to avoid premature introduction of the gaseous carbon source before the formation of catalyst particles, so that the gaseous carbon source is thermally decomposed in large quantities to generate amorphous carbon, and part of the amorphous carbon will wrap the catalyst particles to deactivate the catalyst, thereby reducing the utilization rate of the carbon source and the catalyst; the generated carbon nanotubes move from top to bottom under the action of the negative pressure in the collecting device 14, and are enriched in the collecting device 14, and the collecting device 14 is used in conjunction with other devices to continuously carry out the preparation of single-walled carbon nanotubes.

[0067] The present invention also relates to a method for preparing single-walled carbon nanotubes, comprising:

[0068] S1, heating the reaction vessel 1 to a first temperature and keeping the temperature constant;

[0069] S2, preheating the reducing gas and the inert gas to a second temperature, and transporting them to the reaction vessel 1;

[0070] S3, heating the catalyst precursor, the co-catalyst and the etchant to a third temperature for atomization or vaporization, and inputting the atomized or vaporized catalyst precursor, the co-catalyst and the etchant into the reaction container 1 under the carrier of an inert gas;

[0071] S4, directly inputting a small amount of inert gas into the first position inside the reaction container 1;

[0072] S5, directly inputting the gaseous carbon source into the second position inside the reaction container 1;

[0073] S6, generating single-walled carbon nanotubes, and enriching them in the collecting device 14;

[0074] S7. When the amount of single-walled carbon nanotubes collected is sufficient, close the ball valve 16 of the collection device 14, enable another collection device 14, and clean the single-walled carbon nanotubes in the collection device 14.

[0075] It should be noted that in step S1, the first temperature is 850 - 1400 °C;

[0076] In step S2, the second temperature is 400 - 600 °C;

[0077] In step S3, the catalyst precursor is transported from the catalyst precursor feeding device 10 to the evaporation device 2, the cocatalyst and the etchant are transported from the liquid feeding device 11 to the ultrasonic spraying device, the cocatalyst and the etchant are atomized by the ultrasonic spraying device and then sent to the evaporation device 12. The temperature of the evaporation device 12 is 400 - 550 °C. The catalyst precursor is vaporized in the evaporation device 12, and the vaporized catalyst precursor, the atomized cocatalyst and etchant are all carried by a small amount of inert gas to the reaction vessel 1.

[0078] Example 2

[0079] The following is the preparation method of single-walled carbon nanotubes in the second embodiment of the present invention. Open the ball valve 16 of the left collection device 14 and start the vacuum system of the collection device 14. The central core temperature of the reaction vessel 1 is controlled at 1250 °C. The catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by a powder feeder. The feeding amount of ferrocene is 20 ml / h, the temperature of the evaporation device 12 is 500 °C, the injection rate of the cocatalyst thiophene is 4.8 ml / h, and the injection rate of the etchant water is 20 ml / h. Thiophene and water enter the evaporation device 12 after being atomized by the ultrasonic spraying device. The gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier of argon (1 L / min); the mixture of hydrogen (4 L / min) and argon (0.5 L / min) is preheated to 500 °C by a gas preheater and then enters the reaction vessel 1; part of the argon (0.5 L / min) is directly injected into the reaction vessel 1 at the position corresponding to 900 °C through the first water-cooled tube 4 for cold inert gas, and methane (100 ml / min) is injected into the reaction vessel 1 through the second water-cooled tube 7 for cold gaseous carbon source. The vertical height between the second water-cooled tube 7 and the first water-cooled tube 4 is 20 cm, and continuous growth and collection of single-walled carbon nanotubes are carried out.

[0080] Example 3

[0081] The following is the preparation method of single-walled carbon nanotubes according to the 3rd embodiment of the present invention. Open the ball valve 16 of the left collecting device 14 and start the vacuum system of the collecting device 14. The central core temperature of the reaction vessel 1 is controlled at 1150 °C. The catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by a powder feeder. The feeding rate of ferrocene is 20 ml / h, the temperature of the evaporation device 12 is 500 °C, the injection rate of the co-catalyst thiophene is 4.8 ml / h, and the injection rate of the etching agent water is 20 ml / h. Thiophene and water enter the evaporation device 12 after being atomized by an ultrasonic spraying device. The gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier gas of argon (1 L / min); the mixed gas of hydrogen (4 L / min) and argon (0.5 L / min) enters the reaction vessel 1 after being preheated to 500 °C by a gas preheater; part of the argon (0.5 L / min) is directly injected into the reaction vessel 1 at the position corresponding to 900 °C through the first water-cooled tube 4 of cold inert gas, and methane (100 ml / min) is injected into the reaction vessel 1 through the second water-cooled tube 7 of cold gaseous carbon source. The vertical height between the second water-cooled tube 7 and the first water-cooled tube 4 is 10 cm, and continuous growth and collection of single-walled carbon nanotubes are carried out.

[0082] Example 4

[0083] The following is the preparation method of single-walled carbon nanotubes according to the 4th embodiment of the present invention. Open the ball valve 16 of the left collecting device 14 and start the vacuum system of the collecting device 14. The central core temperature of the reaction vessel 1 is controlled at 1250 °C. The catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by a powder feeder. The feeding rate of ferrocene is 20 ml / h, the temperature of the evaporation device 12 is 500 °C, the injection rate of the co-catalyst thiophene is 4.8 ml / h, and the injection rate of the etching agent water is 20 ml / h. Thiophene and water enter the evaporation device 12 after being atomized by an ultrasonic spraying device. The gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier gas of argon (1 L / min); the mixed gas of hydrogen (4 L / min) and argon (0.5 L / min) enters the reaction vessel 1 after being preheated to 500 °C by a gas preheater; part of the argon (1 L / min) is directly injected into the reaction vessel 1 at the position corresponding to 1000 °C through the first water-cooled tube 4 of cold inert gas, and methane (100 ml / min) is injected into the reaction vessel 1 through the second water-cooled tube 7 of cold gaseous carbon source. The vertical height between the second water-cooled tube 7 and the first water-cooled tube 4 is 20 cm, and continuous growth and collection of single-walled carbon nanotubes are carried out.

[0084] Example 5

[0085] The following is the preparation method of single-walled carbon nanotubes according to the 5th embodiment of the present invention. Open the ball valve 16 of the left collecting device 14 and start the vacuum system of the collecting device 14. The central core temperature of the reaction vessel 1 is controlled at 1250 °C. The catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by the powder feeder. The feeding amount of ferrocene is 20 ml / h, the temperature of the evaporation device 12 is 500 °C, the feeding amount of the cocatalyst elemental sulfur is 8 ml / h, and the injection rate of the etching agent water is 20 ml / h. The water enters the evaporation device 12 after being atomized by the ultrasonic spraying device. The gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier of argon (1 L / min); the mixture of hydrogen (4 L / min) and argon (0.5 L / min) enters the reaction vessel 1 after being preheated to 500 °C by the gas preheater; part of the argon (1 L / min) is directly injected into the reaction vessel 1 at the position corresponding to 900 °C through the first water-cooled tube 4 of the cold inert gas, and methane (100 ml / min) is injected into the reaction vessel 1 through the second water-cooled tube 7 of the cold gaseous carbon source. The vertical height between the second water-cooled tube 7 and the first water-cooled tube 4 is 20 cm, and the continuous growth and collection of single-walled carbon nanotubes are carried out.

[0086] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A reaction device for catalyzing the generation of single-walled nanotubes, characterized in that: include: A reaction container (1), wherein the reaction container (1) has a reaction space (2) inside, and the reaction container (1) is provided with at least a catalyst input channel (3) and a cooling medium channel, wherein the catalyst input channel (3) is at least used for inputting a catalyst precursor into the reaction space (2), and the cooling medium channel is at least used for conveying a cooling medium to an input port of the catalyst input channel (3); The cooling medium channel comprises a first water-cooling tube (4), a first channel (5) is provided inside the first water-cooling tube (4), the catalyst input channel (3) and the first channel (5) are respectively connected to the reaction space (2), the catalyst input channel (3) is used to input a catalyst precursor into the reaction space (2), the first water-cooling tube (4) is at least used to input an inert gas into the reaction space (2) through the first channel (5), and the reaction container (1) is further provided with a second water-cooling tube (7) The second water-cooling tube (7) has a second channel (8) formed inside, the second channel (8) and the reaction space (2) are interconnected, the second water-cooling tube (7) is at least used to input a gaseous carbon source into the reaction space (2) through the second channel (8), the gas flow direction at the outlet of the second water-cooling tube (7) is biased toward the center of the reaction space (2), and the axial length of the wall of the second water-cooling tube (7) close to the side wall of the reaction container (1) is greater than the axial length of the wall of the second water-cooling tube (7) away from the inner wall of the reaction container (1).

2. The reaction device for catalyzing the production of single-walled nanotubes according to claim 1, characterized in that: A plurality of air holes (6) are provided on the side wall of the first water-cooling tube (4), and two ends of the air holes (6) are respectively connected to the first channel (5) and the reaction space (2).

3. The reaction device for catalyzing the production of single-walled nanotubes according to claim 1, characterized in that: The first water-cooling tube (4) and the second water-cooling tube (7) are both provided with water-cooling channels (9), and the water-cooling channels (9) are respectively arranged on the outside of the first channel (5) and the second channel (8).

4. The reaction device for catalyzing the production of single-walled nanotubes according to claim 3, characterized in that: The first water cooling tube (4) and the second water cooling tube (7) are made of metal.

5. The reaction device for catalyzing the production of single-walled nanotubes according to claim 1, characterized in that: The end of the first channel (5) in the reaction space (2) is defined as a first position, and the end of the second channel (8) in the reaction space (2) is defined as a second position. The first position and the second position are used to ensure that the catalyst precursor is input into the reaction space (2) to first form catalyst particles and then contact with the gaseous carbon source.

6. The reaction device for catalyzing the production of single-walled nanotubes according to claim 5, characterized in that: The second position is located downstream of the first position, and the first position and the second position are spaced 10-30 cm apart.

7. A device for preparing single-walled carbon nanotubes, comprising the reaction device for catalyzing the production of single-walled carbon nanotubes according to any one of claims 1 to 6, characterized in that: Also includes: A catalyst injection module, the catalyst injection module is at least used to supply a catalyst precursor and a carrier gas carrying the catalyst precursor to the catalyst input channel (3).

8. The device for preparing single-walled carbon nanotubes according to claim 7, characterized in that: The catalyst injection module comprises: a catalyst precursor feeding device (10), wherein the catalyst precursor feeding device (10) is used to provide a catalyst precursor; A liquid feeding device (11), wherein the liquid feeding device (11) is used to provide a catalyst and an etchant; an evaporation device (12), the evaporation device (12) being connected to the catalyst precursor feeding device (10) and the liquid feeding device (11) respectively, the evaporation device (12) being used to evaporate the catalyst precursor, the co-catalyst and the etchant into gas, the catalyst input channel (3) being connected to the evaporation device (12); A gas preheating device (13), the gas preheating device (13) is connected to the catalyst input channel (3), and the gas preheating device (13) is used to mix and preheat the reducing gas and the inert gas in sequence and input them into the catalyst input channel (3).

9. The device for preparing single-walled carbon nanotubes according to claim 8, characterized in that: The reaction device further comprises a collecting device (14), the collecting device (14) being connected to the reaction container (1), and the collecting device (14) being used to collect the carbon nanotubes generated in the reaction container (1).

10. The device for preparing single-walled carbon nanotubes according to claim 8, characterized in that: An ultrasonic spray device (15) is provided between the liquid feeding device (11) and the evaporation device (12), and the ultrasonic spray device (15) is used to atomize the co-catalyst and the etching agent.

11. The device for preparing single-walled carbon nanotubes according to claim 9, characterized in that: A ball valve (16) is provided between the collecting device (14) and the reaction container (1).

12. The device for preparing single-walled carbon nanotubes according to claim 9, characterized in that: A negative pressure is formed inside the collecting device (14) relative to the reaction space (2).

13. A method for preparing single-walled carbon nanotubes, characterized in that: include: Provided is a device for preparing single-walled carbon nanotubes according to any one of claims 7 to 12, A catalyst precursor is introduced into a reaction space (2) to form atomic vapor. A cold inert gas is then introduced into the reaction space (2) to allow the atomic vapor and the inert gas to react to form catalyst particles. A gaseous carbon source is then introduced into the reaction space (2) to allow the catalyst particles and the gaseous carbon source to meet and form carbon nanotubes.

14. The method for preparing single-walled carbon nanotubes according to claim 13, characterized in that: When the catalyst precursor is introduced, the gaseous promoter and the etchant are introduced.

15. The method for preparing single-walled carbon nanotubes according to claim 14, characterized in that: The catalyst precursor, the co-catalyst and the etchant are carried by an inert gas and introduced into the reaction space (2).

16. The method for preparing single-walled carbon nanotubes according to claim 15, characterized in that: In the reaction space (2), the position for introducing the inert gas is located above the position for introducing the gaseous carbon source in the vertical direction, and is at least used to ensure that the catalyst precursor introduced into the reaction space (2) first forms catalyst particles and then contacts the gaseous carbon source.

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