Reaction device for catalyzing generation of single-walled nanotubes and application of reaction device

Abstract

The invention discloses a reaction device for catalyzing generation of a single-walled nanotube. The reaction device for catalyzing generation of the single-walled nanotubes comprises a reaction container, a reaction space is formed in the reaction container, the reaction container is at least provided with a catalyst input channel and a first water-cooled tube, a first channel is formed in the first water-cooled tube, and the catalyst input channel and the first channel are communicated with the reaction space. The catalyst input channel is used for inputting a catalyst precursor into the reaction space, and the first water cooling pipe is at least used for inputting inert gas into the reaction space through the first channel. The reaction device for catalyzing the generation of the single-wall nanotubes can achieve the effects of facilitating the growth of the single-wall nanotubes, saving the catalysis cost and improving the catalysis efficiency.

Description

Technical Field

[0001] The 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 and electrical properties. They have a wide range of applications in nanoelectronics, electrochemical energy storage materials, catalysis, hydrogen storage and other fields. The main methods for preparing single-walled carbon nanotubes are laser ablation, arc discharge, chemical vapor deposition and the like. The carbon nanotubes prepared by laser ablation are of good quality, but the yield is low and the required equipment is expensive. The arc discharge method has a high reaction temperature, and the prepared carbon nanotubes contain a large number of graphitized carbon and carbon-wrapped iron particles, which are difficult to remove. In the chemical vapor deposition method, gaseous hydrocarbons are adsorbed on catalyst particles at 800-1200°C and decompose to form carbon nanotubes. The conditions of this method are controllable, and the obtained carbon nanotubes are of high purity, which can be easily used for industrial scale-up production of single-walled carbon nanotubes; ferrocene, as a precursor of iron catalyst, is chemically stable and soluble in organic solvents such as ethanol, benzene and toluene. It is widely used in the preparation of single-walled carbon nanotubes using floating chemical vapor deposition. Ferrocene begins to decompose at 650°C, and the generated iron particles will vaporize in the high temperature zone. As the temperature drops, the iron vapor will re-nucleate to form iron particles.

[0003] However, the existing technology is unable to make good use of the property of ferrocene to transform between gas, liquid and solid states with temperature changes to catalyze the growth of single-walled nanotubes and prepare single-walled nanotubes, resulting in low preparation efficiency of single-walled nanotubes during the preparation process. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a reaction device for catalyzing the generation of single-walled nanotubes.

[0005] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes: An embodiment of the present invention provides a reaction device for catalyzing the generation of single-walled nanotubes, comprising: A reaction container, wherein the reaction container has a reaction space inside, and the reaction container is provided with at least a catalyst input channel and a cooling medium channel, wherein the catalyst input channel is at least used for inputting a catalyst precursor into the reaction space, and the cooling medium channel is at least used for conveying a cooling medium to an input port of the catalyst input channel.

[0006] Furthermore, the cooling medium channel includes a first water-cooling tube, a first channel is opened inside the first water-cooling tube, the catalyst input channel and the first channel are respectively connected to the reaction space, the catalyst input channel is used to input the catalyst precursor into the reaction space, and the first water-cooling tube is at least used to input the inert gas into the reaction space through the first channel.

[0007] Furthermore, a plurality of air holes are formed on the side wall of the first water-cooling tube, and two ends of the air holes are respectively connected with the first channel and the reaction space.

[0008] Furthermore, the reaction container is provided with a second water-cooling tube, a second channel is opened inside the second water-cooling tube, the second channel is connected to the reaction space, and the second water-cooling tube is at least used to input the gaseous carbon source into the reaction space through the second channel.

[0009] Furthermore, the first water-cooling tube and the second water-cooling tube are both provided with water-cooling channels, and the water-cooling channels are respectively arranged on the outsides of the first channel and the second channel.

[0010] Furthermore, the first water-cooling tube and the second water-cooling tube are made of metal.

[0011] Furthermore, the gas flow direction at the outlet of the second water-cooling pipe is biased towards the center of the reaction space.

[0012] Furthermore, an axial length of the second water-cooling tube wall close to the side wall of the reaction container is greater than an axial length of the second water-cooling tube wall away from the inner wall of the reaction container.

[0013] Furthermore, the end of the first channel in the reaction space is defined as a first position, and the end of the second channel in the reaction space 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 to first form catalyst particles and then contact with the gaseous carbon source.

[0014] Furthermore, the second position is located downstream of the first position, and the first position and the second position are spaced 10-30 cm apart.

[0015] The embodiment of the present invention further provides a device for preparing single-walled carbon nanotubes, comprising the reaction device for catalyzing the generation of single-walled carbon nanotubes, and further comprising: A catalyst injection module is used at least to supply a catalyst precursor and a carrier gas carrying the catalyst precursor to the catalyst input channel.

[0016] Further, the catalyst injection module comprises: a catalyst precursor feeding device, the catalyst precursor feeding device is used to provide a catalyst precursor; A liquid feeding device, wherein the liquid feeding device is used to provide a catalyst and an etchant; An evaporation device, the evaporation device is connected to the catalyst precursor feeding device and the liquid feeding device respectively, the evaporation device is used to evaporate the catalyst precursor, the co-catalyst, and the etchant into gas, and the catalyst input channel is connected to the evaporation device; A gas preheating device is connected to the catalyst input channel, and is used to mix and preheat the reducing gas and the inert gas in sequence and input them into the catalyst input channel.

[0017] Furthermore, the reaction device also includes a collecting device, which is connected to the reaction container and is used to collect the carbon nanotubes generated in the reaction container.

[0018] Furthermore, an ultrasonic spray device is provided between the liquid feeding device and the evaporation device, and the ultrasonic spray device is used to atomize the catalyst promoter and the etchant.

[0019] Furthermore, a ball valve is provided between the collecting device and the reaction container.

[0020] Furthermore, a negative pressure is formed inside the collecting device relative to the reaction space.

[0021] The embodiment of the present invention further provides a method for preparing single-walled carbon nanotubes, which has the device for preparing single-walled carbon nanotubes, including: The catalyst precursor is input into the reaction space to form atomic vapor. Then, cold inert gas is introduced into the reaction space so that the atomic gas and the inert gas react to form catalyst particles. Then, a gaseous carbon source is introduced into the reaction space so that the catalyst particles and the gaseous carbon source meet to form carbon nanotubes.

[0022] Furthermore, when the precursor catalyst is introduced, the gaseous promoter and the etchant are introduced.

[0023] Furthermore, the catalyst precursor, the co-catalyst and the etchant are carried by an inert gas and input into the reaction space.

[0024] Furthermore, in the reaction space, 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 input into the reaction space first forms catalyst particles and then contacts the gaseous carbon source.

[0025] Compared with the prior art, the advantages of the present invention include: 1. The present invention introduces part of the inert gas to cool the gaseous catalyst, so that the catalyst is transformed from the gaseous state to the solid or liquid state to form catalyst particles. The sulfur-containing species generated by the decomposition of the catalyst can be adsorbed on the surface of the catalyst particles, which is convenient for the subsequent growth of single-walled nanotubes. 2. In the present invention, small pores are opened on the side wall of the first water cooling tube, and the inert gas enters the reaction space from the pores on the side wall, thereby cooling the gaseous catalyst and causing it to nucleate and grow liquid or solid catalyst particles; 3. The present invention sets the second position downstream of the first position, which can ensure that the catalyst reacts with the inert gas first and then contacts the gaseous carbon source, avoiding the premature introduction of the gaseous carbon source causing a large amount of ineffective thermal decomposition of the carbon source, thereby saving catalytic costs and improving catalytic efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic structural diagram of a device for preparing single-walled carbon nanotubes provided in a typical implementation case of the present invention; Figure 2 It is a schematic structural diagram of a first water-cooling tube of a device for preparing single-walled carbon nanotubes provided in a typical implementation case of the present invention; Figure 3 It is a schematic structural diagram of a second water-cooling tube of a device for preparing single-walled carbon nanotubes provided in a typical implementation case of the present invention; Figure 4 is a scanning electron microscope image of a method for preparing single-walled carbon nanotubes provided in another typical implementation case of the present invention; Figure 5 is a Raman spectrum diagram of a method for preparing single-walled carbon nanotubes provided in another typical implementation case of the present invention; Figure 6 is a thermogravimetric curve of a method for preparing single-walled carbon nanotubes provided in another typical implementation case of the present invention; Figure 7 This is a transmission electron microscope image of a method for preparing single-walled carbon nanotubes provided in another typical implementation case of the present invention.

[0027] Description of reference numerals: 1. Reaction container; 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 spray device; 16. Ball valve. DETAILED DESCRIPTION

[0028] In view of the deficiencies in the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows.

[0029] Example 1 like Figure 1 As shown, the device for preparing single-walled carbon nanotubes according to the first embodiment of the present invention comprises a reaction device for catalyzing the generation of single-walled nanotubes, wherein the reaction device for catalyzing the generation of single-walled nanotubes comprises a reaction container 1, wherein the reaction container 1 has a reaction space 2 inside, and the reaction container 1 is provided with a catalyst input channel 3, a pair of first water-cooling tubes 4 and a pair of second water-cooling tubes 7, wherein the first water-cooling tube 4 and the second water-cooling tube 7 are respectively provided with a first channel 5 and a second channel 8, wherein the catalyst input channel 3, the first channel 5 and the second channel 8 are respectively connected with the reaction space 2, the catalyst input channel 3 is used for inputting a catalyst precursor into the reaction space 2, the first water-cooling tube 4 is used for inputting an 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, and the catalyst precursor is input into the reaction space 2 through the first water-cooling tube 4 ... A first water-cooling tube 4 is used to deliver part of the inert gas to the reaction vessel 1 in order to cool the gaseous catalyst, nucleate it 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 particles are formed, part of the amorphous carbon will wrap the catalyst particles and deactivate the catalyst, thereby reducing the utilization rate of the gaseous carbon source and the catalyst. Therefore, the second water-cooling tube 7 is used to deliver the gaseous carbon source to the vicinity of the catalyst nucleation area. When the catalyst enters the reaction space 2, it is first catalyzed by the inert gas to form catalyst particles, and then reacts with the gaseous carbon source to avoid the premature introduction of the gaseous carbon source, which causes 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.

[0030] Preferably, Figure 2 As shown, a plurality of air holes 6 are provided on the side wall of the first water-cooling tube 4, and both ends of the air holes 6 are respectively connected with the first channel 5 and the reaction space 2, so that all the inert gas enters the reaction container 1 from the side wall air holes 6, cools the gaseous catalyst, and causes it to nucleate and grow liquid or solid catalyst particles.

[0031] In detail, the first water-cooling tube 4 and the second water-cooling tube 7 are both provided with a water-cooling channel 9, which is arranged on the outside of the first channel 5 and the second channel 8 respectively. The heat of the inert gas or the gaseous carbon source is taken away by the flowing cooling water in the water-cooling channel 9, so that the inert gas or the gaseous carbon source is kept at a low temperature when entering the reaction vessel 1 from the injection tube. It should be noted that the first water-cooling tube 4 and the second water-cooling tube 7 are made of metal.

[0032] That is to say, the first water-cooling tube 4 and the second water-cooling tube 7 are a cooling device having a double-layer metal shell structure, wherein the inner layer passes gas and the outer layer passes cooling water to achieve the function of cooling the gas.

[0033] Preferably, Figure 3 As shown, the axial length of the wall of the second water-cooling tube 7 close to the side wall of the reaction vessel 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 vessel 1, reducing the contact between the gaseous carbon source and the furnace wall when it is input into the reaction space 2.

[0034] The end of the first channel 5 in the reaction space 2 is defined as the first position, and the end of the second channel 8 in the reaction space 2 is defined as the second position. Specifically, the second position is located downstream of the first position, and the first position and the second position are 10-30 cm apart. The first position and the second position are used to ensure that the catalyst precursor is first formed into catalyst particles after being input into the reaction space 2, and then contacts with the gaseous carbon source, so as to avoid the gaseous carbon source and the catalyst precursor from entering the reaction container 1 from the top together, resulting in a large amount of thermal decomposition of the gaseous carbon source when the catalyst particles are not formed, thereby improving the quality of the carbon tubes and increasing the utilization efficiency of the gaseous carbon source.

[0035] The present invention provides a device for preparing single-walled carbon nanotubes, which also includes: a catalyst precursor feeding device 10, a liquid feeding device 11, an evaporation device 12, a gas preheating device 13 and a collecting device 14. The catalyst precursor feeding device 10 is used to accurately control the feeding amount of the catalyst precursor. The catalyst precursor feeding device 10 includes but is not limited to a powder feeder, a weightless feeder, a syringe pump, and a peristaltic pump. Any device that can accurately control the feeding of solid and liquid can be used as the catalyst precursor feeding device 10; the liquid feeding device 11 is used to accurately control the liquid co-catalyst and etchant to enter the evaporation device 12. The liquid feeding device 11 includes but is not limited to a weightless feeder, a syringe pump, and a peristaltic pump. Any device that can accurately control the feeding of liquid can be used as the catalyst precursor feeding device 10. Any equipment for feeding materials can be used as a liquid feeding device 11; the function of the evaporation device 12 is to evaporate solid or liquid catalyst precursors, co-catalysts and etchants into gases, so that the gaseous catalyst precursors, co-catalysts and etchants can enter the reaction vessel 1 under the carrier of inert gas, and can also preheat the catalyst precursors, co-catalysts, etchants and inert gases used to carry other components; the gas preheating device 13 is connected to the catalyst input channel 3, and 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 collecting devices 14 is two, the collecting device 14 is connected to the reaction vessel 1, and the collecting device 14 is used to collect the carbon nanotubes generated in the reaction vessel 1.

[0036] It should be noted that the catalyst precursor is one or more of easily decomposable or volatile inorganic and organic compounds formed by iron, cobalt, and nickel, such as ferrocene, cobaltocene, nickelocene, ferrous chloride, etc., and its feed rate is 3~80ml / h.

[0037] 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.

[0038] 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.

[0039] It should be noted that the amount of partially cold inert gas introduced into the reaction space 2 at the first position by means of the first water-cooling pipe 4 is 0.2-2 L / min.

[0040] It should be noted that the co-catalyst is one or more of thiophene, elemental sulfur, sulfur, thiourea, methyl mercaptan, butyl mercaptan, dimethyl disulfide, 2-chlorothiophene, polythiophene, and methylamine thiocyanate. The amount of the solid co-catalyst is 0.3-20 ml / h, and the amount of the liquid co-catalyst is 0.02-4 ml / min.

[0041] It should be noted that the etchant is one or more of water, carbon dioxide, and hydrogen, wherein the amount of liquid etchant is 0.01-4 ml / min, and the amount of gaseous etchant is 10-200 ml / min. If a gaseous etchant is selected, a gas mass flow meter or a rotor flow meter can be used for precise feeding of the etchant.

[0042] It should be noted that the gaseous carbon source of the second water-cooling 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.

[0043] It should be noted that the cold gaseous carbon source is introduced into the reaction space 2 at the second position by means of the second water cooling pipe 7, and the gas volume thereof is 20-500 ml / min.

[0044] Preferably, 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 etchant.

[0045] Preferably, a ball valve 16 is provided between the collecting device 14 and the reaction container 1 , and the ball valve 16 is used to control the communication between the collecting device 14 and the reaction container 1 .

[0046] Preferably, a negative pressure is formed inside the collecting device 14 relative to the reaction space 2 .

[0047] The collecting device 14 includes a filter bag, and a hard porous material is installed on one side of the collecting device 14 to support the filter bag. The porous material includes but is not limited to sand core, sintered metal, porous plastic, and honeycomb ceramic. When the collecting device 14 is working normally, the ball valve 16 connecting the reaction device and the collecting device 14 is opened, and the vacuum system is turned on. The generated single-walled carbon nanotubes move from the reaction device to the collecting device 14 under the action of the negative pressure of the collecting device 14 and are enriched in the collecting device 14. When the number of single-walled carbon nanotubes in the collecting device 14 is too large, another collecting device 14 is enabled, the current collecting device 14 is closed, and the single-walled carbon nanotubes in the collecting device 14 are cleaned. When the two collecting devices 14 are used in turn, the continuous collection of single-walled carbon nanotubes can be achieved.

[0048] 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.

[0049] The present invention also relates to a method for preparing single-walled carbon nanotubes, comprising: S1, heating the reaction vessel 1 to a first temperature and keeping the temperature constant; S2, preheating the reducing gas and the inert gas to a second temperature, and transporting them to the reaction vessel 1; 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; S4, directly inputting a small amount of inert gas into the first position inside the reaction vessel 1; S5, directly inputting the gaseous carbon source into the second position inside the reaction container 1; S6, generating single-walled carbon nanotubes, and enriching them in the collecting device 14; S7 . When the amount of collected single-walled carbon nanotubes is sufficient, close the ball valve 16 of the collecting device 14 , activate another collecting device 14 , and clean the single-walled carbon nanotubes in the collecting device 14 .

[0050] It should be noted that in step S1, the first temperature is 850-1400°C; In step S2, the second temperature is 400-600°C; In step S3, the catalyst precursor is transported to the evaporation device 2 by the catalyst precursor feeding device 10, the co-catalyst and the etchant are transported to the ultrasonic spray device by the liquid feeding device 11, the co-catalyst and the etchant are atomized by the ultrasonic spray 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 co-catalyst and the etchant are all carried to the reaction container 1 by a small amount of inert gas.

[0051] Example 2 The following is a method for preparing single-walled carbon nanotubes according to the second embodiment of the present invention. The ball valve 16 of the left collecting device 14 is opened, and the vacuum system of the collecting device 14 is started. The central core temperature of the reaction vessel 1 is controlled at 1250°C, and the catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by a powder feeder, wherein the ferrocene powder feeding amount is 20ml / h, the temperature of the evaporation device 12 is 500°C, the injection rate of the co-catalyst thiophene is 4.8ml / h, and the injection rate of the etchant water is 20ml / h, wherein thiophene and water are atomized by an ultrasonic spray device and enter the evaporation device 12, and the gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier of argon (1L / min); the mixed gas of hydrogen (4L / min) and argon (0.5L / min) is preheated to 500°C by a gas preheater. Then it enters the reaction container 1; part of the argon gas (0.5L / min) is directly injected into the position corresponding to 900°C in the reaction container 1 through the first water-cooling tube 4 of the cold inert gas, and methane (100ml / min) is injected into the reaction container 1 through the second water-cooling tube 7 of the cold gaseous carbon source, wherein the vertical height between the second water-cooling tube 7 and the first water-cooling tube 4 is 20cm, for continuous growth and collection of single-walled carbon nanotubes.

[0052] Example 3 The following is a method for preparing single-walled carbon nanotubes according to the third embodiment of the present invention. The ball valve 16 of the left collecting device 14 is opened, and the vacuum system of the collecting device 14 is started. The central core temperature of the reaction vessel 1 is controlled at 1150°C, and the catalyst precursor (i.e., ferrocene) is fed into the evaporation device 12 by a powder feeder, wherein the ferrocene powder feeding amount is 20ml / h, the temperature of the evaporation device 12 is 500°C, the injection rate of the co-catalyst thiophene is 4.8ml / h, and the injection rate of the etchant water is 20ml / h, wherein thiophene and water are atomized by an ultrasonic spray device and then enter the evaporation device 12, and the gaseous ferrocene, thiophene, and water in the evaporation device 12 enter the reaction vessel 1 under the carrier of argon (1L / min); the mixed gas of hydrogen (4L / min) and argon (0.5L / min) is preheated to 500°C by a gas preheater. Then it enters the reaction container 1; part of the argon gas (0.5L / min) is directly injected into the position corresponding to 900°C in the reaction container 1 through the first water-cooling tube 4 of the cold inert gas, and methane (100ml / min) is injected into the reaction container 1 through the second water-cooling tube 7 of the cold gaseous carbon source, wherein the vertical height between the second water-cooling tube 7 and the first water-cooling tube 4 is 10cm, for continuous growth and collection of single-walled carbon nanotubes.

[0053] Example 4 The following is a method for preparing single-walled carbon nanotubes according to the fourth embodiment of the present invention. The ball valve 16 of the left collecting device 14 is opened to 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, wherein the ferrocene powder feeding amount 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 etchant water is 20 ml / h. Thiophene and water are atomized by an ultrasonic spray device and then enter the evaporation device 12. 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 mixed gas of hydrogen (4 L / min) and argon (0.5 L / min) is preheated to 500°C by a gas preheater. Then it enters the reaction container 1; part of the argon gas (1L / min) is directly injected into the position corresponding to 1000°C in the reaction container 1 through the first water-cooling tube 4 of the cold inert gas, and methane (100ml / min) is injected into the reaction container 1 through the second water-cooling tube 7 of the cold gaseous carbon source, wherein the vertical height between the second water-cooling tube 7 and the first water-cooling tube 4 is 20cm, for continuous growth and collection of single-walled carbon nanotubes.

[0054] Example 5 The following is a method for preparing single-walled carbon nanotubes according to the fifth embodiment of the present invention. The ball valve 16 of the left collecting device 14 is opened to 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, wherein the ferrocene powder feeding amount is 20 ml / h, the temperature of the evaporation device 12 is 500°C, the feed amount of the co-catalyst elemental sulfur is 8 ml / h, and the injection rate of the etchant water is 20 ml / h. The water is atomized by an ultrasonic spray device and then enters the evaporation device 12. 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 mixed gas of hydrogen (4 L / min) and argon (0.5 L / min) is preheated to 500°C by a gas preheater. Then it enters the reaction container 1; part of the argon gas (1L / min) is directly injected into the position corresponding to 900°C in the reaction container 1 through the first water-cooling tube 4 of the cold inert gas, and methane (100ml / min) is injected into the reaction container 1 through the second water-cooling tube 7 of the cold gaseous carbon source, wherein the vertical height between the second water-cooling tube 7 and the first water-cooling tube 4 is 20cm, for continuous growth and collection of single-walled carbon nanotubes.

[0055] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in 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).

2. The reaction device for catalyzing the production of single-walled nanotubes according to claim 1, characterized in that: 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), and 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 / or, 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 generation of single-walled nanotubes according to claim 2, characterized in that: The reaction container (1) is also provided with a second water-cooling tube (7), a second channel (8) is provided inside the second water-cooling tube (7), the second channel (8) and the reaction space (2) are interconnected, and 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).

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 both provided with water-cooling channels (9), and the water-cooling channels (9) are arranged on the outside of the first channel (5) and the second channel (8), respectively; And / or, 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 3, characterized in that: The gas flow direction at the outlet of the second water-cooling pipe (7) is biased towards the center of the reaction space (2).

6. The reaction device for catalyzing the production of single-walled nanotubes according to claim 3, characterized in that: 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); and / or, defining the end of the first channel (5) in the reaction space (2) as a first position, defining the end of the second channel (8) in the reaction space (2) as a second position, the first position and the second position being used to ensure that the catalyst precursor is input into the reaction space (2) to form catalyst particles first and then contact with the gaseous carbon source; And / or, 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) being connected to the catalyst input channel (3), the gas preheating device (13) being used to sequentially mix and preheat the reducing gas and the inert gas and input them into the catalyst input channel (3); And / or, the reaction device further comprises a collecting device (14), the collecting device (14) is connected to the reaction container (1), and the collecting device (14) is used to collect the carbon nanotubes generated in the reaction container (1); And / or, 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 etchant; and / or, a ball valve (16) is provided between the collecting device (14) and the reaction container (1); And / or, a negative pressure is formed inside the collecting device (14) relative to the reaction space (2).

9. A method for preparing single-walled carbon nanotubes, comprising the device for preparing single-walled carbon nanotubes as claimed in claim 8, characterized in that: include: A catalyst precursor is introduced into the reaction space (2) to form atomic gas. A cold inert gas is then introduced into the reaction space (2) to allow the atomic gas 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.

10. The method for preparing single-walled carbon nanotubes according to claim 9, characterized in that: When the precursor catalyst is introduced, the gaseous promoter and the etchant are introduced; and / or, using an inert gas to carry the catalyst precursor, the co-catalyst and the etchant and inputting them into the reaction space (2); And / or, 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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