CN117899781A - Plasma single-walled carbon nanotube continuous production system and method - Google Patents
Plasma single-walled carbon nanotube continuous production system and method Download PDFInfo
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Abstract
The invention discloses a continuous production system and a continuous production method of plasma single-wall carbon nanotubes, wherein the system comprises a feeder, a preprocessor, a plasma cracking furnace and a water cooling tank; the plasma cracking furnace is provided with a plasma anode and a plasma cathode; the plasma cracking furnace is provided with a plasma power supply by a plasma power supply and generates arc plasma between a plasma cathode and a plasma anode; the plasma cathode is connected with a plasma gas generator, and the plasma cracking furnace is connected with an inert gas generator. According to the invention, the catalyst is reduced by the reducing gas through the preprocessor from the high-temperature tail gas waste heat, so that the catalyst reduction step is eliminated, the transportation and storage of the catalyst are facilitated, and the catalyst activity is improved; in addition, the high-temperature tail gas of the plasma is utilized to provide heat required by catalyst reduction, so that the energy is saved and the environment is protected; the continuous collection of the single-walled carbon nanotubes is realized by using a bubbling collection and filter pressing mode, and the problems that the catalyst of the existing equipment is difficult to store, low in energy utilization rate, incapable of continuous production and the like after reduction are solved.
Description
Technical Field
The invention relates to the technical field of carbon nanotube production, in particular to a plasma single-wall carbon nanotube continuous production system and method.
Background
Single-walled carbon nanotubes (SWCNTs for short) are one type of carbon nanotubes, which have unique structures and properties, and have wide application prospects in the fields of material science, electronics, biomedicine and the like. Currently, the preparation methods of single-walled carbon nanotubes mainly include arc discharge method, laser evaporation method, chemical Vapor Deposition (CVD) method, pyrolysis method, and the like. Among them, the arc discharge method is one of the most commonly used preparation methods, and the principle is to generate carbon nanotubes including single-walled carbon nanotubes and multi-walled carbon nanotubes by arc discharge of a graphite electrode at a high temperature. The laser evaporation method is to evaporate graphite target material with laser to produce carbon nanotube, including single-wall carbon nanotube and multi-wall carbon nanotube. The chemical vapor deposition method is to crack carbon-containing gas (such as methane) at high temperature to form carbon nanotubes, including single-wall carbon nanotubes and multi-wall carbon nanotubes, by controlling the reaction conditions. The pyrolysis method is to prepare single-wall carbon nanotubes by utilizing a high-temperature pyrolysis reaction, wherein a compound containing a carbon source is subjected to pyrolysis reaction at a high temperature, and carbon atoms generated by the pyrolysis reaction form the single-wall carbon nanotubes, and the diameter and the length of the single-wall carbon nanotubes prepared by the method can be controlled by adjusting the pyrolysis temperature and the pyrolysis time. However, the mass production of existing single-walled carbon nanotubes has the following difficulties:
1. The preparation process is complex; currently, the main methods for preparing single-walled carbon nanotubes include arc discharge, laser evaporation, chemical Vapor Deposition (CVD), template, and the like. The methods require strict control of reaction conditions, such as temperature, pressure, atmosphere, etc., during the preparation process to obtain high quality single-walled carbon nanotubes. However, these preparation processes are relatively complicated, and it is difficult to achieve continuous mass production.
2. The purification difficulty is high; the single-walled carbon nanotubes produced often contain significant amounts of impurities, such as carbon and metal impurities. The presence of these impurities limits the practical properties of single-walled carbon nanotubes. However, it is difficult to completely remove impurities in single-walled carbon nanotubes, especially single-walled carbon nanotubes, by a single purification method. Therefore, how to purify single-walled carbon nanotubes efficiently is an important challenge currently faced.
3. The quality is unstable; the single-wall carbon nano tube prepared by the traditional method has unstable quality and has the problems of uneven tube diameter distribution, structural defects and the like. These problems can affect the performance and application of single-walled carbon nanotubes. Therefore, how to improve the yield and quality stability of single-walled carbon nanotubes is another difficulty in mass production.
4. The cost is high; at present, the cost for preparing the high-quality single-wall carbon nano tube is still high, which limits the popularization of the high-quality single-wall carbon nano tube in large-scale application, and the reduction of the preparation cost is one of the problems to be solved in the mass production process of the single-wall carbon nano tube.
Disclosure of Invention
In order to solve the problems, the invention provides a continuous production system and a continuous production method of a plasma single-wall carbon nanotube, so that the yield and the quality stability of the single-wall carbon nanotube are improved, the preparation cost is reduced, and the system and the method can be popularized in large-scale application.
In a first aspect, the invention provides a continuous production system of plasma single-walled carbon nanotubes, which comprises a feeder, a preprocessor, a plasma cracking furnace and a water cooling tank; the feeder is connected with a carrier gas generator which is used for storing and generating carrier gas; the pretreatment device comprises a first pipeline and a second pipeline, wherein an inlet of the first pipeline is connected with an outlet of the feeder;
The bottom in the plasma cracking furnace is provided with a plasma anode, the top of the plasma cracking furnace is provided with a plasma cathode in a penetrating way, the plasma cracking furnace is provided with a plasma control module, the plasma cathode and the plasma anode are connected with a plasma power supply, and the plasma control module is used for controlling the height of the plasma cathode so as to maintain the stability of an electric arc; the plasma cracking furnace is provided with a plasma power supply by the plasma power supply and generates arc plasma between the plasma cathode and the plasma anode; the plasma cathode is connected with a plasma gas generator which is used for storing and generating plasma gas, the plasma cracking furnace is connected with an inert gas generator, and the inert gas generator is used for generating inert gas and purging products in the plasma cracking furnace;
One side of the plasma cracking furnace is provided with a gas and catalyst inlet, the other side of the plasma cracking furnace is provided with a discharge outlet, and the catalyst inlet and the discharge outlet are positioned between the plasma cathode and the plasma anode; the discharge port is connected with an inlet of a second pipeline of the preprocessor, and an outlet of the second pipeline is connected with an inlet of the water cooling tank; the outlet of the first pipeline is connected with the gas and catalyst inlet.
In one embodiment of the invention, the plasma cracking furnace is further provided with a gas spray head, the inert gas generator is connected with the gas spray head, and inert gas generated by the inert gas generator sweeps products in the plasma cracking furnace through the gas spray head; the plasma cathode is a hollow electrode, and the plasma gas generator introduces plasma gas into the interior of the plasma cathode to maintain a plasma arc.
In one embodiment of the invention, the feeder is provided with a control module, and the control module is used for controlling the feeding rate of the feeder; the preprocessor comprises a temperature control module, wherein the temperature control module controls the temperature inside the preprocessor by adjusting the gas flow; the plasma pyrolysis furnace is provided with a thermocouple, and the thermocouple is used for detecting the temperature in the plasma pyrolysis furnace.
In one embodiment of the present invention, a surface of the plasma anode facing the plasma cathode is a concave surface; the number of the gas spray heads is multiple, and one gas spray head is arranged above one side of the concave plasma anode.
In one embodiment of the invention, the device further comprises a bubbling collection tank and a filter press; the bottom of the water cooling tank is connected with an inlet pipeline, the inlet pipeline stretches into the bubbling collection tank, a water supplementing ball float valve is arranged in the bubbling collection tank, and the water supplementing ball float valve is connected with a pure water pipeline; the inlet pipeline extends below the water surface in the bubbling collection tank, and the bubbling collection tank is also connected with a tail gas pipeline; the filter press is connected with the bubbling collection tank, and the filter press comprises a receiving groove which is used for collecting products.
In a second aspect, the present invention provides a continuous production method of single-walled carbon nanotubes, using the continuous production system of single-walled carbon nanotubes, comprising the steps of:
step 1: introducing plasma gas into the plasma cathode, starting a plasma power supply to generate plasma between the plasma cathode and the plasma anode, and heating the plasma cracking furnace to a set temperature;
Step 2: opening a carrier gas generator, introducing carrier gas, opening a feeder after the preprocessor reaches a set temperature and is stable, and introducing reducing gas and carbon source gas from the carrier gas generator to reduce the catalyst through the preprocessor;
Step 3: the reduced catalyst, carrier gas, carbon source gas and reducing gas synchronously enter the gas and catalyst inlet of the plasma cracking furnace, the catalyst is instantaneously evaporated through the excitation of arc plasma and reacts with the carbon source to generate a crude product, the inert gas of the plasma cracking furnace sweeps the crude product from a discharge port to the inlet of a second pipeline of the preprocessor to provide heat for catalyst reduction, and the crude product enters a water cooling tank through the outlet of the second pipeline of the preprocessor;
Step 4: cooling the crude product by a water cooling tank, and then taking the cooled crude product into pure water in a bubbling collection tank by air flow, wherein the air is discharged through a tail gas pipeline, the materials are left in the water to form suspension, a filter press is started, the pure water is recovered into the bubbling collection tank after the product in the water is subjected to filter pressing, and the product is in a filter cake form and is collected by a material collecting tank of the filter press;
step 5: continuously adding a catalyst, introducing a carbon source and a reducing gas, and continuously collecting products to realize continuous production.
In one embodiment of the present invention, the plasma gas in the step 1 comprises one or more of nitrogen, argon, helium, neon, hydrogen, methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide, carbon dioxide, and water vapor; the carrier gas comprises one or more of nitrogen, argon, helium, neon and the like; the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide and methane; the carbon source gas comprises one or more of methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide and carbon dioxide.
In one embodiment of the present invention, the set temperature range of the plasma pyrolysis furnace in the step 1 is 800 ℃ to 2000 ℃; the set temperature range of the preprocessor in the step 2 is 100-800 ℃.
In one embodiment of the invention, the uniform powder feeding rate of the feeder is in the range of 5-2000g/h; the carrier gas flow is 10-2000SLM; the air flow range of the carbon source is 5-500SLM; the plasma gas flow is 10-2000SLM.
In a third aspect, the present invention also provides a single-walled carbon nanotube, which is prepared by using the continuous production method of plasma single-walled carbon nanotubes.
The invention has the beneficial effects that:
The invention provides a plasma single-wall carbon nanotube continuous production system and a method, which adopt a feeder to control the uniform and continuous feeding of a catalyst, so that the catalyst is reduced by reducing gas through high-temperature tail gas waste heat by a preprocessor, the catalyst reduction step is eliminated, the transportation and storage of the catalyst are convenient, and the catalyst activity is improved; in addition, the high-temperature tail gas of the plasma is utilized to provide heat required by catalyst reduction, so that the energy is saved and the environment is protected; the invention realizes continuous collection of the single-walled carbon nanotubes by using a bubbling collection tank pressurizing filter, solves the problems of difficult storage, low energy utilization rate of a plasma furnace, incapability of continuous production and the like of the catalyst of the existing equipment after reduction, and provides a feasible solution for large-scale mass production of the single-walled carbon nanotubes. The plasma vapor deposition method based on the chemical vapor deposition method combines the catalyst design, the reaction condition control and the post-treatment technology, and can effectively improve the yield and the quality of the single-walled carbon nanotubes.
Drawings
Fig. 1 is a schematic structural diagram of a continuous production system for plasma single-walled carbon nanotubes according to the present invention.
FIG. 2 is a scanning electron microscope image of a crude single-walled carbon nanotube product prepared in example 3.
Fig. 3 is a raman spectrum of single-walled carbon nanotubes prepared in example 3.
Fig. 4 is a raman spectrum of single-walled carbon nanotubes prepared in example 4.
Fig. 5 is a raman spectrum of single-walled carbon nanotubes prepared in example 5.
In the figure: 1. a feeder; 2. a preprocessor; 3. a plasma pyrolysis furnace; 4. a plasma cathode; 5. a plasma anode; 6. a water-cooling tank; 7. a bubbling collection tank; 8. a filter press; 9. a plasma power supply; 10. a first pipeline; 11. a second pipeline; 12. gas and catalyst inlets; 13. a discharge port; 14. a temperature control module; 15. a thermocouple; 16. an inert gas generator; 17. a gas shower; 18. a plasma control module; 19. a plasma gas generator; 20. a carrier gas generator; 21. a control module; 22. a float valve; 23. an inlet duct; 24. a tail gas pipeline; 25. a material collecting groove; 26. pure water pipeline.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Wherein the terms "first position" and "second position" are two different positions.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixed or removable, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1
Referring to fig. 1, the present embodiment provides a continuous production system of single-walled carbon nanotubes, which comprises a feeder 1, a preprocessor 2, a plasma pyrolysis furnace 3, a plasma cathode 4, a plasma anode 5, a water cooling tank 6, a bubbling collection tank 7, a filter press 8 and a plasma power supply 9.
Optionally, the feeder 1 is connected with a carrier gas generator 20 which is used for storing and generating carrier gas, the feeder 1 is provided with a control module 21, and the control module 21 is used for controlling the feeding rate of the feeder 1; the feeder 1 automatically and accurately controls the feeding rate by the control module 21 to realize uniform powder feeding; wherein the carrier gas may be one or more gases.
Optionally, the preprocessor 2 comprises a temperature control module 14, the temperature control module 14 controlling the temperature inside the preprocessor 2 by adjusting the gas flow; the pretreatment device 2 comprises a first pipeline 10 and a second pipeline 11, wherein an inlet of the first pipeline 10 is connected with an outlet of the feeder 1, and an outlet of the first pipeline 10 is connected with a gas and catalyst inlet 12 arranged in the plasma cracking furnace 3.
Optionally, a plasma anode 5 is disposed at the bottom of the plasma pyrolysis furnace 3, a plasma cathode 4 is disposed on the top of the plasma pyrolysis furnace 3 in a penetrating manner, a plasma control module 18 is disposed on the plasma pyrolysis furnace 3, the plasma cathode 4 and the plasma anode 5 are both connected with a plasma power supply 9, and the plasma control module 18 is used for automatically adjusting the height of the plasma cathode 4 to maintain the stability of the electric arc; the plasma cracking furnace 3 is provided with a plasma power supply by the plasma power supply 9 and generates arc plasma between the plasma cathode 4 and the plasma anode 5; the plasma cathode 4 is connected with a plasma gas generator 19 for storing and generating plasma gas, the plasma cathode 4 is a hollow electrode, and the plasma gas generator 19 is used for introducing the plasma gas into the plasma cathode 4 to maintain a plasma arc.
Optionally, the plasma anode 5 is a high temperature resistant, non-volatile conductive material.
Optionally, the plasma pyrolysis furnace 3 is provided with a thermocouple 15, and the thermocouple 15 is used for detecting the temperature of a reaction chamber in the furnace of the plasma pyrolysis furnace 3.
Optionally, the plasma cracking furnace 3 is further provided with a gas nozzle 17, the plasma cracking furnace 3 is connected with an inert gas generator 16, the inert gas generator 16 is connected with the gas nozzle 17, the inert gas generator 16 is used for generating inert gas, and the inert gas sweeps products in the plasma cracking furnace 3 through the gas nozzle 17, so that the discharging is facilitated.
Optionally, the surface of the plasma anode 5 facing the plasma cathode 4 is concave, which facilitates gas and material flow.
Optionally, the number of the gas shower nozzles 17 is plural, wherein one of the gas shower nozzles 17 is disposed above one side of the concave plasma anode 5 to further enhance the gas and material flow.
Optionally, one side of the plasma cracking furnace 3 is provided with a gas and catalyst inlet 12, the other side is provided with a discharge outlet 13, and the catalyst inlet 12 and the discharge outlet 13 are positioned between the plasma cathode 4 and the plasma anode 5; the discharge port 13 is connected with an inlet of a second pipeline 11 of the preprocessor 2, and an outlet of the second pipeline 11 is connected with an inlet of the water cooling tank 6.
Optionally, an inlet pipeline 23 is connected to the bottom of the water-cooling tank 6, the inlet pipeline 23 extends into the bubbling collection tank 7, a water replenishing ball float valve 22 is arranged in the bubbling collection tank 7, and the water replenishing ball float valve 22 is connected with a pure water pipeline 26 to automatically replenish water to a proper liquid level; the inlet pipeline 23 extends into the bubbling collection tank 7 at a position 20cm below the water surface, and the bubbling collection tank 7 is also connected with a tail gas pipeline 24.
Optionally, the filter press 8 is connected to the bubble collection tank 7, and the filter press 8 comprises a receiving tank 25, and the receiving tank 25 is used for collecting the product.
Example 2
The embodiment provides a continuous production method of plasma single-walled carbon nanotubes, which uses the continuous production system of plasma single-walled carbon nanotubes provided in embodiment 1, and comprises the following steps:
step 1: introducing plasma gas into the plasma cathode 4, starting the plasma power supply 9 to generate plasma between the plasma cathode 4 and the plasma anode 5, and heating the plasma cracking furnace 3 to a set temperature;
Step 2: opening a carrier gas generator 20, introducing carrier gas, opening a feeder 1 after the preprocessor 2 reaches a set temperature and is stable, and introducing reducing gas and carbon source gas from the carrier gas generator 20 to reduce the catalyst through the preprocessor 2;
Step 3: the reduced catalyst, carrier gas, carbon source gas and reducing gas synchronously enter the gas of the plasma cracking furnace 3 and the catalyst inlet 12, the catalyst is instantaneously evaporated through the excitation of arc plasma and reacts with the carbon source to generate a crude product, the inert gas of the plasma cracking furnace 3 sweeps the crude product from the discharge port 13 to the inlet of the second pipeline 11 of the preprocessor 2 to provide heat for catalyst reduction, and then enters the water cooling tank 6 through the outlet of the second pipeline 11 of the preprocessor 2;
step 4: the crude product is cooled by a water cooling tank 6 and then is carried into pure water in a bubbling collection tank 7 by an air flow, wherein the air is discharged through a tail gas pipeline 24, the materials are left in the water to form suspension, a filter press 8 is started, the pure water is recovered into the bubbling collection tank 7 after the product in the water is filtered, and the product is in a filter cake form and is collected by a receiving tank of the filter press 8;
step 5: continuously adding a catalyst, introducing a carbon source and a reducing gas, and continuously collecting products to realize continuous production.
Optionally, the plasma gas in the step 1 comprises one or more of nitrogen, argon, helium, neon, hydrogen, methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide, carbon dioxide, and water vapor.
Alternatively, the set temperature of the plasma pyrolysis furnace 3 in the step 1 ranges from 800 ℃ to 2000 ℃.
Optionally, the set temperature range of the preprocessor 2 in the step 2 is 100 ℃ to 800 ℃; the constant-speed powder feeding speed range of the feeder 1 is 5-2000g/h.
Optionally, the carrier gas comprises one or more of nitrogen, argon, helium, neon, and the like.
Optionally, the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide, methane.
Optionally, the carbon source gas comprises one or more of methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide, carbon dioxide.
Optionally, the carrier gas flow is 10-2000SLM; the air flow range of the carbon source is 5-500SLM; the plasma gas flow is 10-2000SLM.
Example 3
The embodiment provides a continuous production method of plasma single-walled carbon nanotubes, which uses the continuous production system of plasma single-walled carbon nanotubes provided in embodiment 1, and comprises the following steps:
step 1: opening a carrier gas generator 20, introducing nitrogen gas of 100slm, and continuously introducing the nitrogen gas for 3 hours to replace the air in the plasma cracking furnace 3;
Step 2: opening a plasma generator 19, adjusting argon 100SLM to be introduced into a plasma cathode 4 of a plasma cracking furnace 3, opening the plasma generator 19 and a plasma control module 18 to generate stable plasma, and starting to heat and maintaining at 800 ℃;
Step 3: opening a temperature control module 14 of the preprocessor 2, adjusting carrier gas to be hydrogen 100SLM, wherein the temperature control module 14 automatically adjusts the flow of argon, and the fluctuation range is about 120-180SLM, so that the temperature of the preprocessor 2 is maintained at 400 ℃;
step 4: and (3) opening the feeder 1, setting the catalyst flow to 10g/H, simultaneously adjusting the plasma generator 3 to introduce 30SLM hydrogen into the plasma, and adjusting the carrier gas generator 20 to introduce 100SLM methane to generate a crude product of the single-walled carbon nanotubes.
Step 5: the receiving chute 25 of the filter press 8 is opened and the final product is collected. The yield of the dried initial product is about 1.9kg/h, and the production system can continuously run for 113h. Fig. 2 is a scanning electron microscope image of a crude single-walled carbon nanotube product prepared in example 3, and it can be seen that the diameter of the single-walled carbon nanotube is small, but the carbon deposition is more.
The average IG/ID ratio of the product obtained in example 3 was 54 as shown in FIG. 3, and 20% as measured by ash as shown in Table 1.
Example 4
The embodiment adopts the continuous production method of the plasma single-walled carbon nanotube provided in the embodiment 3 to produce the single-walled carbon nanotube, and the difference is that: the carrier gas comprises argon 300SLM and hydrogen 200SLM; the plasma gas comprises argon 300SLM, methane 200SLM and water vapor 10SLM; the temperature of the preprocessor 2 is 500 ℃, the temperature of the plasma cracking furnace 3 is 900 ℃, and the produced products are collected through a receiving groove 25 of the filter press 8. The yield of the primary product after drying was about 3.2kg/h. The production system may be run continuously for 130 hours.
The average IG/ID ratio of the product obtained in example 4 was 50 as shown in FIG. 4, and 15% as measured by ash as shown in Table 1.
Example 5
The embodiment adopts the continuous production method of the plasma single-walled carbon nanotube provided in the embodiment 3 to produce the single-walled carbon nanotube, and the difference is that: the carrier gas comprises argon 100SLM, hydrogen 100SLM and methane 200SLM; the plasma gas comprises argon 600SLM, water vapor 10SLM and carbon dioxide 40SLM; the temperature of the preprocessor 2 is 400 ℃, the temperature of the plasma cracking furnace 3 is 1000 ℃, and the produced products are collected through a receiving groove 25 of the filter press 8. The yield of the primary product after drying is about 4.1kg/h. The production system can be run continuously for 186 hours.
The average IG/ID ratio of the product obtained in example 5 was 60 as shown in FIG. 5, and 13% was measured from the ash as shown in Table 1.
Table 1: comparative tables of the products obtained in examples 3, 4 and 5
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it would be obvious to those skilled in the art that various improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications fall within the scope of the claims of the present invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The continuous production system of the plasma single-walled carbon nanotubes is characterized by comprising a feeder (1), a preprocessor (2), a plasma cracking furnace (3) and a water cooling tank (6); the feeder (1) is connected with a carrier gas generator (20) which is used for storing and can generate carrier gas; the pretreatment device (2) comprises a first pipeline (10) and a second pipeline (11), wherein an inlet of the first pipeline (10) is connected with an outlet of the feeder (1);
A plasma anode (5) is arranged at the bottom in the plasma cracking furnace (3), a plasma cathode (4) is arranged at the top of the plasma cracking furnace (3) in a penetrating way, a plasma control module (18) is arranged on the plasma cracking furnace (3), the plasma cathode (4) and the plasma anode (5) are both connected with a plasma power supply (9), and the plasma control module (18) is used for controlling the height of the plasma cathode (4) so as to maintain the stability of an electric arc; the plasma cracking furnace (3) is provided with a plasma power supply by the plasma power supply (9) and generates arc plasma between the plasma cathode (4) and the plasma anode (5); the plasma cathode (4) is connected with a plasma gas generator (19) which is used for storing and generating plasma gas, the plasma cracking furnace (3) is connected with an inert gas generator (16), and the inert gas generator (16) is used for generating inert gas and purging products in the plasma cracking furnace (3);
One side of the plasma cracking furnace (3) is provided with a gas and catalyst inlet (12), the other side is provided with a discharge outlet (13), and the catalyst inlet (12) and the discharge outlet (13) are positioned between the plasma cathode (4) and the plasma anode (5); the discharge port (13) is connected with an inlet of a second pipeline (11) of the preprocessor (2), and an outlet of the second pipeline (11) is connected with an inlet of the water cooling tank (6); the outlet of the first conduit (10) is connected to the gas and catalyst inlet (12).
2. The continuous production system of the single-walled carbon nanotubes according to claim 1, wherein the plasma pyrolysis furnace (3) is further provided with a gas nozzle (17), the inert gas generator (16) is connected with the gas nozzle (17), and inert gas generated by the inert gas generator (16) sweeps products in the plasma pyrolysis furnace (3) through the gas nozzle (17); the plasma cathode (4) is a hollow electrode, and the plasma gas generator (19) is used for introducing plasma gas into the plasma cathode (4) to maintain a plasma arc.
3. A continuous production system of single-walled carbon nanotubes according to claim 2 characterized in that the feeder (1) is provided with a control module (21), the control module (21) being adapted to control the feed rate of the feeder (1); the preprocessor (2) comprises a temperature control module (14), and the temperature control module (14) controls the temperature inside the preprocessor (2) by adjusting the gas flow; the plasma pyrolysis furnace (3) is provided with a thermocouple (15), and the thermocouple (15) is used for detecting the temperature in the plasma pyrolysis furnace (3).
4. A continuous production system for single-walled carbon nanotubes according to claim 3 characterized in that the surface of the plasma anode (5) facing the plasma cathode (4) is concave; the number of the gas spray heads (17) is multiple, and one gas spray head (17) is arranged above one side of the concave plasma anode (5).
5. A continuous production system for single-walled carbon nanotubes according to claim 4 further comprising a bubbling collection tank (7) and a filter press (8); the bottom of the water cooling tank (6) is connected with an inlet pipeline (23), the inlet pipeline (23) stretches into the bubbling collection tank (7), a water supplementing floating ball valve (22) is arranged in the bubbling collection tank (7), and the water supplementing floating ball valve (22) is connected with a pure water pipeline (26); the inlet pipeline (23) stretches into the bubbling collection tank (7) below the water surface, and the bubbling collection tank (7) is also connected with a tail gas pipeline (24); the filter press (8) is connected with the bubbling collection tank (7), the filter press (8) comprises a receiving tank (25), and the receiving tank (25) is used for collecting products.
6. A continuous production method of plasma single-walled carbon nanotubes, characterized in that a continuous production system of plasma single-walled carbon nanotubes as described in any of claims 1-5 is used, comprising the steps of:
step 1: introducing plasma gas into the plasma cathode (4), starting a plasma power supply (9) to generate plasma between the plasma cathode (4) and the plasma anode (5), and heating the plasma cracking furnace (3) to a set temperature;
Step 2: opening a carrier gas generator (20), introducing carrier gas, opening a feeder (1) after the preprocessor (2) reaches a set temperature and is stable, and introducing reducing gas and carbon source gas from the carrier gas generator (20) to reduce the catalyst through the preprocessor (2);
Step 3: the reduced catalyst, carrier gas, carbon source gas and reducing gas synchronously enter a gas and catalyst inlet (12) of a plasma cracking furnace (3), the catalyst is instantaneously evaporated through excitation of arc plasma and reacts with the carbon source to generate a crude product, the crude product is purged from a discharge hole (13) to an inlet of a second pipeline (11) of a preprocessor (2) by inert gas of the plasma cracking furnace (3), heat is provided for catalyst reduction, and the crude product enters a water cooling tank (6) through an outlet of the second pipeline (11) of the preprocessor (2);
step 4: the crude product is cooled by a water cooling tank (6) and then is carried into pure water in a bubbling collection tank (7) by airflow, wherein the gas is discharged through a tail gas pipeline (24), the materials are left in the water to form suspension, a filter press (8) is started, after the product in the water is filtered, the pure water is recovered into the bubbling collection tank (7), and the product is in a filter cake form and is collected by a material collecting tank of the filter press (8);
step 5: continuously adding a catalyst, introducing a carbon source and a reducing gas, and continuously collecting products to realize continuous production.
7. The continuous production method of single-walled carbon nanotubes according to claim 6, wherein the plasma gas in step 1 contains one or more of nitrogen, argon, helium, neon, hydrogen, methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide, carbon dioxide, and water vapor; the carrier gas comprises one or more of nitrogen, argon, helium, neon and the like; the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide and methane; the carbon source gas comprises one or more of methane, ethylene, propylene, ethane, propane, liquefied petroleum gas, natural gas, carbon monoxide and carbon dioxide.
8. The continuous production method of plasma single-walled carbon nanotubes according to claim 6 wherein the set temperature of the plasma pyrolysis furnace (3) in step 1 is 800 ℃ to 2000 ℃; the set temperature range of the preprocessor (2) in the step 2 is 100 ℃ to 800 ℃.
9. The continuous production method of the plasma single-walled carbon nanotubes according to claim 6, wherein the uniform powder feeding rate of the feeder (1) is in the range of 5-2000g/h; the carrier gas flow is 10-2000SLM; the air flow range of the carbon source is 5-500SLM; the plasma gas flow is 10-2000SLM.
10. A single-walled carbon nanotube, wherein the single-walled carbon nanotube is produced by a continuous production method of a plasma single-walled carbon nanotube according to any of claims 6 to 9.
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| CN105777511A (en) * | 2016-04-06 | 2016-07-20 | 衢州信步化工科技有限公司 | Energy-saving and efficient acetylacetone synthesis process |
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