CN103395774B - Reaction device and method for producing graphene or carbon nanotubes - Google Patents

Abstract

The invention provides a reaction device and method for producing graphene or carbon nanotubes. The reaction device comprises an enlarging section, a reaction section and a plurality of bins, wherein the upper end of the enlarging section is connected with a catalyst feeding device, the reaction section is connected to the lower end of the enlarging section, gas distribution boards can axially move and pass in the reaction section, a plurality of vent holes are formed in the gas distribution boards, an electric furnace surrounds the reaction section externally, the lower end of the reaction section is connected with a first gas inlet pipe, the bins are connected with the reaction section through inlet pipes, valves are arranged on the inlet pipes, and protection gas inlets are formed in the bins. According to the reaction device and method for producing the graphene or carbon nanotubes, continuous addition of a catalyst and continuous extraction of a solid-phase product can be realized, the production can be carried out continuously, and the production process efficiency is greatly improved.

Description

Reaction device and method for producing graphene or carbon nanotubes

technical field

The present invention relates to a reaction device and method, in particular to a reaction device and method for producing graphene or carbon nanotubes in the technical field of chemical equipment.

Background technique

Carbon nanomaterials such as carbon nanotubes and graphene have been research hotspots in the field of carbon materials in the past ten years, because of their good electrical conductivity, physical and chemical stability and high mechanical strength, they are used in conductive additives, catalysis and composite reinforcement. Tough materials and other aspects have good application prospects.

The premise of the wide application of carbon nanomaterials is the development and maturity of low-cost batch technology. At present, the gas phase chemical deposition method is mostly used in the production of carbon nanotubes. The process and reaction of the fluidized bed production of carbon nanotubes proposed in the prior art However, a fully continuous production process cannot be realized, and the addition of catalyst or the removal of final product is carried out in batches. However, the process of preparing graphene by vapor phase chemical deposition has not yet been implemented industrially, and there are no reports on efficient and continuous production devices and process flows.

Therefore, it is necessary to provide a new reaction device and method to overcome the above-mentioned defects.

Contents of the invention

The object of the present invention is to provide a reaction device for producing graphene or carbon nanotubes, which can realize the continuous addition of catalysts and the continuous extraction of solid-phase products, and can carry out uninterrupted production, greatly improving the efficiency of the production process.

Another object of the present invention is to provide a method for producing graphene or carbon nanotubes, which can realize the continuous addition of catalysts and the continuous extraction of solid-phase products, and can produce without interruption, greatly improving the efficiency of the production process .

Above-mentioned purpose of the present invention can adopt following technical scheme to realize:

The invention provides a reaction device for producing graphene or carbon nanotubes, the reaction device for producing graphene or carbon nanotubes comprises:

An enlarged section, the upper end of which is connected with a catalyst feeding device;

The reaction section is connected to the lower end of the expansion section, and a gas distribution plate is axially movable in the reaction section, and a plurality of air holes are opened on the gas distribution plate, and the outer circumference of the reaction section An electric furnace is provided, and a first air inlet pipe is connected to the lower end of the reaction section;

A plurality of feed bins, which are connected to the reaction section through inlet pipes, valves are provided on the inlet pipes, and protective gas inlets are opened on the feed bins;

Wherein, there are two feed bins, and the inlet pipes of the two feed bins are respectively connected to the first position and the second position of the reaction section, and the first position is located above the second position; In the state where the reaction for preparing graphene or carbon nanotubes is carried out in the reaction section, the gas distribution plate is located above the first position of the reaction section.

In a preferred embodiment, the reaction section includes a first reaction section and a second reaction section, the first reaction section is connected to the upper end of the second reaction section, and the diameter of the first reaction section is larger than the The diameter of the second reaction section.

In a preferred embodiment, the expansion section is connected with a second inlet pipe, and the second inlet pipe extends into the bottom of the first reaction section of the reaction section, and the gas distribution plate can axially move through It is located in the second reaction section of the reaction section.

The present invention also provides a method for producing graphene or carbon nanotubes, the method for producing graphene or carbon nanotubes adopts the above-mentioned reaction device for producing graphene or carbon nanotubes, and the method for producing graphene or carbon nanotubes The method includes the following steps:

a) providing a catalyst, placing said catalyst into a catalyst feeding device;

b) Inject argon or nitrogen from the first inlet pipe connected to the lower end of the reaction section, and inject the argon or nitrogen into the reaction section through a plurality of ventilation holes provided on the gas distribution plate in the reaction section, and at the same time , open the electric furnace surrounding the outside of the reaction section;

c) After the electric furnace finishes heating the reaction section, inject the catalyst in the catalyst feeding device into the reaction section connected to the lower end of the expansion section through the expansion section connected with the catalyst feeding device, At this time, a hydrocarbon carbon source gas is injected into the reaction section, and the catalyst, the argon or nitrogen gas, and the hydrocarbon carbon source gas are prepared by chemical vapor deposition in the reaction section to obtain a solid phase product;

d) discharging the solid phase product into a plurality of silos connected to the lower part of the reaction section;

Wherein, there are two feed bins, and the inlet pipes of the two feed bins are respectively connected to the first position and the second position of the reaction section, and the first position is located above the second position; In the step c), the gas distribution plate in the reaction section is located above the first position of the reaction section.

In a preferred embodiment, step e) is further included after the step d): purifying the solid phase products in the plurality of silos.

In a preferred embodiment, in the step d), the gas distribution plate in the reaction section is moved to below the second position, or to the first position and the second position Between, the solid phase products are respectively discharged into the corresponding storage bins.

In a preferred embodiment, the gas velocity of argon or nitrogen injected into the reaction section is 0.01-10 m/s.

The characteristics and advantages of the reaction device and method for producing graphene or carbon nanotubes of the present invention are:

1. The reaction device and method for producing graphene or carbon nanotubes of the present invention, in the whole production process, the catalyst feeding device of the reaction device can continuously feed into the reaction section, in addition, the material connected to the bottom of the reaction section The warehouse allows the solid phase products prepared in the reaction section to be continuously extracted, and the invention can carry out uninterrupted production, greatly improving the efficiency of the production process.

Two, the reaction device and method for producing graphene or carbon nanotubes of the present invention, because the catalyst density that does not have coke deposit or less coke deposit is less, and the gas distribution plate that can axially move and be installed in the reaction section, Under the action of the gas flow pressure below it, it is further ensured that the catalyst in the reaction section does not fall below the gas distribution plate, so that it will not be extracted as the final product; when the catalyst carbon deposition in the reaction section is fully completed, its accumulation When the density increases, it will enter the silo through the bottom of the reaction section and be extracted as the final product. In addition, the nitrogen or argon gas flow introduced from the multiple air holes of the gas distribution plate can also help the solid phase product to be transported smoothly, so that the solid phase product has good fluidity and avoids coking.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained based on these drawings without creative effort.

Fig. 1 is a front view of an embodiment of a reaction device for producing graphene or carbon nanotubes of the present invention.

Fig. 2 is a front view of another embodiment of a reaction device for producing graphene or carbon nanotubes of the present invention.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

This embodiment provides a reaction device for producing graphene or carbon nanotubes, and the application of this device in the production of graphene or carbon nanotubes.

As shown in FIG. 1 , the present invention provides a reaction device for producing graphene or carbon nanotubes, which includes an expansion section 1 , a reaction section 2 and a plurality of storage bins 3 . Wherein: the upper end of the expansion section 1 is connected with a catalyst feeding device 4; the reaction section 2 is connected with the lower end of the expansion section 1, and a gas distribution plate 21 is axially movable in the reaction section 2, and the gas The distribution plate 21 is provided with a plurality of ventilation holes (not shown in the figure), the outside of the reaction section 2 is surrounded by an electric furnace 5, and the lower end of the reaction section 2 is connected with a first air inlet pipe 22; 3 is connected to the reaction section 2 through an inlet pipe 31, the inlet pipe 31 is provided with a valve 32, and the feed bin 3 is provided with a protective gas inlet 33.

Specifically, the catalyst feeding device 4 is connected to the upper end of the enlarged section 1 and extends into the enlarged section 1. The catalyst feeding device 4 is used to contain the catalyst. In the present invention, the catalyst feeding device 4 adopts screw transmission or pulse Continuous or intermittent feeding is realized by means of air jetting, and the catalyst feeding device 4 which adopts screw conveying or pulsed jetting mode of feeding is already in the prior art, and its specific structure will not be repeated here. The upper end of the expansion section 1 is provided with an exhaust gas outlet 11, and its lower part forms a rounded platform shape, so that the catalyst in the catalyst feeding device 4 can be smoothly poured into the reaction section 2 connected to the lower end of the expansion section 1.

Reaction section 2 is used to perform chemical vapor deposition on the catalyst to prepare the desired graphene or carbon nanotubes. The electric furnace 5 surrounding the reaction section 2 is used for heat treatment of the reaction section 2 . In the present invention, the gas distribution plate 21 movably installed in the reaction section 2 is controlled by a motor 23 connected to the lower end of the gas distribution plate 21. According to actual production needs, the motor 23 can drive the gas distribution plate 21 Axial displacement up and down in the reaction section 2. A plurality of ventilation holes provided on the gas distribution plate 21 are used to inject the gas into the first gas inlet pipe 22 connected to the lower end of the reaction section 2 into the reaction section 2 through the ventilation holes. In this embodiment, the distance between the outer edge of the gas distribution plate 21 and the inner wall of the reaction section 2 is 0 to 0.5mm, which can ensure that the gas distribution plate 21 and the inner wall of the reaction section 2 are carried out at 400-950°C. Good cooperation, to prevent the powdery material above the gas distribution plate 21 from falling into the reaction section 2 below the gas distribution plate 21, and be extracted as the final product; The gas in 2 can form a certain air pressure below the gas distribution plate 21, which further ensures that the powdery material does not leak out.

A plurality of feed bins 3 are connected to the lower outer wall of the reaction section 2, and the feed bins 3 are used to contain the solid-phase products obtained in the reaction section 2 through chemical vapor deposition. In the present invention, the feed bin 3 is connected to the reaction section 2 through an inlet pipe 31, the inlet pipe 31 is provided with a valve 32, and the valve 32 is used to open or close the inlet pipe 31; The protective gas inlet 33 is used to pass protective gas such as nitrogen or argon into the silo 3 to prevent air from entering. In this embodiment, the reaction device for producing graphene or carbon nanotubes has two feed bins 3, and the inlet pipes 31 of the two feed bins 3 are respectively connected to the first position 24 and the second position 25 of the reaction section 2, The first position 24 is located above the second position 25 . When the solid-phase product of graphene or carbon nanotubes is prepared in the reaction section 2, and the gas distribution plate 21 moves to between the first position 24 and the second position 25 of the reaction section 2, that is, at position B in Fig. 1 At this time, the valve 32 on the inlet pipe 31 of the feed bin 3 on the left side of the reaction section 2 is opened, and the solid phase product in the reaction section 2 will fall into the feed bin 3 on the left side of the reaction section 2; when the gas distribution plate 21 moves To the below of the second position 25 of the reaction section 2, that is, when the C position in Fig. Phase products will fall into the silo 3 located on the right side of the reaction section 2.

The present invention prepares the production process of graphene by the reaction device of this production graphene or carbon nanotube as follows: first, pass into argon gas from the first inlet pipe 22 below reaction section 2, argon gas passes through a plurality of gas distribution plates 21 The air vent is injected into the reaction section 2, and at this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 900°C; after that, methane is introduced into the reaction section 2 from the first air inlet pipe 22, and the motor 23 is started. , move the gas distribution plate 21 to the top of the first position 24 of the reaction section 2, that is, the position A shown in Figure 1; then, pour the MgO template agent in the catalyst feeding device 4 through the expansion section 1 In the reaction section 2, during this period, argon and methane are continuously introduced into the first inlet pipe 22, and the feeding is suspended after adding about 100 g of the MgO template agent, so that the MgO template agent, methane and argon react in the reaction section 2 for 20 minutes , and then start the motor 23 to move the gas distribution plate 21 down to between the first position 24 and the second position 25 of the reaction section 2, that is, at the position B shown in Figure 1, so that the gas prepared in the reaction section 2 The solid phase product is discharged into the feed bin 3 on the left side of the reaction section 2. During this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as the protective gas; after that, the motor is started 23. Move the gas distribution plate 21 up to the top of the first position 24 of the reaction section 2, that is, at position A shown in FIG. After a few minutes, move the gas distribution plate 21 to the B position shown in Figure 1 to discharge the material, and operate in such a cycle; when the feed bin 3 on the left side of the reaction section 2 is about to be filled, close the feed bin 3 on the left side of the reaction section 2 The valve 32 on the inlet pipe 31 moves the gas distribution plate 21 to below the second position 25 of the reaction section 2, that is, at position C shown in Fig. 1, so that the solid phase product prepared in the reaction section 2 is discharged into the bunker 3 on the right side of the reaction section 2, during this period, from the protective gas inlet 33 of the bunker 3 on the right side of the reaction section 2, argon gas is introduced as a protective gas. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excessive hydrochloric acid is used to mix and stir the solid-phase products, and then suction filtered and dried to obtain graphene products.

The present invention prepares the production process of single-wall or double-wall carbon nanotubes through the reaction device for producing graphene or carbon nanotubes as follows: first, feed argon gas from the first inlet pipe 22 below the reaction section 2, and the argon gas passes through A plurality of ventilation holes of the gas distribution plate 21 are injected into the reaction section 2, and at this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 900°C; Feed methane, start the motor 23, and move the gas distribution plate 21 between the first position 24 and the second position 25 of the reaction section 2, that is, the B position shown in Figure 1; then, the catalyst feeding device The FeMo/MgO catalyst in 4 is poured into the reaction section 2 through the expansion section 1. During this period, the first inlet pipe 22 is continuously fed with argon and methane, and the FeMo/MgO catalyst enters the reaction section 2 to form a single-wall or double-wall After the carbon nanotubes directly fall into the feed bin 3 on the left side of the reaction section 2, during this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as the protective gas; When the silo 3 on the left side of the reaction section 2 is almost full, close the valve 32 on the inlet pipe 31 of the silo 3 on the left side of the reaction section 2, and move the gas distribution plate 21 down to the second position 25 of the reaction section 2 , that is, at position C shown in Figure 1, the solid-phase product in the reaction section 2 will fall into the bin 3 on the right side of the reaction section 2; solid phase product, and pass into argon gas from the protective gas inlet 33 of the feed bin 3 to empty the air in the feed bin 3 on the left side of the reaction section 2; when the feed bin 3 on the right side of the reaction section 2 is almost full , move the gas distribution plate 21 to between the first position 24 and the second position 25 of the reaction section 2, that is, at position B shown in Figure 1, the solid phase product in the reaction section 2 will fall into the In the bin 3 on the left side of 2, this cycle is carried out. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excess hydrochloric acid is used to mix and stir the products, and then suction filtered and dried to obtain single-wall or double-wall carbon nanotube products.

The present invention prepares the production process of multi-walled carbon nanotubes by the reaction device of this production graphene or carbon nanotubes as follows: first, pass into nitrogen gas from the first inlet pipe 22 below reaction section 2, and this nitrogen gas passes through the gas distribution plate 21 A plurality of ventilation holes are injected into the reaction section 2. At this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 1000°C; after that, methane is introduced into the reaction section 2 from the first air inlet pipe 22 to start the process. The motor 23 moves the gas distribution plate 21 to the top of the first position 24 of the reaction section 2, that is, the position A shown in Figure 1; then, the NiMo/MgO catalyst in the catalyst feeding device 4 is passed through the expansion section 1 is poured into the reaction section 2. During this period, nitrogen and methane are continuously introduced into the first inlet pipe 22. After the NiMo/MgO catalyst, methane and nitrogen react in the reaction section 2 for 30 minutes, the gas distribution plate 21 is moved down to Between the first position 24 and the second position 25 of the reaction section 2, that is, at position B shown in FIG. 3, during this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as a protective gas; when the feed bin 3 on the left side of the reaction section 2 is almost full, the reaction section is closed 2 The valve 32 of the silo 3 on the left side moves the gas distribution plate 21 down to below the second position 25 of the reaction section 2, that is, at the position C shown in Figure 1, the solid phase product in the reaction section 2 will be Fall into the feed bin 3 on the right side of the reaction section 2, at this time, take out the solid phase product in the feed bin 3 on the left side of the reaction section 2, and feed argon gas from the protective gas inlet 33 of the feed bin 3 to be evacuated The air in it; when being positioned at the feed bin 3 on the right side of the reaction section 2 is almost full, the gas distribution plate 21 is moved to between the first position 24 and the second position 25 of the reaction section 2, that is, as shown in Fig. 1 At the position B shown, the solid phase product in the reaction section 2 will fall into the feed bin 3 on the left side of the reaction section 2, and so on. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excess hydrochloric acid is used to mix and stir the products, and then suction filtered and dried to obtain single-wall or double-wall carbon nanotube products.

The reaction device for producing graphene or carbon nanotubes of the present invention, in the whole production process, its catalyst feeding device 4 can constantly feed into the reaction section 2, in addition, the feed bin 3 connected to the reaction section 2 bottom, The solid-phase product prepared in the reaction section 2 can be continuously extracted, and the present invention can carry out uninterrupted production, greatly improving the efficiency of the production process. Furthermore, due to the low density of the catalyst with no carbon deposit or less carbon deposit, and the gas distribution plate 21 that can move axially through the reaction section 2, under the action of the air flow pressure below it, the reaction rate is further ensured. The catalyst in section 2 does not fall below the gas distribution plate 21, so it will not be extracted as the final product; when the carbon deposition of the catalyst in the reaction section 2 is fully completed, its bulk density increases, and it will pass through the reaction section 2 The bottom enters the silo 3 and is withdrawn as the final product. In addition, the nitrogen or argon gas flow introduced from the multiple air holes of the gas distribution plate 21 also helps to transport the solid-phase product smoothly, so that the solid-phase product has good fluidity and avoids coking.

According to one embodiment of the present invention, as shown in Figure 2, the reaction section 2 includes a first reaction section 26 and a second reaction section 27, the first reaction section 26 is connected to the upper end of the second reaction section 27 , the diameter of the first reaction section 26 is greater than the diameter of the second reaction section 27 . In the present invention, the diameter of the second reaction section 27 of the reaction section 2 is designed to be smaller than the diameter of the first reaction section 26, so that the air flow that passes through the gas distribution plate 21 can blow out the materials with less bulk density out of the second reaction section 27 , so that the materials with higher bulk density can be smoothly discharged into the designated bin 3.

According to one embodiment of the present invention, the expansion section 1 is connected with a second gas inlet pipe 12, and the second gas inlet pipe 12 extends into the bottom of the first reaction section 26 of the reaction section 2, and the gas distribution plate 21 is axially movable through the second reaction section 27 of the reaction section 2 . The second gas inlet pipe 12 is used to feed methane, so that the first gas inlet pipe 21 can only be fed with nitrogen or argon during the whole production flow process, preventing that in the subsequent process of feeding methane through the first gas inlet pipe 21, There are security risks.

Example 2

This embodiment provides a process for producing graphene or carbon nanotubes.

The present invention also provides a kind of method of producing graphene or carbon nanotube, the method for described production graphene or carbon nanotube adopts above-mentioned reaction device (as shown in Figure 1 and Figure 2) of producing graphene or carbon nanotube , the method for producing graphene or carbon nanotubes may further comprise the steps:

a) providing a catalyst, which is put into the catalyst feeding device 4;

b) Inject argon or nitrogen from the first inlet pipe 22 connected to the lower end of the reaction section 2, and inject the argon or nitrogen into the reaction through a plurality of air holes provided on the gas distribution plate 21 in the reaction section 2. In the section 2, at the same time, open the electric furnace 5 surrounding the outside of the reaction section 2;

c) After the electric furnace 5 finishes heating the reaction section 2, the catalyst in the catalyst feeding device 4 is injected into the lower end of the expanding section 1 through the expansion section 1 connected to the catalyst feeding device 4. In the reaction section 2, at this time, a hydrocarbon carbon source gas is injected into the reaction section 2, and the catalyst, the argon or nitrogen, and the hydrocarbon carbon source gas pass through the reaction section 2 Chemical vapor deposition to prepare solid phase products;

d) Discharging the solid phase product into a plurality of silos 3 connected to the lower part of the reaction section 2 .

Specifically, the structure, working principle and beneficial effects of the reaction device for producing graphene or carbon nanotubes in Example 2 are the same as those in Example 1, and will not be repeated here.

In the present invention, step e) is further included after the step d): purifying the solid phase products in the plurality of silos 3 . That is, the product is mixed and stirred with excess hydrochloric acid, then suction-filtered and dried to obtain a single-wall or double-wall carbon nanotube product.

In this embodiment, the gas velocity of argon or nitrogen injected into the reaction section 2 is 0.01-10 m/s. The gas velocity of the argon or nitrogen flowing through the plurality of vent holes of the gas distribution plate 21 is 0.1˜100 m/s. In the step c), the heating temperature of the electric furnace is 900-1000°C. The hydrocarbon carbon source gas may be methane.

In the present embodiment, there are two feed bins 3 of the reaction device producing graphene or carbon nanotubes, and the inlet pipes 31 of the two feed bins 3 are respectively connected to the first position 24 and the second position 25 of the reaction section 2, The first location 24 is located above the second location 25 . In said step c), the gas distribution plate 21 in the reaction section 2 is located above the first position 24 of the reaction section 2 .

Further, in the step d), the gas distribution plate in the reaction section is respectively moved below the second position, or between the first position and the second position, so that The solid phase products are respectively discharged into the corresponding feed bins.

The present invention prepares the production process of graphene by the reaction device of this production graphene or carbon nanotube as follows: first, pass into argon gas from the first inlet pipe 22 below reaction section 2, argon gas passes through a plurality of gas distribution plates 21 The air vent is injected into the reaction section 2, and at this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 900°C; after that, methane is introduced into the reaction section 2 from the first air inlet pipe 22, and the motor 23 is started. , move the gas distribution plate 21 to the top of the first position 24 of the reaction section 2, that is, the position A shown in Figure 1; then, pour the MgO template agent in the catalyst feeding device 4 through the expansion section 1 In the reaction section 2, during this period, argon and methane are continuously introduced into the first inlet pipe 22, and the feeding is suspended after adding about 100 g of the MgO template agent, so that the MgO template agent, methane and argon react in the reaction section 2 for 20 minutes , and then start the motor 23 to move the gas distribution plate 21 down to between the first position 24 and the second position 25 of the reaction section 2, that is, at the position B shown in Figure 1, so that the gas prepared in the reaction section 2 The solid phase product is discharged into the feed bin 3 on the left side of the reaction section 2. During this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as the protective gas; after that, the motor is started 23. Move the gas distribution plate 21 up to the top of the first position 24 of the reaction section 2, that is, at position A shown in FIG. After a few minutes, move the gas distribution plate 21 to the B position shown in Figure 1 to discharge the material, and operate in such a cycle; when the feed bin 3 on the left side of the reaction section 2 is about to be filled, close the feed bin 3 on the left side of the reaction section 2 The valve 32 on the inlet pipe 31 moves the gas distribution plate 21 to below the second position 25 of the reaction section 2, that is, at position C shown in Fig. 1, so that the solid phase product prepared in the reaction section 2 is discharged into the bunker 3 on the right side of the reaction section 2, during this period, from the protective gas inlet 33 of the bunker 3 on the right side of the reaction section 2, argon gas is introduced as a protective gas. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excessive hydrochloric acid is used to mix and stir the solid-phase products, and then suction filtered and dried to obtain graphene products.

The present invention prepares the production process of single-wall or double-wall carbon nanotubes through the reaction device for producing graphene or carbon nanotubes as follows: first, feed argon gas from the first inlet pipe 22 below the reaction section 2, and the argon gas passes through A plurality of ventilation holes of the gas distribution plate 21 are injected into the reaction section 2, and at this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 900°C; Feed methane, start the motor 23, and move the gas distribution plate 21 between the first position 24 and the second position 25 of the reaction section 2, that is, the B position shown in Figure 1; then, the catalyst feeding device The FeMo/MgO catalyst in 4 is poured into the reaction section 2 through the expansion section 1. During this period, the first inlet pipe 22 is continuously fed with argon and methane, and the FeMo/MgO catalyst enters the reaction section 2 to form a single-wall or double-wall After the carbon nanotubes directly fall into the feed bin 3 on the left side of the reaction section 2, during this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as the protective gas; When the silo 3 on the left side of the reaction section 2 is almost full, close the valve 32 on the inlet pipe 31 of the silo 3 on the left side of the reaction section 2, and move the gas distribution plate 21 down to the second position 25 of the reaction section 2 , that is, at position C shown in Figure 1, the solid-phase product in the reaction section 2 will fall into the bin 3 on the right side of the reaction section 2; solid phase product, and pass into argon gas from the protective gas inlet 33 of the feed bin 3 to empty the air in the feed bin 3 on the left side of the reaction section 2; when the feed bin 3 on the right side of the reaction section 2 is almost full , move the gas distribution plate 21 to between the first position 24 and the second position 25 of the reaction section 2, that is, at position B shown in Figure 1, the solid phase product in the reaction section 2 will fall into the In the bin 3 on the left side of 2, this cycle is carried out. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excess hydrochloric acid is used to mix and stir the products, and then suction filtered and dried to obtain single-wall or double-wall carbon nanotube products.

The present invention prepares the production process of multi-walled carbon nanotubes by the reaction device of this production graphene or carbon nanotubes as follows: first, pass into nitrogen gas from the first inlet pipe 22 below reaction section 2, and this nitrogen gas passes through the gas distribution plate 21 A plurality of ventilation holes are injected into the reaction section 2. At this time, the electric furnace 5 surrounded by the reaction section 2 is opened, and the temperature of the electric furnace 5 is raised to 1000°C; after that, methane is introduced into the reaction section 2 from the first air inlet pipe 22 to start the process. The motor 23 moves the gas distribution plate 21 to the top of the first position 24 of the reaction section 2, that is, the position A shown in Figure 1; then, the NiMo/MgO catalyst in the catalyst feeding device 4 is passed through the expansion section 1 is poured into the reaction section 2. During this period, nitrogen and methane are continuously introduced into the first inlet pipe 22. After the NiMo/MgO catalyst, methane and nitrogen react in the reaction section 2 for 30 minutes, the gas distribution plate 21 is moved down to Between the first position 24 and the second position 25 of the reaction section 2, that is, at position B shown in FIG. 3, during this period, argon is introduced from the protective gas inlet 33 of the feed bin 3 on the left side of the reaction section 2 as a protective gas; when the feed bin 3 on the left side of the reaction section 2 is almost full, the reaction section is closed 2 The valve 32 of the silo 3 on the left side moves the gas distribution plate 21 down to below the second position 25 of the reaction section 2, that is, at the position C shown in Figure 1, the solid phase product in the reaction section 2 will be Fall into the feed bin 3 on the right side of the reaction section 2, at this time, take out the solid phase product in the feed bin 3 on the left side of the reaction section 2, and feed argon gas from the protective gas inlet 33 of the feed bin 3 to be evacuated The air in it; when being positioned at the feed bin 3 on the right side of the reaction section 2 is almost full, the gas distribution plate 21 is moved to between the first position 24 and the second position 25 of the reaction section 2, that is, as shown in Fig. 1 At the position B shown, the solid phase product in the reaction section 2 will fall into the feed bin 3 on the left side of the reaction section 2, and so on. Finally, the solid-phase products in the two silos 3 are taken out for purification treatment, that is, excess hydrochloric acid is used to mix and stir the products, and then suction filtered and dried to obtain single-wall or double-wall carbon nanotube products.

The method for producing graphene or carbon nanotubes of the present invention, in the whole production process, the catalyst feeding device of the reaction device that produces graphene or carbon nanotubes that the method adopts can constantly feed in the reaction zone, in addition , connected to the feed bin at the lower part of the reaction section, the solid-phase products prepared in the reaction section can be continuously extracted, and the method of the present invention can carry out uninterrupted production, greatly improving the efficiency of the production process.

The above are only a few embodiments of the present invention, and those skilled in the art can make various changes or modifications to the embodiments of the present invention according to the contents disclosed in the application documents without departing from the spirit and scope of the present invention.

Claims (7)

1. a reaction unit producing graphene or carbon nanotube, is characterized in that, the reaction unit of described production graphene or carbon nanotube comprises: An enlarged section, the upper end of which is connected with a catalyst feeding device; The reaction section is connected to the lower end of the expansion section, and a gas distribution plate is axially movable in the reaction section, and a plurality of air holes are opened on the gas distribution plate, and the outer circumference of the reaction section An electric furnace is provided, and a first air inlet pipe is connected to the lower end of the reaction section; A plurality of feed bins, which are connected to the reaction section through inlet pipes, valves are provided on the inlet pipes, and protective gas inlets are opened on the feed bins; Wherein, there are two feed bins, and the inlet pipes of the two feed bins are respectively connected to the first position and the second position of the reaction section, and the first position is located above the second position; In the state where the reaction for preparing graphene or carbon nanotubes is carried out in the reaction section, the gas distribution plate is located above the first position of the reaction section. 2. the reaction device of producing graphene or carbon nanotube as claimed in claim 1, is characterized in that, described reaction section comprises first reaction section and second reaction section, and described first reaction section is connected in described first reaction section The upper end of the second reaction section, the diameter of the first reaction section is larger than the diameter of the second reaction section. 3. the reaction device of producing graphene or carbon nanotube as claimed in claim 2, is characterized in that, is connected with the second air inlet pipe on the described expansion section, and described second air inlet pipe stretches into the first air inlet pipe of described reaction section The bottom of a reaction section, the gas distribution plate is axially movable through the second reaction section of the reaction section. 4. a method for producing graphene or carbon nanotubes, characterized in that, the method for producing graphene or carbon nanotubes adopts the production of graphene or carbon nanotubes as described in any one of claims 1 to 3 A reaction device, the method for producing graphene or carbon nanotubes may further comprise the steps: a) providing a catalyst, placing said catalyst into a catalyst feeding device; b) Inject argon or nitrogen from the first inlet pipe connected to the lower end of the reaction section, and inject the argon or nitrogen into the reaction section through a plurality of ventilation holes provided on the gas distribution plate in the reaction section, and at the same time , open the electric furnace surrounding the outside of the reaction section; c) After the electric furnace finishes heating the reaction section, inject the catalyst in the catalyst feeding device into the reaction section connected to the lower end of the expansion section through the expansion section connected with the catalyst feeding device, At this time, a hydrocarbon carbon source gas is injected into the reaction section, and the catalyst, the argon or nitrogen gas, and the hydrocarbon carbon source gas are prepared by chemical vapor deposition in the reaction section to obtain a solid phase product; d) discharging the solid phase product into a plurality of silos connected to the lower part of the reaction section; Wherein, there are two feed bins, and the inlet pipes of the two feed bins are respectively connected to the first position and the second position of the reaction section, and the first position is located above the second position; In the step c), the gas distribution plate in the reaction section is located above the first position of the reaction section. 5. the method for producing graphene or carbon nanotube as claimed in claim 4, is characterized in that, also comprises step e) after described step d): the solid-phase product in described multiple feed bins is purified deal with. 6. the method for producing graphene or carbon nanotube as claimed in claim 4, it is characterized in that, in described step d), the gas distribution plate in the described reaction section is moved to respectively in the described second position. Below, or moving to between the first position and the second position, the solid phase products are respectively discharged into the corresponding silos. 7. The method for producing graphene or carbon nanotubes according to claim 4, characterized in that the gas velocity of argon or nitrogen injected into the reaction section is 0.01-10m/s.