KR100712690B1 - Carbon nanotubes mass fabrication device with loop reactor and carbon nanotubes mass fabrication method - Google Patents

Abstract

The present invention relates to a carbon nanotube synthesizer, in which a catalyst and a carbon source are continuously introduced into a loop reactor, carbon nanotubes are generated while the introduced catalyst and carbon source circulate in the reactor, And the nanotubes are continuously discharged through a discharge tube. BACKGROUND OF THE INVENTION [0002] The present invention relates to a method for mass synthesis of a looped carbon nanotube and a method for mass synthesis of a carbon nanotube.

Carbon nanotubes, loop type, centrifugal force, gas phase synthesis, continuous process, mass production

Description

FIELD OF THE INVENTION [0001] The present invention relates to a carbon nanotube bulk synthesizing apparatus and a carbon nanotube bulk synthesis method,

FIG. 1 is a plan view schematically showing a loop-shaped carbon nanotube synthesizer according to the present invention,

FIG. 2 is a side view showing a part of a reactor in which a reactor discharge pipe of the carbon nanotube synthesis apparatus of FIG. 1 is formed,

3 is a plan view schematically showing a loop-shaped carbon nanotube synthesizer according to another embodiment of the present invention,

FIG. 4 is a side view showing a part of a reactor having a reactor discharge pipe of the carbon nanotube synthesizer of FIG. 3,

5 is a schematic view of a vertically erected type looped carbon nanotube synthesizer according to another embodiment of the present invention.

* Description of main reference numerals *

10: Catalyst supply part 20: Reactor

30: gas supply unit 40: reactor outlet pipe

50: Cleaning device

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a loop-type carbon nanotube synthesizer and a method of mass-synthesizing carbon nanotubes, wherein a catalyst and a carbon source are continuously injected into a loop-shaped reactor, and the injected catalyst and carbon source circulate Synthesizing carbon nanotubes, and continuously discharging the synthesized carbon nanotubes through a discharge tube. The method for mass synthesis of carbon nanotubes of the present invention can be considered as a vapor phase synthesis method.

Methods for synthesizing carbon nanotubes include arc discharge, laser vaporization, vapor phase synthesis, and pyrolysis.

In the chemical vapor deposition method, a carbon source gas containing carbon is injected into a reactor and decomposed by heat to adsorb carbon on the catalyst material to grow carbon nanotubes.

However, in the conventional method of synthesizing carbon nanotubes, it is difficult to synthesize carbon nanotubes in large quantities in order to synthesize carbon nanotubes in large quantities or when the size of the apparatus is small.

In addition, according to the conventional method of synthesizing carbon nanotubes, it is necessary to shut off the inside of the reactor to the atmosphere in order to maintain the internal pressure of the reactor at a set value because the reaction is performed while maintaining the inside of the reactor at a vacuum or above atmospheric pressure.

It is an object of the present invention to provide a carbon nanotube synthesis device for continuously synthesizing and discharging carbon nanotubes while circulating a catalyst and a carbon source in a reactor, .

The above object of the present invention can be achieved by a catalyst apparatus comprising: a catalyst supply unit for supplying a catalyst; A loop-shaped reactor having an internal space connected to the catalyst supply unit and connected in a loop and having a heater; A gas supply unit having a carbon source tank connected to the loop reactor to supply a carbon source to the loop reactor; A reactor outlet pipe formed in the loop reactor; And a blowing fan installed inside the loop-shaped reactor.

The gas supply unit may further include a hydrogen gas tank and an inert gas tank connected to the loop-shaped reactor to supply the hydrogen gas and the inert gas to the loop-shaped reactor.

In addition, the reactor discharge pipe is preferably connected to the inside of the loop-shaped reactor.

Wherein the catalyst supply unit comprises: a hydrogen supply pipe to which hydrogen is supplied; A hydrogen discharge pipe through which the hydrogen is discharged; And a heater are further formed.

The apparatus may further include a cleaning device connected to the reactor discharge pipe and having an air inlet and a gas discharge pipe formed with a filter and a suction pump.

The above object of the present invention can be achieved by a catalyst apparatus comprising: a catalyst supply unit for supplying a catalyst; A loop-shaped reactor having an internal space connected to the catalyst supply unit and connected in a loop and having a heater; A carbon source, a hydrogen gas tank, and an inert gas tank connected to the loop-shaped reactor for supplying carbon source, hydrogen gas, and inert gas, wherein the catalyst, the carbon source, the hydrogen gas, and the inert gas A gas supply part for injecting at least one of a carbon source, a hydrogen gas and an inert gas with a spraying force enough to form a circulating flow of the inert gas; And a reactor discharge pipe formed in the loop-shaped reactor.

Another embodiment of the present invention includes a catalyst supply unit for injecting a catalyst; A loop-type first reactor having an internal space connected to the catalyst supply unit and connected in a loop, and having a heater; A first reactor outlet pipe connected to the loop-like first reactor; A loop-like second reactor having an inner space connected to the first reactor discharge pipe and connected in a loop, and having a heater; A second reactor outlet pipe connected to the loop-like second reactor; A gas supply unit connected to the loop-type first reactor and the loop-type second reactor to supply a carbon source gas and an inert gas; And a blowing fan installed in at least one of the first reactor and the second reactor in the loop.

An object of the present invention is to provide a catalyst system, A loop-type first reactor having an internal space connected to the catalyst supply unit and connected in a loop, and having a heater; A first reactor outlet pipe connected to the loop-like first reactor; A loop-like second reactor having an inner space connected to the first reactor discharge pipe and connected in a loop, and having a heater; A second reactor outlet pipe connected to the second reactor; And a carbon source tank connected to at least one of the first reactor and the second reactor to supply a carbon source, a hydrogen gas, and an inert gas, a hydrogen gas tank, and an inert gas tank, And a gas supply unit for injecting at least one of carbon source, hydrogen gas and inert gas with a spraying force enough to form a circulating flow of the catalyst, the carbon source, the hydrogen gas and the inert gas. .

Also, an object of the present invention is to provide a process for producing a polymer electrolyte membrane, which comprises supplying a catalyst, a carbon source, a hydrogen gas and an inert gas into a loop-shaped reactor having a closed- Synthesizing carbon nanotubes while circulating the catalyst, carbon source, hydrogen gas, and inert gas in one direction; And discharging the synthesized carbon nanotube through a reactor discharge pipe of the loop reactor.

The mass synthesis method preferably includes a step of heating the loop-type reactor to maintain the temperature inside the loop-type reactor at 600 ° C to 1200 ° C.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a loop carbon nanotube synthesizer will be described in detail with reference to the accompanying drawings.

FIG. 1 is a plan view schematically showing a loop-shaped carbon nanotube synthesizer according to the present invention, and FIG. 2 is a side view showing a part of a reactor having a reactor discharge tube of the carbon nanotube synthesizer of FIG. 1, a carbon nanotube synthesis apparatus according to the present invention uses gas phase synthesis, and includes a catalyst supply unit 10, a loop-shaped reactor 20 (hereinafter referred to as a 'reactor 20'), (30), a reactor discharge pipe (40) and a blowing fan (25).

The catalyst supply unit 10 is means for reducing the catalyst and supplying it to the reactor 20. The catalyst may be a solid state metal, or it may be a liquid catalyst prepared by melting a metal in a solvent. In this embodiment, a case of using a catalyst metal in a solid state will be described. The catalyst supply part 10 includes a housing part 11 which is a space for accommodating the catalyst metal, a heater 12 installed in the housing part 11 for heating the catalyst metal accommodated in the housing part 11, A hydrogen supply pipe 13 for supplying hydrogen gas to the reactor 20 and a catalyst supply pipe 15 for connecting the reactor 20 to the lower part of the accommodating portion 11. A water discharge pipe 18 for discharging the water generated in the reduction process of the catalyst to the outside of the receiving part is formed in the lower part of the receiving part 11. A catalyst metal charging part and a hydrogen gas discharge pipe 14 Is formed. The catalytic metal charging portion is connected to the accommodating portion 11 through an opening / closing valve.

The catalyst supply pipe 15 is provided with a transfer screw 16 for transferring the catalyst metal to the reactor, and the hydrogen supply pipe 13 and the hydrogen gas discharge pipe 14 are connected to each other. . Iron, nickel, cobalt or the like is used as the catalyst metal.

As shown in FIGS. 1 and 2, the reactor 20 connected to the catalyst supply unit 10 under the catalyst supply unit 10 includes a cyclic ring-shaped internal space in which carbon nanotubes are synthesized, And the outside of the reactor 20 is surrounded by the heater 22. [ The internal space of the reactor 20 is connected to the catalyst supply pipe 15, the reactor discharge pipe 40 and the gas supply pipe 31 to be described later. A jaw 24 is formed in the reactor 20 in front of the gas supply pipe.

The gas supply unit 30 includes inert gas tanks 36 for storing inert gas such as argon or nitrogen, a hydrogen gas tank 35 for storing hydrogen gas, and a carbon source gas tank for storing carbon source gas such as ethylene 37 and a gas supply pipe 31 connecting the respective gas tanks 35, 36, 37 and the reactor 20 so as to supply the respective gases to the internal space of the reactor 20. As the inert gas, nitrogen, argon, or the like is used, and as the carbon source gas, a hydrocarbon compound (C ₂ H ₂ , C ₂ H ₄ , CH _{4 ,} alcohol, etc.) containing carbon is used.

The reactor discharge pipe 40 is a pipe connected to the reactor 20 for discharging the carbon nanotubes synthesized from the reactor 20, and a cooling means is installed around the pipe and connected to the cleaning device 50. The reactor discharge pipe (40) is provided with an opening / closing valve (44).

As shown in Fig. 2, the reactor discharge pipe 40 is connected to the inside of the reactor when viewed from the circulating flow direction. However, it is also possible that the reactor discharge pipe 40 is connected to a part other than the inside of the reactor.

The cleaning device 50 includes a collecting part 51 for collecting and cleaning carbon nanotubes and having a space connected to the reactor discharge pipe 40. The collecting part 51 is provided with a stirring blade 53 are formed. An air inlet 54 for introducing outside air is provided at one side of the collecting part 51 and an amount of gas corresponding to the amount of air flowing through the air inlet 54 is provided at an upper part of the collecting part 51 And a carbon nanotube outlet 59 for discharging the cleaned carbon nanotube is installed at the bottom of the collecting part 51. [ The gas discharge pipe 56 is provided with a blower 57 and a filter 58. The air inlet 54, the gas discharge pipe 56, and the carbon nanotube outlet 59 are respectively provided with on / off valves so that they can be selectively opened and closed.

FIG. 3 is a plan view schematically showing a loop-shaped carbon nanotube synthesis apparatus according to another embodiment of the present invention, and FIG. 4 is a side view illustrating a portion of a reactor having a reactor discharge tube of the carbon nanotube synthesis apparatus of FIG. 3 . The looped carbon nanotube synthesis apparatus shown in FIGS. 3 and 4 is similar to the carbon nanotube synthesis apparatus of FIG. 1 except that it has two reactors 120 and 220.

The reactors 120 and 220 are composed of a first reactor 120 and a second reactor 220. The first reactor 120 is connected to the catalyst supply unit 10 so that the catalyst is first introduced and the first reactor 120 is connected to the second reactor 220 through the reactor discharge pipe 140. The second reactor 220 is connected to the cleaning device 150 via a reactor outlet pipe 240. No cooling means is formed in the reactor discharge pipe 140 connecting the first reactor 120 and the second reactor 220.

The second reactor 220 has a blowing fan 225 for forming a circulating flow, and is connected to a carbon source gas tank for receiving a carbon source gas. The second reactor 220 is disposed below the first reactor 120 in consideration of the direction of gravity so as to prevent the catalyst metal and carbon nanotubes flowing into the second reactor 220 from flowing back to the first reactor 120 again. And the cleaning device 150 is also located below the second reactor 220 to prevent the carbon nanotubes flowing into the cleaning device 150 from flowing back to the second reactor 220. The reactor discharge pipe 240 connecting the second reactor 220 and the cleaning apparatus 150 is provided with a cooling means 242 for cooling the carbon nanotubes.

5 is a schematic view of a vertically erected type looped carbon nanotube synthesizer according to another embodiment of the present invention. 5, the vertically erected looped carbon nanotube synthesis apparatus includes a vertically erected reactor 300 and the reactor is provided with a catalyst feed pipe 310, a gas feed pipe 331, (340).

The reactor discharge pipe 340 through which the synthesized carbon nanotubes are discharged is formed on the upper part of the reactor 300 and has a flow direction of less than 90 degrees with respect to the direction of the circulation flow. And is formed to be inclined. The catalyst feed pipe 310 is formed on the left side of the reactor discharge pipe 340 at the upper portion of the reactor and has an inclination of 90 degrees or more from the direction of the circulating flow. If the catalyst feed pipe is located on the right side of the reactor discharge pipe, there is a risk of escaping through the reactor discharge pipe before the first introduced catalyst circulates inside the reactor. Therefore, the catalyst supply pipe 310 is formed on the left side of the reactor discharge pipe 340.

Since the reactor discharge pipe 340 is located at an upper portion of the reactor 300, the catalyst having a small volume and a large specific gravity and having a low kinetic energy for lifting stops rising at a point near the reactor discharge pipe 340, So that the catalyst is not discharged through the reactor discharge pipe 340. On the contrary, since the carbon nanotubes are large in volume and small in specific gravity, they receive kinetic energy for lifting, so that the carbon nanotubes rise in a predetermined direction (304) against gravity and are discharged through the reactor discharge pipe (340).

Next, a process of synthesizing carbon nanotubes by a loop-type carbon nanotube synthesizer according to an embodiment of the present invention will be described.

First, the heater is operated to raise the inside of the reactor 20 to 600 to 1200 ° C, and hydrogen gas and argon gas are injected into the reactor 20 to make the inside of the reactor 20 an inert atmosphere.

Next, the catalyst metal is reduced in the catalyst supply unit 10, and the reduced catalyst metal is supplied to the reactor 20. The process of reducing the catalyst metal in the catalyst supply unit 10 is as follows.

The temperature of the storage portion 11 is increased to 600 to 1200 DEG C by the heater provided in the storage portion 11 and hydrogen gas is supplied through the hydrogen supply pipe 13 connected to the storage portion 11 to cool the storage portion 11 It is made into a reducing atmosphere. Thereafter, the catalytic metal is continuously introduced into the accommodating portion 11 through the catalytic metal charging portion. In the accommodating portion 11, the catalytic metal reacts with the hydrogen gas, and the catalytic metal generates water. The generated water is vaporized by water vapor and discharged to the outside of the accommodating portion 11 through the water discharge pipe 18. The reduced catalytic metal is supplied to the reactor 20 through the transfer screw 16 of the catalyst supply pipe 15.

Water generated in the reduction process is vaporized by water vapor, but the water vapor is smaller in specific gravity than hydrogen, so that it sinks below the hydrogen, and the water vapor that has settles is discharged to the outside of the receiving portion through the water discharge pipe formed at the lower portion of the receiving portion. Also, since the hydrogen gas is discharged through the hydrogen gas discharge pipe 14 by an amount that the hydrogen gas flows into the accommodation portion through the hydrogen supply portion, the pressure inside the accommodation portion is kept constant.

Hydrogen gas and argon gas are supplied to the reactor 20 through the gas supply pipe 31 and the blowing fan 25 is operated to generate a circulating flow in the reactor 20 in one direction. The carbon source gas, the hydrogen gas, the inert gas and the catalyst metal flowing into the reactor 20 circulate in the reactor 20 together with the blowing fan. The catalyst and the carbon nanotube circulating in the reactor 20 pass through the gas supply pipe in the process of passing over the jaw 24, so that the catalyst and the carbon nanotube are prevented from flowing back to the gas supply pipe. Since the inside of the reactor 20 is in a high temperature state, ethylene gas, which is a carbon source gas, is pyrolyzed and separated into carbon and hydrogen, and the separated carbon is adsorbed on the catalyst metal to grow carbon nanotubes from the catalyst metal. The synthesis of the carbon nanotubes is carried out in the course of circulating the catalyst metal and the carbon source gas in the reactor 20.

Since the catalyst metal is continuously injected into the reactor 20, the inside of the reactor 20 is separated from the catalyst metal which has not yet started to react at a certain point, and the catalyst metal and the carbon nanotube Tube " means " catalyst metal with grown carbon nanotubes ").

The catalyst metal and the pure catalyst metal having less growth of the carbon nanotubes rotate around the outside of the reactor 20 due to the centrifugal force because the specific gravity is larger than that of the carbon nanotubes circulating in the reactor 20.

However, since the synthesized carbon nanotube has a relatively large volume and a small specific gravity as compared with the catalytic metal, it has a large kinetic energy at the time of blowing by the blowing fan. Therefore, it is possible to overcome the centrifugal force and move inward from the outside of the reactor.

Also, considering the gravity, the catalytic metal moves along the bottom of the reactor. However, since the carbon nanotube has a large kinetic energy obtained by blowing, if the reactor outlet pipe is formed above the reactor, the carbon nanotubes And can therefore be discharged through the reactor discharge pipe.

Therefore, most of the carbon nanotubes are discharged through the reactor discharge pipe 40 formed inside the reactor 20.

In addition, since the carbon nanotubes have a small specific gravity and a large volume compared to the catalytic metal, the gases inside the reactor are easily entrained by the gases when they are discharged to the reactor discharge pipe 40, thereby easily escaping the reactor.

Since the process is continuously performed, the catalyst metal injected into the reactor 20 is exhausted from the reactor 20 through the reactor discharge pipe 40 after the carbon nanotubes are grown, and the carbon nanotubes The catalytic metal can not escape from the reactor 20 and circulates and continues to react with the carbon source gas.

The carbon nanotubes discharged through the reactor discharge pipe 40 are cooled by the cooling means provided in the reactor discharge pipe 40 and the cooled carbon nanotubes are introduced into the collecting part 51 of the cleaning device 50.

In addition to the carbon nanotubes, hydrogen gas, carbon source gas, and argon gas are introduced into the collecting unit 51, so that gases other than carbon nanotubes need to be washed away. Therefore, when outside air is introduced into the collecting part 51 through the air inlet 54 and the remaining gases are washed out, the air and the remaining gases are discharged through the gas discharge pipe 56, and only the carbon nanotubes It remains. At this time, since the gas discharge pipe is provided with a filter, the carbon nanotubes are filtered and only air and residual gases are discharged. In the course of the air scrubbing of the remaining gases, the agitating wings 53 stir the carbon nanotubes evenly, so that the residual gases contained in the carbon nanotubes are effectively washed away.

Carbon nanotubes that have undergone this cleaning process are now ready for shipment.

Next, the operation and effect of the loop-shaped carbon nanotube synthesizer having two reactors 120 and 220 will be described.

The synthesis of carbon nanotubes in the first reactor 120 and the washing in the apparatus 150 are performed in the same manner as the synthesis apparatus of the embodiment shown in FIG. 1, so that the second reactor 220, This paper focuses on the reactions performed in

Carbon nanotubes are mostly introduced into the second reactor 220 through the reactor discharge pipe 140 in the first reactor 120, but sometimes carbon nanotubes or catalyst metal having less growth may be introduced into the second reactor 220. Therefore, the catalytic metal and the carbon source continue to react in the second reactor 220, thereby improving the synthesis yield of the carbon nanotubes. The carbon nanotubes discharged through the reactor discharge pipe 240 of the second reactor 220 are cooled by the cooling means 242 of the reactor discharge pipe 240 and flow into the cleaning apparatus 150.

In the synthesis apparatus according to the embodiment of the present invention described above, the catalyst metal is reduced in the catalyst supply unit 10, but when the reduced catalyst metal is input, the reduction process may not be performed in the catalyst supply unit 10 have.

Although the synthesis apparatus of the above embodiment has described a type in which the reactor 20 is laid on a plane, as long as a circulating flow is performed in the reactor, the reactor 20 may be a sloped type, a standing type, or a type that is bent and occupies one or more planes .

The loop type carbon nanotube synthesis apparatus according to the preferred embodiment of the present invention uses a blowing fan to supply energy for circulating flow of catalyst and gases in the reactor, It is also possible to adopt a configuration in which the catalyst and the gases circulate by the gas injection force without installing a fan. The energy forming the circulating flow is then supplied by at least one of hydrogen gas, carbon source and inert gas injected into the reactor. The spraying force of the gas required to form the circulating flow will be determined by preferentially taking into account the specific gravity of the catalyst, and those skilled in the art will be able to easily determine the flow rate of the gas required to circulate the inside of the reactor and calculate the flow rate according to the flow rate The detailed description will be omitted.

The catalyst that reacts with the carbon source may be not only a catalyst metal in a solid state but also a liquid catalyst in which a catalyst metal is dissolved in a solvent, for example, an iron dissolved in an alcohol.

The loop-shaped carbon nanotube synthesizer and the carbon nanotube synthesis method according to the present invention are characterized in that the catalytic metal and the carbon source gas are continuously injected into the loop-shaped reactor to circulate the inside of the reactor, The carbon nanotubes that can not escape and are circulated and synthesized are allowed to escape from the reactor. Therefore, the new catalyst metal is continuously introduced into the reactor and the carbon nanotubes are continuously discharged from the reactor, whereby the yield of carbon nanotube synthesis is improved and mass synthesis is possible.

Claims (10)

A catalyst supply unit for supplying a catalyst; A loop-shaped reactor having an internal space connected to the catalyst supply unit and connected in a loop and having a heater; A gas supply unit having a carbon source tank, a hydrogen gas tank, and an inert gas tank connected to the loop reactor to supply carbon source, hydrogen gas, and inert gas to the loop reactor; A reactor outlet pipe formed in the loop reactor; And And a blowing fan installed inside the loop reactor. delete 2. The looped carbon nanotube synthesizer of claim 1, wherein the reactor outlet tube is connected to the inside of the loop reactor. 2. The fuel cell system according to claim 1, A hydrogen supply pipe to which hydrogen is supplied; A hydrogen discharge pipe through which the hydrogen is discharged; And Wherein a heater is further formed. The method according to any one of claims 1, 3, and 4, Further comprising a cleaning device connected to the reactor discharge pipe to form an air inlet and a gas discharge pipe, and a filter and a suction pump are formed in the gas discharge pipe. A catalyst supply unit for supplying a catalyst; A loop-shaped reactor having an internal space connected to the catalyst supply unit and connected in a loop and having a heater; A carbon source, a hydrogen gas tank, and an inert gas tank connected to the loop-shaped reactor for supplying carbon source, hydrogen gas, and inert gas, wherein the catalyst, the carbon source, the hydrogen gas, and the inert gas A gas supply part for injecting at least one of a carbon source, a hydrogen gas and an inert gas with a spraying force enough to form a circulating flow of the inert gas; And And a reactor outlet tube formed in the loop reactor. A catalyst supply unit for supplying a catalyst; A loop-type first reactor having an internal space connected to the catalyst supply unit and connected in a loop, and having a heater; A first reactor outlet pipe connected to the loop-like first reactor; A loop-like second reactor having an inner space connected to the first reactor discharge pipe and connected in a loop, and having a heater; A second reactor outlet pipe connected to the loop-like second reactor; A gas supply unit connected to the loop-type first reactor and the loop-type second reactor to supply a carbon source gas and an inert gas; And And a blowing fan installed in at least one of the first reactor and the second reactor in the loop. A catalyst supply unit for supplying a catalyst; A loop-type first reactor having an internal space connected to the catalyst supply unit and connected in a loop, and having a heater; A first reactor outlet pipe connected to the loop-like first reactor; A loop-like second reactor having an inner space connected to the first reactor discharge pipe and connected in a loop, and having a heater; A second reactor outlet pipe connected to the loop-like second reactor; And A carbon source tank connected to at least one of the first reactor and the second reactor to supply a carbon source, a hydrogen gas, and an inert gas, a hydrogen gas tank, and an inert gas tank, And a gas supply part for injecting at least one of carbon source, hydrogen gas and inert gas with a spraying force enough to form a circulating flow of the carbon source, the hydrogen gas and the inert gas. Supplying a catalyst, a carbon source, a hydrogen gas, and an inert gas into a loop-shaped reactor having a closed loop inner space and a reactor discharge pipe formed on one side; Synthesizing carbon nanotubes while circulating the catalyst, carbon source, hydrogen gas, and inert gas in one direction; And And discharging the synthesized carbon nanotube through a reactor discharge pipe of the loop reactor. 10. The method of claim 9, further comprising heating the loop reactor to maintain the temperature within the loop reactor at 600 < 0 > C to 1200.

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