KR101981675B1 - Apparatus for manufacturing CNT and Method of manufacturing CNT using the same - Google Patents

Abstract

The present invention relates to an apparatus for manufacturing carbon nanotubes and a method for manufacturing carbon nanotubes using the same. The apparatus for manufacturing carbon nanotubes according to the present invention comprises: a reactor including a reaction space; a heating unit for heating the reaction space; and a supply unit for supplying a raw material to the reaction space, wherein the supply unit comprises: an injection tube through which the raw material passes and in which an outlet is located in the reaction space; and a cooling portion at least partially surrounding at least a portion of the injection tube in the reaction space. According to the present invention, provided are: the apparatus for manufacturing carbon nanotubes which stably and continuously feeds the raw material into the reactor; and the method for manufacturing carbon nanotubes using the same.

Description

TECHNICAL FIELD The present invention relates to an apparatus for manufacturing carbon nanotubes and a method for manufacturing carbon nanotubes using the CNTs.

The present invention relates to an apparatus for manufacturing carbon nanotubes and a method for manufacturing carbon nanotubes using the same, and more particularly, to an apparatus for manufacturing carbon nanotubes that stably and continuously feeds a raw material into a reactor and a method for manufacturing carbon nanotubes ≪ / RTI >

Carbon nanotubes are a kind of carbon isotope, which is a structure in which graphene is dried in a cylindrical shape and has a diameter of several nm. Due to its excellent mechanical and physical properties, it has been actively studied in academia. Its tensile strength is tens GPa, electrical conductivity is 10,000 S / cm, and thermal conductivity is 6,600 W / mK.

Carbon nanotubes are produced by introducing a raw material such as a carbon precursor, a catalyst precursor and / or a cocatalyst precursor into a reactor. However, since the raw materials to be supplied to the reactor have different vaporization temperatures, it is difficult to supply stable carbon nanotubes and it is difficult to continuously synthesize high-quality carbon nanotubes.

To solve this problem, a method has been developed in which each raw material is vaporized using a vaporizing device for each raw material, and then introduced into the reactor. However, in this method, it is difficult to quantitatively confirm the mixing ratio of the raw materials, and there is a problem that the device configuration is complicated.

Japanese Patent Application Laid-Open No. 2009-137805 (published on June 25, 2009)

An object of the present invention is to provide an apparatus for manufacturing carbon nanotubes which stably and continuously feeds a raw material into a reactor and a method for manufacturing carbon nanotubes using the same.

The object of the present invention is to provide an apparatus for producing carbon nanotubes, comprising: a reactor including a reaction space; A heating unit for heating the reaction space; And a supply unit for supplying a raw material to the reaction space, the supply unit including an injection tube through which a raw material is passed and an outlet is located in the reaction space; And a cooling section at least partially surrounding at least a portion of the injection tube within the reaction space.

The reaction space may be elongated in the horizontal direction.

The outlet of the injection tube may protrude from the cooling section.

The outlet of the injection tube may protrude from the cooling part by 1 cm to 4 cm.

The supply unit may be provided so as to be capable of changing an outlet position of the injection tube.

The supply unit may be provided so as to be capable of changing the protruding distance of the outlet of the injection tube.

According to another aspect of the present invention, there is provided a method of manufacturing a carbon nanotube, comprising: injecting at least two raw materials having different boiling points into the reaction space through an injection tube extending into the reaction space; And producing the carbon nanotube in the reaction space, wherein at least a part of the injection tube located in the reaction space is cooled by keeping the raw material in a liquid state.

The reaction space may be elongated in the horizontal direction.

The cooling may be performed through a cooling part surrounding the injection tube and at least a part of which is located in the reaction space, and an outlet of the injection tube may protrude from the cooling part.

The outlet of the injection tube may protrude from the cooling part by 1 cm to 4 cm.

And adjusting an outlet position of the injection tube before the injection.

The cooling may be performed at 20 ° C or lower than the lowest boiling point of the at least two raw materials.

According to the present invention, there is provided an apparatus for manufacturing carbon nanotubes which stably and continuously feeds a raw material into a reactor, and a method for manufacturing carbon nanotubes using the same.

1 shows an apparatus for manufacturing a carbon nanotube according to an embodiment of the present invention,
2 is a three-dimensional schematic view of an apparatus for manufacturing a carbon nanotube according to an embodiment of the present invention,
3 is a view for explaining a method of manufacturing a carbon nanotube using an apparatus for manufacturing a carbon nanotube according to an embodiment of the present invention,
4A and 4B show the distribution of IG / ID of carbon nanotubes prepared in the experimental example of the present invention.

The carbon nanotubes referred to in the present specification include carbon nanotube fibers and the like.

In the present invention, raw materials used for synthesizing carbon nanotubes include not only substances containing a carbon atom (carbon source) and a catalyst containing a metal, additives including sulfur, but also all materials used for the reaction It can mean.

The present invention provides an apparatus and a method for simultaneously supplying various raw materials in a liquid or solid state to a reactor stably. As a result, it is possible to solve the unstable supply problem caused by irregular vaporization of the raw materials by the heat of the reactor, simply and economically. In the present invention, various raw materials in liquid or solid state are simultaneously vaporized in the reactor to produce high-quality carbon nanotubes.

Hereinafter, an apparatus for manufacturing a carbon nanotube according to the present invention will be described with reference to FIGS. 1 and 2. FIG.

2 is a three-dimensional schematic view of an apparatus for manufacturing a carbon nanotube according to an embodiment of the present invention.

The manufacturing apparatus 1 includes a reactor 10, a cover 20, a heater 30, a supply unit 40, and a transfer gas inlet 51 and a transfer gas outlet 52.

The reactor 10 forms a reaction space 11 therein and has a long cylindrical shape. Accordingly, the reaction space 11 is elongated in one direction. In another embodiment, the form of the reactor 10 and the reaction space 11 may vary widely.

The reactor 10 is arranged such that the reaction space 11 is elongated in the horizontal direction, but in other embodiments it can be arranged to extend in the vertical direction.

The cover 20 covers one side of the reactor 10 and has a through hole for the supply unit 40 and the inflow and outflow of the transfer gas. In another embodiment, the cover 20 may be integrally formed with the reactor 10, and the cover 20 may be provided with additional through holes for entering and exiting the measuring instrument.

The heater (30) is formed around the reactor (10). By the position of the heater 30, the temperature of the reaction space 11 increases as the distance from the cover 20 increases.

The supply unit 40 supplies the raw material of the carbon nanotubes to the reaction space 11. The raw material may comprise a carbon source precursor, a catalyst precursor and / or a cocatalyst precursor. These precursors may be liquid or solid at room temperature.

The supply unit 40 includes an injection pipe 41 and cooling units 42 and 43 extending from the outside of the reactor 10 into the reaction space 11. The cooling units 42 and 43 include a cooling body 42 and a cooling space 43. The cooling space 43 surrounds the injection tube 41, and the cooling space 43 can perform cooling while the cooling fluid flows. As the cooling fluid, water may be used although not limited thereto.

The cooling temperature of the cooling space 43 may be controlled to be lower than the lowest boiling point of the raw material, for example, 20 ° C or higher, 30 ° C or 50 ° C or lower than the lowest boiling point. Specifically, the cooling temperature of the cooling space 43 may be 0 ° C to 30 ° C, 10 ° C to 30 ° C, or 10 ° C to 20 ° C.

A part of the cooling sections 42 and 43 is located in the reaction space 11 so that a part of the injection tube 41 located in the reaction space 11 is surrounded by the cooling sections 42 and 43. The injection tube 41 has a projecting end 41a that is not surrounded by the cooling part 40 and the projecting end 41a has an outlet through which the raw material is discharged into the reaction space 11. The length B of the projecting end 41a may be 1 cm to 4 cm or 2 cm to 3 cm. If the length B of the protruding end portion 41a is 1 cm or less, the raw material may not vaporize during the discharge and may be dropped from the outlet of the injection tube 41. On the other hand, if the length B of the projecting end portion 41a is 4 cm or more, non-uniform vaporization may occur in the projecting end portion 41a.

The supply unit 40 is provided so as to be movable laterally along the adjustment direction in the drawing. As a result, the length A of the cooling portions 42 and 43 located in the reaction space changes along the adjustment direction. The length A of the cooling units 42 and 43 located in the reaction space can be controlled so that the raw material is discharged from the injection tube 41 at a desired temperature. have.

The supply unit 40 is also provided so as to change the relative positions of the cooling units 42, 43 and the injection pipe 41. Whereby the length B of the projecting end portion 41a also changes along the adjustment direction.

The cooling space 43 has an inlet 43a through which the cooling fluid flows and an outlet 43b through which the cooling fluid flows. Although not shown, the manufacturing apparatus 1 may further comprise a cooler and / or a pump for maintaining and circulating the temperature of the cooling fluid.

The transfer gas is supplied to the reactor through the transfer gas inlet portion 51 and discharged from the reactor via the transfer gas outlet portion 52.

Hereinafter, a method for producing carbon nanotubes according to the present invention will be described with reference to FIG.

First, the length (A) of the cooling portions (42, 43) and the length (B) of the projecting end portion (41a) located in the reaction space are adjusted. The length (A, B) is controlled in consideration of the desired carbon nanotube type, the desired production amount, the type of the raw material to be introduced and / or the shape and temperature of the reactor 10.

Next, the raw material is supplied through the injection tube 41 and the transfer gas is injected through the transfer gas injecting part 51 to produce carbon nanotubes. In this process, the temperature of the reaction space is adjusted to a desired temperature by the heater 30 and the cooling temperature of the cooling units 42 and 43 is also controlled to a desired temperature.

By the action of the cooling portions 42 and 43, the raw material is supplied to a considerable position of the reaction space while maintaining the liquid state. Accordingly, when the raw material is discharged into the reaction space, substantially all of the raw materials are vaporized and the reaction is started.

Since the raw material is supplied while maintaining the liquid state, vaporization in the injection tube 41 is minimized and stable supply of the raw material is possible. In addition, it is easy to control the injection amount of the raw material.

The produced carbon nanotubes are discharged from the reactor through the transfer gas discharge portion 52.

Hereinafter, the present invention will be described in detail by way of examples.

The raw materials used in the experiment were 97.97% by weight of acetone, 1.56% by weight of ferrocene and 0.71% by weight of thiophene. The boiling points are 56 ° C for acetone, 249 ° C for ferrocene, and 84 ° C for thiophene.

The maximum temperature in the reaction space 11 was 1170 캜 and the cooling temperature was 15 캜. The flow rate of the hydrogen gas as the transfer gas was 3000 sccm.

The length A of the cooling units 42 and 43 located in the reaction space was 18.5 cm and the length B of the protruding end 41a was 2 cm. The length of the reactor was 120 cm and the inside diameter was 5.4 cm. The inner diameter of the injection tube 41 was 2 mm.

In the comparative example, the raw material was supplied in a state in which the cooling portions 42 and 43 were not provided.

4A and 4B show the distribution of IG / ID of carbon nanotubes prepared in the experimental example of the present invention. 4A shows the data of the embodiment, and FIG. 4B shows the data of the comparative example.

4A and 4B show data obtained by measuring Raman at various positions of the synthesized carbon nanotubes. Referring to FIG. 4A, it can be seen that the IG / ID is about 9 on the average in the embodiment and there is almost no numerical deviation according to the position. These results indicate that high-quality carbon nanotubes can be obtained with uniform quality according to the embodiment. On the other hand, FIG. 4B shows that the IG / ID is low at an average of about 4.2 in the comparative example, and the deviation according to the position is also very severe.

The difference is that in the embodiment, the raw material material stably maintains the liquid state in the most part of the injection tube 41 by cooling and vaporizes simultaneously at the time of discharge, while in the comparative example, the injection tube 41, which is located in the reaction space 11, The supply of raw materials was unstable due to uneven vaporization.

Table 1 shows the relationship between the length A of the cooling portions 42 and 43 and the length B of the projecting end portion 41a in the reaction space under the conditions of the above experimental example, And observing the state of the raw material to be discharged.

In Table 1, " 1 " indicates that the raw material falls into droplets, " 2 " indicates continuous unstable discharge, " 3 " indicates occasionally unstable discharge, " 4 & Is discharged.

As shown in Table 1, when A is 16.5 cm and B is 2 cm, the discharge is steadily and stably discharged. The results in Table 1 may vary depending on the raw material and the reactor conditions.

<Table 1>

Claims (12)

In an apparatus for producing carbon nanotubes,
A reactor comprising a reaction space;
A heating unit for heating the reaction space;
And a supply unit for supplying a raw material to the reaction space,
Wherein the supply unit comprises: an injection tube through which the raw material passes and an outlet is located in the reaction space; And
At least a portion of which surrounds at least a portion of the injection tube within the reaction space,
The reaction space is elongated in the horizontal direction,
And an outlet of the injection tube is protruded from the cooling part. delete delete The method according to claim 1,
And the outlet of the injection tube is protruded by 1 cm to 4 cm from the cooling part. The method according to claim 1,
Wherein the supply unit is provided so as to be capable of changing an outlet position of the injection tube. The method according to claim 1,
Wherein the supply unit is provided so as to be capable of changing the protruding distance of the outlet of the injection tube. In a method for producing a carbon nanotube,
Injecting at least two raw materials having different boiling points into the reaction space through an injection tube extending into the reaction space; And
And preparing the carbon nanotube in the reaction space,
Wherein at least a portion of the injection tube located in the reaction space is cooled to maintain the raw material liquid state,
The reaction space is elongated in the horizontal direction,
Said cooling being carried out through a cooling section which surrounds said injection tube and which at least part is located in said reaction space,
And the outlet of the injection tube protrudes from the cooling part. delete delete 8. The method of claim 7,
And the outlet of the injection tube is protruded by 1 cm to 4 cm from the cooling part. 8. The method of claim 7,
Further comprising the step of adjusting an exit position of the injection tube before the injection. 8. The method of claim 7,
Wherein the cooling is performed at a temperature lower than the lowest boiling point of the at least two raw materials by 20 ° C or more.

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