KR101819707B1 - Device for manufacturing carbon nanotube aggregate - Google Patents

Abstract

The present invention proposes an apparatus for producing a carbon nanotube aggregate. The apparatus for manufacturing a carbon nanotube aggregate according to an embodiment of the present invention includes: a synthesis furnace having a space for synthesizing a carbon nanotube aggregate; A raw material supply part for supplying the liquid carbon nanotube aggregate raw material into the synthesis furnace; A gas supply unit for supplying a transfer gas into the synthesis furnace; A raw material injection pipe to which a raw material supply unit and a gas supply unit are connected to one end and a synthetic furnace is connected to a lower end; And heating means for heating an internal space of the synthesis furnace, wherein the raw material injection pipe is formed in a curved shape and includes at least one inflection point.

Description

TECHNICAL FIELD [0001] The present invention relates to a device for manufacturing a carbon nanotube aggregate,

The present invention relates to an apparatus for producing a carbon nanotube aggregate.

The carbon nanotube aggregate refers to aggregates of carbon nanotubes, and exists in the form of fibers and films. Also, the preparation of carbon nanotube aggregates is made by mixing polymers with carbon nanotubes to form a composite, and pure carbon nanotubes alone.

In the case of the former, the polymer is dissolved in a solvent or heat and then mixed with the carbon nanotubes in the form of particles to prepare a composite material. The carbon nanotube dispersion technique is a key technology.

The latter method refers to a method of synthesizing carbon nanotubes having a network structure. There are methods of forming an aggregate after synthesizing carbon nanotubes on a substrate and forming aggregates without a substrate. Since the method of using the substrate is a discontinuous process, the production cost is high, and the direct spinning method without using a substrate forms a continuous carbon nanotube aggregate, resulting in a low production cost.

On the other hand, Korean Patent Registration No. 10-1415078 (entitled "Carbon Nanotube Fiber Production Apparatus") relates to a synthetic furnace that provides a space in which carbon nanotube fibers are synthesized inside; A raw material supply part for supplying the liquid carbon nanotube fiber raw material into the inside of the synthesis furnace; A gas supply unit for supplying a transfer gas into the synthesis furnace; A secondary synthetic furnace disposed at an inner upper end of the synthesis furnace in a tubular shape and supplied with a fiber raw material flowing on an inner peripheral surface thereof; A nozzle for spraying the fiber raw material supplied by the raw material supply unit to the inner wall of the auxiliary synthesis furnace; And a heater disposed along the outer periphery of the synthetic furnace.

However, in the conventional apparatus for manufacturing carbon nanotube fibers, it is difficult to improve the homogeneity of carbon nanotube fibers because the thermal energy of the synthesis furnace is directly transferred to the raw material injection portion by using a straight injection tube, .

It is an object of the present invention to provide an apparatus for producing a carbon nanotube aggregate capable of synthesizing a carbon nanotube aggregate having improved uniformity.

It is another object of the present invention to provide a carbon nanotube aggregate production apparatus capable of preventing the nozzles of a raw material supply unit from being damaged by heat.

It is to be understood, however, that the technical scope of the present invention is not limited to the above-described technical problems, and other technical problems may exist.

According to an aspect of the present invention, there is provided an apparatus for producing a carbon nanotube aggregate according to an embodiment of the present invention, including: a synthesis chamber having a space for synthesizing a carbon nanotube aggregate; A raw material supply part for supplying the liquid carbon nanotube aggregate raw material into the synthesis furnace; A gas supply unit for supplying a transfer gas into the synthesis furnace; A raw material injection pipe to which a raw material supply unit and a gas supply unit are connected to one end and a synthetic furnace is connected to a lower end; And heating means for heating an internal space of the synthesis furnace, wherein the raw material injection pipe is formed in a curved shape and includes at least one inflection point.

According to the present invention, the effect of synthesizing a carbon nanotube aggregate having a good uniformity can be greatly improved by using a curved raw material injection tube to buffer the raw material solution.

Further, it is possible to prevent the inner heat energy of the synthesis furnace from directly approaching the raw material supply portion, thereby preventing the nozzle of the raw material supply portion from being damaged by heat.

1 is a perspective view of an apparatus for producing a carbon nanotube aggregate according to an embodiment of the present invention.
2 is a cross-sectional view of an apparatus for producing a carbon nanotube aggregate according to an embodiment of the present invention.
3 is a plan view of a raw material injection tube according to an embodiment of the present invention.
4 is a perspective view of a raw material injection tube according to an embodiment of the present invention.
5 (a) is a photograph of a carbon nanotube aggregate manufactured using a conventional vertical feed pipe, and FIG. 5 (b) is a photograph of a carbon nanotube aggregate manufactured using the curved feed pipe of the present invention. It is a photograph of the tube assembly.
6 is a view showing various embodiments of the raw material injection tube of the present invention.
7 is a graph showing changes in purity and carbon conversion rate of carbon nanotubes according to the number of inflection points of a raw material injection tube according to an embodiment of the present invention.
8 is a graph showing changes in IG / ID in Raman analysis according to temperature of a raw material injection tube according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

The present invention relates to an apparatus for producing a carbon nanotube aggregate.

FIG. 1 is a perspective view of an apparatus for producing a carbon nanotube aggregate according to an embodiment of the present invention, FIG. 2 is a sectional view of an apparatus for producing a carbon nanotube aggregate according to an embodiment of the present invention, and FIG. 4 is a perspective view of a raw material injection tube according to an embodiment of the present invention. FIG. 5 (a) is a plan view of a raw material injection tube according to an example of the present invention. FIG. 5 (b) is a photograph of a carbon nanotube aggregate manufactured using the curved raw material injection tube of the present invention, and FIG. 6 is a view showing various embodiments of the raw material injection tube of the present invention And FIG. 7 is a graph showing changes in purity and carbon conversion rate of carbon nanotubes according to the number of inflection points of a raw material injection tube according to an embodiment of the present invention. FIG. Temperature dependent The graph shows the IG / ID of the change in ten thousand minutes seats

First, an apparatus 100 for manufacturing a carbon nanotube aggregate according to an embodiment of the present invention (hereinafter referred to as a 'apparatus for manufacturing a carbon nanotube aggregate 100') will be described.

1 and 2, a carbon nanotube aggregate production apparatus 100 includes a synthesis furnace 110, a raw material supply unit 120, a gas supply unit 130, a raw material injection pipe 140, and a heating unit 150, .

The method for producing the carbon nanotube aggregate by the manufacturing apparatus 100 according to the present invention can be carried out by the method described in JP-A-2008-0090383. Therefore, detailed description of the production process of the carbon nanotube aggregate is omitted.

The synthesis furnace 110 is provided with a space for synthesizing the carbon nanotube aggregate therein. In addition, although the synthesis furnace 110 may be cylindrical, its shape and size may be variously set according to the needs of the user.

The heating means 150 is disposed on the outer circumferential surface of the synthesis furnace 110 to heat the synthesis furnace 110. Illustratively, the heating means 150 may be, but not limited to, gas heating, electric heating, and the like. In addition, the heating temperature of the heating means 150 may be 800 to 1500 degrees.

The raw material supply unit 120 supplies a raw material for synthesizing the carbon nanotube aggregate to the synthesis furnace 110. At this time, it is preferable that the raw material to be supplied is in a liquid state.

Further, the raw material solution may be composed of a carbon source, a catalyst, and a cocatalyst. The carbon source includes organic solvents such as acetone, ethanol, and butanol, the catalyst includes a metallocene such as ferrocene, and the cocatalyst includes thiophene Thiophene) or carbon disulfide (CS2). The composition of the solution, which is a raw material of carbon, may vary depending on the type of carbon nanotubes to be produced. In general, 0.1 to 4.0 wt% of ferrocene and 0.05 to 3.0 wt% of thiophene are used. can do.

The raw material supply unit 120 may be configured to adjust the amount of the raw material supplied to the synthesis furnace 110 as needed. For this purpose, a flow control valve may be disposed.

The gas supply part 130 supplies a transfer gas for facilitating transfer of the vaporized raw material after the raw material supplied for synthesis of the carbon nanotube aggregate is vaporized. At this time, the transfer gas may be hydrogen gas, and may be supplied at 300 to 4000 sccm.

The gas supply unit 130 is preferably configured to adjust the amount of gas supplied to the synthesis furnace 110 as needed, and a flow control valve may be provided for the gas supply unit 130. At this time, the control of the amount of gas can be performed independently of the control of the feed amount of the raw material.

The raw material supply pipe 140 is connected to the raw material supply unit 120 and the gas supply unit 130 at one end and the synthesis path 110 is connected to the lower end. That is, the raw material solution supplied from the raw material supply unit 120 may be supplied to the synthesis furnace 110 through the raw material injection pipe 140.

The raw material supply unit 120 may include a spraying unit 121 for spraying a liquid carbon nanotube aggregate raw material. That is, the raw material supply unit 120 can spray the raw material solution in a mist state using the spray unit 121 so as to facilitate vaporization and atomization of the raw material solution.

Referring to FIG. 1, the raw material injection tube 140 is formed in a curved shape, and is formed to include at least one inflection point.

In addition, the raw material injection tube 140 may be formed in a spiral shape. That is, as shown in FIG. 4, the raw material injection tube 140 may be formed in a spiral shape along the outer circumferential surface of a cylinder having a predetermined height and radius. Accordingly, it can be confirmed that the raw material injection pipe 140 has a circular shape with a predetermined radius when viewed from above. The ratio between the inner diameter of the material injection tube 140 and the radius of the circle formed by the spiral shape of the material injection tube 140 and the distance between the inlet and the outlet of the material injection tube 140 are appropriately selected, The raw material injection pipe 140 can be designed.

In other words, the raw material injection tube 140 may be formed to be bent on a two-dimensional plane or may be formed into a three-dimensional spiral shape.

1, the raw material injection pipe 140 includes a linear inlet 141 into which the raw material and the transfer gas are introduced, a curved portion 142 formed to extend from the inlet 141 and formed into a curved shape, And a linear outlet portion 143 extending from the curved portion 142 and discharged from the synthesis furnace 110 to the raw material and the transfer gas.

Specifically, the raw material supplied from the raw material supply unit 120 and the transfer gas supplied from the gas supply unit 130 are buffered while passing through the curved portion 142 of the raw material injection pipe 140, A uniform amount of the raw material can be supplied to the inside of the synthesis furnace 110 through the through-

Fig. 5 is a graph showing the relationship between the temperature of the synthesis furnace 110, the temperature of the synthesis furnace 110, the inner diameter of the raw material feed pipe 10 mm, the feed rate of the feedstock 1 is a photograph of a carbon nanotube aggregate manufactured using a linear feed pipe 140 and a curved feed pipe 140 in an experimental environment of an injection rate of 11 ml / h.

Referring to FIG. 5 (a), when a linear raw material injection tube is used, a droplet of the raw material solution may vertically fall into the synthesis furnace 110 before being vaporized in the raw material injection tube, It can be seen that the uniformity is decreased.

5 (b), when the curved raw material injection tube 140 is used, the droplet of the raw material solution is vaporized and atomized inside the raw material injection tube 140, and the vaporized raw material is buffered And a uniform amount of raw material is supplied into the synthesis furnace 110. Accordingly, when the curved raw material injection tube 140 is used, a carbon nanotube aggregate having excellent uniformity can be produced.

Referring to FIG. 6, the raw material injection pipe 140 may have a curved shape as well as a spiral structure. The raw material injection pipe 140 may have at least one inflection point. That is, as shown in Fig. 6 (a), it may have a curved shape having one inflection point, an S-shaped curved shape having two inflection points as shown in Fig. 6 (b) It is possible to have a curved shape having three inflection points as shown in Fig. 6 (c). However, the number of inflection points of the raw material injection tube 140 may be four or more.

Referring to FIG. 6, as the number of inflection points increases, the buffering effect is further improved and the purity and homogeneity of the carbon nanotube aggregate are increased.

In other words, as the inflection point of the material injection tube 140 is increased, the buffer effect is further improved inside the material injection tube 140, and the carbon solution is supplied more uniformly into the synthesis furnace 110, The purity and carbon conversion of the carbon nanotube aggregate increases.

In addition, it is preferable to appropriately select the inner diameter, the length, and the bent angle of the curved portion 142 of the raw material injection pipe 140 so that the raw material injection pipe 140 is efficiently vaporized from the inside. By way of example, the curved angle of the curved portion 142 may be between 90 degrees and 180 degrees.

In other words, when the inner diameter of the raw material injection pipe 140 is small, the raw material solution can be injected into the synthesis furnace 110 without vaporization, and when the inner diameter of the raw material injection pipe 140 is large, There is a problem that this is not smooth. Illustratively, the inner diameter of the feed inlet can be between 1 and 50 mm, and preferably about 10 mm.

Further, the longer the length of the raw material injection tube 140 is, the more efficient the buffer acts, but the heat enough to vaporize the raw material solution in the synthesis furnace 110 is not transferred to the raw material injection tube 140 The raw material solution flows on the inner wall of the raw material injection pipe 140 in the liquid state, and the catalyst is deposited on the inner wall, so that the quality of the carbon nanotube aggregate is not constant. Illustratively, referring to FIG. 4, the distance L from one end to the lower end of the raw material injection pipe 140 may be 100 to 1000 mm, and preferably 300 mm. The distance L from one end of the raw material injection pipe 140 to the lower end of the raw material injection pipe 140 is a straight line distance from the plane where one end of the raw material injection pipe 140 is located to the plane where the lower end of the raw material injection pipe 140 is located .

When the bent angle of the curved portion 142 of the raw material injection pipe 140 is large, the thermal energy in the synthesis furnace 110 flows through the raw material injection pipe 140 to damage the injection portion 121 If the bent angle of the curved portion 142 of the raw material injection pipe 140 is small, the raw material solution collides with the inner wall of the raw material injection pipe 140, have.

Referring to FIG. 1, the carbon nanotube aggregate production apparatus 100 may further include a tube heating unit 160 for heating the interior of the raw material injection tube 140. For example, the tube heating unit 160 may be a band heater that surrounds the outer periphery of the raw material injection tube 140.

Also, the tube heating unit 160 may heat the inside of the material injection tube 140 at 60 to 200 degrees, and it is preferable that the tube heating unit 160 is appropriately selected according to the vaporization point of the carbon source to be supplied.

Referring to FIG. 8, the temperature of the raw material injection tube 140 was set to 20 to 80 degrees, and the change in the IG / ID, which is an index indicating the degree of crystallization of the carbon nanotube aggregate, was analyzed.

8, it can be seen that the IG / ID gradually increases as the temperature of the raw material injection tube 140 increases. It is preferable that the raw material injection tube 140 has an IG / ID of 4.0 or more at 60 to 80 degrees It can be seen that it is stable. Also, the IG / ID is the largest at 80 ° C above the vaporization point of acetone.

In other words, the temperature of the raw material injection tube 140 can be appropriately selected according to the vaporization point of the carbon source to be supplied. Illustratively, when the carbon source as described above is acetone, the temperature of the feed tube 140 may be 80 degrees higher than the vaporization point of acetone. In addition, when the carbon source is 1-butanol, the raw material injection tube 140 can be heated to 120 degrees higher than the vaporization point of 1-butanol.

Hereinafter, an operation method of the carbon nanotube composite manufacturing apparatus 100 will be described.

The operator operates the carbon nanotube aggregate production apparatus 100.

It is preferable that the synthesis furnace 110 and the material injection tube 140 are preheated by operating the heating means 150 and the tube heating unit 160 in operation of the apparatus 100 for producing a carbon nanotube aggregate.

Thereafter, the raw material solution used for producing the carbon nanotube aggregate is supplied through the raw material supply unit 120, and the transfer gas is supplied through the gas supply unit 130. At this time, the raw material solution may be injected into the raw material injection pipe 140 through the injection part 121.

At this time, the raw material solution injected into the raw material injection pipe 140 preheated to a predetermined temperature is vaporized and atomized, so that a uniform amount of raw material can be supplied into the synthesis furnace 110.

The injection part 121 injects the raw material into the synthesis furnace 110 through the raw material injection pipe 140 without spraying directly into the interior of the synthesis furnace 110, It is possible to prevent direct contact with the carcass to prevent damage.

The vaporized raw material supplied into the synthesis furnace 110 can be synthesized into a carbon nanotube aggregate while being transported together with the transfer gas.

[Example]

Next, acetone was used as a carbon source as an example showing conditions for synthesizing carbon nanotube aggregates.

The temperature of the synthesis furnace 110 was 1200 占 폚, the inner diameter of the raw material injection tube 140 was 10 mm, and the temperature of the synthesis furnace 110 was set at 100 占 폚.

The solution synthesized under the above conditions was fed into the synthesis furnace 110 at a rate of 11 ml / h, and a curved feed pipe 140 was used.

5 (b) is an optical microscope photograph of the carbon nanotube aggregate produced under the above conditions. Thus, it can be seen that the carbon nanotube aggregate produced through the apparatus 100 for producing a carbon nanotube aggregate of the present invention has excellent uniformity.

Referring to FIG. 7, the carbon nanotube aggregate production apparatus 100 has a carbon conversion rate of about 1.2% when using the raw material injection tube 140 having three inflection points, and a carbon nanotube aggregate Can be produced.

In addition, the distance from one end to the lower end of the raw material injection pipe 140 may be 300 mm.

In addition, when the temperature of the material injection tube 140 is heated to 80 ° C. by the tube heating unit 160, the carbon nanotube aggregate production apparatus 100 can have a very high IG / ID of about 4.5. This result is possible because the raw material solution is vaporized in the raw material injection tube 140 and the vaporized raw material is supplied to the synthesis furnace 110 and synthesized.

The carbon nanotube aggregate produced by the apparatus according to the present invention can be applied to various fields such as electromagnetic wave shielding, electromagnetic wave absorption, sensor, battery, medical use, power cable, smart clothing, field emission device, And can be used in various applications such as a battery electrode, a piezoelectric element, and an ultra lightweight composite material.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

100: Carbon nanotube aggregate manufacturing apparatus
110:
120: raw material supply unit 121:
130: gas supply unit
140: raw material injection tube 141: inlet part
142: Curved portion 143:
150: Heating means
160: tube heating section

Claims (8)

In a carbon nanotube aggregate production apparatus,
A synthetic furnace having a space for synthesizing the carbon nanotube aggregate therein;
A raw material supply unit for supplying a liquid carbon nanotube aggregate raw material into the synthesis furnace;
A gas supply unit for supplying a transfer gas into the synthesis furnace;
A raw material injection pipe connected to the raw material supply part and the gas supply part at one end thereof and connected to the synthesis path at a lower end thereof and to vaporize the liquid carbon nanotube aggregate raw material;
A pipe heating unit heating the inside of the raw material injection pipe; And
And heating means for heating the inner space of the synthesis furnace,
The raw material injection pipe
Wherein the carbon nanotube aggregate is formed in a spiral shape and is formed to include at least one inflection point.
delete The method according to claim 1,
The raw material injection pipe
The distance from one end to the lower end is 100 to 1000 mm,
Wherein the inner diameter is 1 to 50 mm.
The method according to claim 1,
The raw material injection pipe
A straight inlet portion through which the raw material and the transfer gas are introduced,
A curved portion extending from the inlet portion and formed in a curved shape; And
And a rectilinear outlet portion extending from the curved portion and discharging the raw material and the transfer gas to the synthesis furnace.
The method according to claim 1,
Wherein the raw material supply part includes a spray part for spraying a liquid carbon nanotube aggregate raw material.
delete The method according to claim 1,
The tube heating section
Wherein the inside of the raw material feed pipe is heated from 60 to 200 degrees.
The method according to claim 1,
Wherein the raw material supply unit and the gas supply unit are configured to be adjustable in amount of supply.

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