KR20150039072A

KR20150039072A - Carbon nanotube and method for preparing the same

Info

Publication number: KR20150039072A
Application number: KR20140038825A
Authority: KR
Inventors: 배승용; 이윤택; 김병열; 김중인; 안성희
Original assignee: 제일모직주식회사
Priority date: 2013-09-30
Filing date: 2014-04-01
Publication date: 2015-04-09

Abstract

The present invention relates to a carbon nanotube and a method for producing the same, wherein the carbon nanotube includes one or more elements of aluminum (Al), magnesium (Mg), and silicon (Si); and one or more metals of cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn), and molybdenum (Mo). An intensity ratio (ID/IG) by Raman spectroscopy is 1.1 or less, and C purity is 98% or more. The purity and yield of the carbon nanotube can be adjusted through a change in a metal content of a catalyst, and a post-refining process is not needed.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbon nanotube,

The present invention relates to carbon nanotubes and a method of manufacturing the same.

The carbon nanotubes (CNTs) discovered by Iijima in 1991 have a hexagonal honeycomb structure consisting of three carbon atoms adjacent to one carbon atom, and these hexagonal structures are repeatedly formed into cylindrical shapes or tubes It is.

Since the discovery of carbon nanotubes (CNTs), a large number of articles have been published and patent applications are increasing, and many theoretical studies and development of industrial applications have been attempted. In particular, carbon nanotubes (CNTs) are known as perfect new materials with excellent mechanical properties, electrical selectivity, excellent field emission characteristics, high-efficiency hydrogen storage medium characteristics, polymer complexes and the like.

Carbon nanotubes (CNTs) are mainly manufactured by arc discharge, laser ablation, and chemical vapor deposition. Depending on their shape, a single wall, a double wall (double wall), and multi-wall carbon nanotubes (CNT). Despite the various synthesis methods and structures, there are still many limitations in producing high-yield carbon nanotubes, high yields, and high purity carbon nanotubes.

Therefore, in recent years, researches on new synthetic techniques capable of synthesizing a large amount of carbon nanotubes at one time as well as appropriate catalyst synthesis are actively carried out in order to synthesize carbon nanotubes having high purity and high yield. Among the various synthesis methods, the thermochemical vapor deposition method is simple in apparatus and has an absolutely advantageous characteristic in mass synthesis. The thermochemical vapor deposition method can be broadly classified into a fixed bed reactor and a fluidized bed reactor depending on the synthesis method.

Among these, a fixed bed reactor can synthesize carbon nanotubes without being greatly influenced by the shape or size of the metal carrier, but there is a limitation in the space in the reactor for synthesizing high yield carbon nanotubes at a time. The other is a fluidized-bed reactor in which the reactor stands vertically and can synthesize carbon nanotubes more easily than fixed-bed reactors.

Fluidized bed reactors are capable of continuously synthesizing large amounts of carbon nanotubes at a time as compared with fixed bed reactors, and thus many studies are underway. However, unlike a fixed-bed reactor, a fluidized bed reactor has a problem in that it is required to keep the shape and the size of the metal slurry uniformly in order to uniformly fluidize the slurry.

Korean Patent Publication No. 2007-7010697 discloses a catalyst for synthesizing carbon nanotubes with a high yield by using a catalyst containing Mn, Co and a supporting material. However, the preparation process of the catalyst is complicated by using a precipitation method, It has a problem in that it is not easy to apply to the handling and continuous process of the particles because of the shape of the uneven catalyst.

Carbon nanotubes require high purity carbon nanotubes in order to expand their applications. Especially, recently, carbon nanotubes are expected to be used as a conductive material and an auxiliary additive for a secondary battery, but impurities due to the metal catalyst contained in the carbon nanotube may affect the stability of the secondary battery. As a stumbling block.

Carbon 41, 2585-2590 (2003) discloses a process for removing impurities by high temperature heat treatment in order to increase the purity of carbon nanotubes. In addition, a lot of researches such as a process of treating with strong acid have been carried out come. However, the method of improving the purity of carbon nanotubes through the introduction of such a post-treatment process deteriorates the intrinsic properties of the carbon nanotubes when the impurities are removed. In addition, it is difficult to apply carbon nanotubes to a secondary battery due to an increase in manufacturing cost due to the application of a post-treatment process.

Accordingly, the present inventors have developed a supported catalyst and a carbon nanotube for synthesizing carbon nanotubes which are high in purity, excellent in yield and do not require a post-treatment purification process.

It is an object of the present invention to provide a high purity carbon nanotube.

It is another object of the present invention to provide a method for producing carbon nanotubes that does not require a post-treatment step.

It is another object of the present invention to provide a method for producing carbon nanotubes having excellent synthesis yield.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention is a nitride semiconductor device comprising at least one element selected from aluminum (Al), magnesium (Mg), and silicon (Si); And at least one metal selected from the group consisting of cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn) and molybdenum (Mo), wherein the intensity ratio (ID / IG) To provide a carbon nanotube having a purity of 98% or more.

The carbon nanotube may include 20 to 2,000 ppm of aluminum (Al), magnesium or silicon, 40 to 9,000 ppm of cobalt (Co), and 40 to 9,000 ppm of manganese (Mn).

The carbon nanotubes may have an average diameter of 10 to 35 nm.

Another object of the present invention is to provide a process for producing a metal catalyst comprising at least one metal catalyst selected from the group consisting of Co, Ni, Fe, Mn and Mo; And at least one carrier selected from the group consisting of aluminum oxide, magnesium oxide, and silica, and to provide a supported catalyst for hollow carbon nanotube synthesis.

The supported catalyst may have an average particle diameter of 10 to 500 mu m.

The supported catalyst may have the following molar ratio:

(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y

(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0)

The supported catalyst may have a sphericity of 0.1 to 1.

Yet another aspect of the present invention provides a method for preparing a catalyst, comprising: preparing a catalyst aqueous solution; Spraying the catalyst aqueous solution with a droplet; And firing the sprayed droplets, wherein the catalyst aqueous solution comprises at least one metal catalyst selected from the group consisting of Co, Ni, Fe, Mn and Mo; And at least one carrier selected from the group consisting of aluminum oxide, magnesium oxide, and silica.

The catalyst aqueous solution may have the following molar ratio.

(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y

(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0)

The droplet size of the catalyst aqueous solution sprayed in the spraying step may be 10 to 1000 mu m.

The catalyst aqueous solution may further include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), or an epoxy polymer as a polymer binder.

The firing step may be a heat treatment at 450 to 650 ° C.

Another aspect of the present invention relates to a method for producing carbon nanotubes using the supported catalyst.

The carbon nanotubes may be prepared by charging the supported catalyst into a furnace, and then injecting a carbon source at 650 to 750 ° C to synthesize carbon nanotubes for 40 to 90 minutes.

The carbon source may be ethylene, methane, or LPG.

The production method of carbon nanotubes may be 80 to 200 (g _CNT / g _catalyst ).

The carbon nanotube according to the present invention has a high purity, and its preparation method does not require a post-treatment purification step and has excellent synthesis yield.

FIG. 1 is a graph showing synthesis yields of carbon nanotubes synthesized over time according to one embodiment of the present invention.
FIG. 2 is a Raman spectroscopic graph of carbon nanotubes synthesized according to Example 1. FIG.
FIG. 3 is a Raman spectroscopic graph of carbon nanotubes synthesized according to Comparative Example 1. FIG.
FIG. 4 is a graph showing a thermogravimetric analysis (TGA) of carbon nanotubes synthesized according to Example 4. FIG.

Carbon nanotube

One aspect of the present invention relates to carbon nanotubes. In the present invention, the carbon nanotubes are catalyst-carbon nanotube aggregates synthesized on a supported catalyst and containing a metal component of the supported catalyst.

In one embodiment of the present invention, the carbon nanotubes include at least one element selected from aluminum (Al), magnesium (Mg), and silicon (Si); And at least one metal selected from the group consisting of cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn) and molybdenum (Mo), wherein the intensity ratio (ID / IG) The purity may be greater than 98%.

The carbon nanotube may include 20 to 2,000 ppm of aluminum (Al), magnesium or silicon, 40 to 9,000 ppm of cobalt (Co), and 40 to 9,000 ppm of manganese (Mn). The content of the metal contained in the carbon nanotubes can be measured using, for example, ICP-OES (Inductively Coupled Plasma Optic Emission Spectrometer) equipment.

The carbon nanotubes may have an average diameter of 10 to 35 nm, and more specifically 12 to 30 nm.

In the carbon nanotube of the present invention, the degree of surface crystallinity can be relatively determined by measuring the intensity ratio (ID / IG) of the Raman spectroscopic graph to determine the degree of surface crystallinity.

Referring to FIG. 2, carbon nanotubes in the Raman spectroscopic graph can be observed at a peak near 1340 cm ^-1 , which is known as D-mode, and a peak near 1580 cm ^-1 , which is referred to as G-mode.

Each peak is a peak appearing in a carbon material such as a typical graphite material. The D mode peak is a characteristic peak showing a bond in the crystal. The G mode peak is a characteristic peak that is common in a typical graphite material. Means vibrating in opposite directions to atoms. That is, it is an index indicating that the hexagonal crystal structure is well arranged without defects. Therefore, the intensity value (ID) of the D mode peak and the intensity ratio (ID / IG) value of the intensity value (IG) of the G mode peak are measured. The carbon nanotubes prepared from the supported catalyst containing Co and Mn of the present invention have an intensity ratio (ID / IG) of 1.1 or less by Raman spectroscopy.

The carbon nanotube according to the present invention has a C purity of 98% or more, so that there is almost no impurity, and a post-treatment step for removing impurities is not required. Therefore, the carbon nanotube according to the present invention can be used as a conductive material for a secondary battery and an auxiliary additive.

Supported catalyst

The present invention provides a supported catalyst for synthesizing carbon nanotubes. The supported catalyst has a hollow type in which a metal catalyst is supported on a support and hollow is formed.

In order to synthesize carbon nanotubes of high purity and excellent yield, the supported catalyst of the present invention contains a metal catalyst containing Co and Mn in an oxide support, and a metal catalyst is added to the surface and inside of the supported catalyst . In one embodiment, the oxide carrier may be aluminum oxide (Al ₂ O ₃ ), magnesium oxide or silica, and preferably aluminum oxide.

The present invention relates to a supported catalyst comprising a metal catalyst and a support containing the metal catalyst, wherein the metal catalyst is selected from the group consisting of Co, Ni, Fe, Mn and Mo and specifically Co and Mn, Specifically in the form of oxides or hydrates of Co and Mn. When it is applied to the conductive material of the secondary battery, it is advantageous not to include Fe and Mo as the metal catalyst.

In one embodiment, the porous support catalyst may have the following molar ratio.

(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y

(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0)

The synthesis yield is excellent within the above molar ratio range, the C purity is high, no post-treatment is required, the crystallinity is excellent, and the diameter of the carbon nanotubes is large.

The supported catalyst has a particle diameter of 10 to 500 탆, and the contents of metal catalysts Co and Mn are controlled to synthesize single wall carbon nanotubes (SWNT), double wall carbon nanotubes (DWNT) or multiwall carbon nanotubes (MWNT) .

The supported catalyst may have a sphericity of 0.1 to 1.

Method for preparing supported catalyst

A method for preparing a supported catalyst according to an embodiment of the present invention includes: preparing a catalyst aqueous solution; Spraying the catalyst aqueous solution with a droplet; And firing the sprayed droplets, wherein the catalyst aqueous solution comprises at least one metal catalyst selected from the group consisting of Co, Ni, Fe, Mn and Mo; And at least one carrier selected from the group consisting of aluminum oxide, magnesium oxide, and silica.

The metal catalyst may have the form of Co (NO ₃ ) ₂ and Mn (NO ₃ ) ₂ or an oxide or hydrate of Co and Mn. For example, Cobalt nitrate nonahydrate. The carrier may be aluminum oxide, magnesium oxide, silica, or the like, but is not limited thereto. These may be used alone or in combination of two or more. Preferably, aluminum oxide may be used.

(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y

(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0)

The metal catalyst and the carrier are each dissolved in water and mixed in an aqueous liquid phase. The catalyst aqueous solution in which the metal catalyst and the support are mixed is completely dissociated by stirring. If necessary, molybdenum (Mo) activators such as Ammonium Molybate tetrahydrate may be added to prevent agglomeration of nanoscale metal catalysts during sintering at high temperatures. Activation systems such as citric acid and the like may also be used.

The catalyst aqueous solution may further include polyvinyl alcohol (PVA), polyvinyl chloride (PVC), or an epoxy-based polymer as a polymer binder in order to prevent particles from being broken during sphere formation and firing.

The catalyst aqueous solution in which the metal catalyst and the support are mixed is then formed into a spherical particle form by a spray drying method. By the spray drying method, a supported catalyst having a uniform spherical shape and size can be produced, and mass production can be achieved. Spray drying causes spraying of the feedstock in a hot dry gas and drying takes place almost instantaneously. The reason why the drying takes place very quickly is because the feed is atomized by the atomizer and the surface area becomes very large.

In one embodiment, the droplet size of the catalyst aqueous solution sprayed in the spraying step may be 10 to 1000 mu m. Within the above range, the particle diameter of the supported catalyst can be controlled within the range of the specific examples described below.

In one embodiment, the supported catalyst may have a particle size of 10 to 500 탆, and the content of the metal catalysts Co and Mn may be controlled to control the concentration of the single wall carbon nanotube (SWNT), the double wall carbon nanotube (DWNT) (MWNT) can be synthesized.

In one embodiment, the supported catalyst may have a sphericity of 0.1 to 1.

The spray drying equipment affects the size of the catalyst powder formed depending on the density of the solution, the amount of spray, the rotation speed of the atomizer disk, and the like.

The spraying method includes a spraying method using a nozzle and a method in which a water droplet is formed by the rotation of the disk using a disk and sprayed. In a preferred embodiment, a disk type is applied to produce a supported catalyst powder of a more uniform size. The disk type may be a vane type or a pin type. The particle size and distribution can be controlled according to the rotation speed of the disk, the amount of the solution, and the density.

The catalyst powder prepared by spray drying is heat treated through firing. Through such a calcination process, a supported catalyst of spherical particles having crystallization as a supported catalyst and having pores on its surface is produced. At this time, the diameter and properties of the carbon nanotubes can be controlled according to the temperature and time for calcining the catalyst powder. The firing step may be a heat treatment at 450 to 650 ° C.

Method for manufacturing carbon nanotubes

The carbon nanotube manufacturing method of the present invention can synthesize carbon nanotubes by TCVD (thermal chemical vapor deposition) using the supported catalyst. The supported catalyst may be charged into a reactor and then injected with a carbon source at a temperature of 650 to 800 ° C under atmospheric pressure. More specifically, after the supported catalyst is charged into the reactor, the carbon source may be injected at a temperature of 650 to 750 ° C under atmospheric pressure to produce carbon nanotubes for 40 to 90 minutes.

The carbon source may be methane, ethylene, acetylene, LPG, or a mixed gas thereof. However, the gas source is not limited to the hydrocarbon gas, and hydrogen gas may be introduced together with the hydrocarbon gas. Hydrogen gas is used to prevent the decomposition of carbon nanotubes that may occur at high temperatures by reducing oxygen attached to the catalyst.

The carbon nanotubes synthesized by the method for producing carbon nanotubes according to the present invention have a C purity of 98% or more and do not require post-treatment such as acid treatment.

FIG. 1 is a graph showing synthesis yields of carbon nanotubes synthesized over time according to one embodiment of the present invention. Referring to FIG. 1, the carbon nanotube manufacturing method of the present invention requires about 45 minutes to reach 100 (g _CNT / g _catalyst ) and has a high growth rate.

The carbon nanotube production method of the present invention may have a synthesis yield of 80 to 200 (g _CNT / g _catalyst ).

The carbon nanotubes synthesized by the method for producing carbon nanotubes according to the present invention are excellent in crystallinity because their intensity ratio (ID / IG) by Raman spectroscopy is 1.1 or less.

The average diameter of the carbon nanotubes synthesized by the carbon nanotube manufacturing method according to the present invention may be 10 to 35 nm, and more specifically 12 to 30 nm.

The carbon nanotubes synthesized by the method of the present invention include 20 to 2,000 ppm of aluminum (Al), magnesium or silicon, 40 to 9,000 ppm of cobalt (Co), and 40 to 9,000 ppm of manganese (Mn) . The content of the metal contained in the carbon nanotubes can be measured using, for example, ICP-OES (Inductively Coupled Plasma Optic Emission Spectrometer) equipment.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1

Preparation of catalyst : A hydrate of 7.5 g of Al (NO ₃ ) ₃ .9H ₂ O, 17.5 g of Co (NO ₃ ) ₂ .6H ₂ O and 28.8 g of Mn (NO ₃ ) ₂ .6H ₂ O was dissolved in 50 ml of water , Spray drying method was used to prepare spherical particles. In order to prevent the particles from being broken during the sphere formation and firing process, a polymer binder (PVP) was added together at the time of preparing the solution, and the catalyst was prepared while varying the metal content. The spray dried particles were thermally treated at 550 ° C in air to increase the crystallization of the catalyst metal, thereby increasing the catalytic activity.

Preparation of Carbon Nanotubes : Carbon nanotubes were prepared by growing carbon nanotubes in a supported catalyst by injecting ethylene at 700 ° C for 60 minutes. Each of the catalysts was synthesized as carbon nanotubes under the same conditions. The weight of the synthesized carbon nanotubes was subtracted from the weight of the supported catalyst, and the yield was calculated.

Examples 2-17 and 1-5

A supported catalyst was prepared in the same manner as in Example 1 except that a metal catalyst was used in the composition shown in the following Table 1, and carbon nanotubes were synthesized from the prepared supported catalyst. The surface crystallinity of the carbon nanotubes was measured by Raman analysis of the synthesized carbon nanotubes and is shown in Table 2. The Raman spectroscopic graphs of Example 1 and Comparative Example 1 are shown in FIG. 2 and FIG.

Raman analysis

The carbon nanotubes were analyzed using a laser of 514.5 nm in a Renishaw inVia (Saclay, France) Raman instrument. ID / IG intensity ratios were compared by repeating the measurement three times under the same conditions as shown in Table 1 below.

division Measuring conditions Laser 514.5 nm Grating 2400 l / mm Exposure time 10 sec Accumulations 3 Measuring area 100 - 3200 cm ^-1

Yield per 1 g of catalyst

The yield per g of _catalyst (g _CNT / g _catalyst ) = (total weight - weight of used catalyst) / (weight of catalyst used).

Purity of carbon nanotubes

Using a TGA (Thermo Gravimetric Analysis, TA instrument Q-5000), the temperature was increased at 10 ° C / min to 900 ° C. The weight change of carbon nanotubes was measured at the air condition and the carbon purity Respectively.

Carbon nanotube diameter measurement

The diameters of the synthesized carbon nanotubes were measured by scanning electron microscope (Hitachi S-4800), and the average diameter of more than 100 carbon nanotubes was measured in a 100,000 magnification image.

Table 2 summarizes the catalyst compositions of the examples and comparative examples. Table 3 shows the yields (g _CNT / g _catalyst ), carbon purity (%) per 1 g catalyst of the carbon nanotubes prepared according to Examples and Comparative Examples, , Diameter, and D / G intensity ratio.

Metal mole ratio Al Co Fe Mn Mo Example 1 1.0 3.0 - 5.0 - Example 2 1.0 3.0 - 4.0 - Example 3 1.0 3.0 - 3.0 - Example 4 1.0 3.0 - 2.0 - Example 5 1.0 2.5 - 4.0 - Example 6 1.0 2.5 - 3.0 - Example 7 1.0 2.5 - 2.5 - Example 8 1.0 2.5 - 2.0 - Example 9 1.0 2.0 - 3.0 - Example 10 1.0 2.0 - 2.0 - Example 11 1.0 2.0 - 1.5 - Example 12 1.0 2.0 - 1.0 - Example 13 1.0 1.5 - 2.0 - Example 14 1.0 1.5 - 1.5 - Example 15 1.0 1.0 - 2.0 - Example 16 1.0 1.0 - 1.5 - Example 17 1.0 1.0 - 1.0 - Comparative Example 1 12.0 3.0 1.0 - 0.5 Comparative Example 2 1.0 0.75 - 2.0 - Comparative Example 3 1.0 0.50 - 2.0 - Comparative Example 4 1.0 3.0 - - - Comparative Example 5 2.0 1.0 - 2.0 -

yield
(g _CNT / g _catalyst ) C purity
(%) diameter
(nm) Raman analysis
(ID / IG) Example 1 103 99.2 25.2 ± 6.8 0.8 Example 2 128 99.5 21.8 ± 5.7 0.85 Example 3 121 99.5 22.1 ± 6.1 0.81 Example 4 115 99.5 21.5 ± 5.8 0.86 Example 5 97 99.1 19.7 ± 4.6 0.89 Example 6 113 99.2 19.2 ± 4.3 0.81 Example 7 121 99.5 18.6 ± 3.9 0.9 Example 8 126 99.6 18.9 ± 4.1 0.86 Example 9 120 99.3 21.6 ± 5.3 0.84 Example 10 113 99.5 19.4 ± 6.9 0.86 Example 11 106 99.2 18.3 ± 3.1 0.84 Example 12 101 99.3 17.2 ± 3.6 0.91 Example 13 93 99 13.0 ± 2.3 0.95 Example 14 107 99.2 16.5 ± 4.8 0.95 Example 15 91 98.8 12.9 ± 4.3 1.07 Example 16 102 99.1 15.0 + - 4.2 1.02 Example 17 95 98.9 14.6 ± 3.4 0.98 Comparative Example 1 32 96.8 10.2 ± 1.4 1.25 Comparative Example 2 47 97.5 10.2 ± 2.4 1.24 Comparative Example 3 37 97 10.2 ± 1.9 1.17 Comparative Example 4 4.1 75.1 8.9 ± 4.0 1.32 Comparative Example 5 36 97.1 15.4 ± 3.7 1.16

As shown in Tables 2 and 3, in Examples 1 to 17, it can be confirmed that the yield of carbon nanotubes relative to 1 g of the catalyst is 90 (g _CNT / g _catalyst ) or more by controlling the metal content. Also, the higher the yield, the larger the diameter of the carbon nanotubes and the lower the intensity ratio (ID / IG) of the Raman spectroscopic graph. Therefore, it can be confirmed that the yield and diameter of the carbon nanotube can be controlled by changing the content of the metal.

Figure 4 also shows a thermogravimetric analysis (TGA) graph of Example 4, which shows that the residual mineral content was about 0.5% at about 650 ° C and about 99.5% carbon was contained in the sample And it can be confirmed that a high purity carbon nanotube is synthesized. (In Example 4, there is no substantial change in the residual mineral content even at a temperature of 650 ° C or higher)

On the other hand, Comparative Examples 1 to 5, which have a different molar ratio from those of Examples 1 to 17 and further contain Fe or Fe and Mo, showed low yields of carbon nanotubes to 1 g of the catalyst, And the intensity ratio (ID / IG) of the Raman graph increases.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

One or more elements of aluminum (Al), magnesium (Mg), and silicon (Si); And
And at least one metal selected from the group consisting of cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn) and molybdenum (Mo)
The intensity ratio (ID / IG) by Raman spectroscopy is 1.1 or less,
C Carbon nanotubes having a purity of 98% or more.

The method according to claim 1,
Wherein the carbon nanotube comprises aluminum (Al), magnesium or silicon of 20 to 2,000 ppm, cobalt (Co) of 40 to 9,000 ppm, and manganese (Mn) of 40 to 9000 ppm.

The method according to claim 1,
Wherein the carbon nanotube has an average diameter of 10 to 35 nm.

At least one metal catalyst selected from the group consisting of Co, Ni, Fe, Mn and Mo; And
At least one carrier selected from the group consisting of aluminum oxide, magnesium oxide, and silica,
Wherein the carbon nanotubes are hollow type carbon nanotubes.

5. The method of claim 4,
Wherein the supported catalyst has an average particle diameter of 10 to 500 mu m.

5. The method of claim 4,
Supported catalyst having the following molar ratio:
(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y
(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0).

5. The method of claim 4,
Wherein the supported catalyst has a sphericity of 0.1 to 1.

Preparing a catalyst aqueous solution;
Spraying the catalyst aqueous solution with a droplet; And
And firing said sprayed droplets,
The catalyst aqueous solution
At least one metal catalyst selected from the group consisting of Co, Ni, Fe, Mn and Mo; And
Wherein the catalyst comprises at least one carrier selected from the group consisting of aluminum oxide and silica.

9. The method of claim 8,
Wherein the catalyst aqueous solution has the following molar ratio:
(Al, Mg or Si): metal catalyst (Co): metal catalyst (Mn) = 1: x: y
(In the above, 0.8? X? 4.0 and 0.1? Y? 8.0).

9. The method of claim 8,
Wherein the droplet size of the catalyst aqueous solution sprayed in the spraying step is 10 to 1000 占 퐉.

9. The method of claim 8,
Wherein the catalyst aqueous solution further comprises polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), or an epoxy-based polymer as a polymeric binder.

9. The method of claim 8,
Wherein the calcining step is a heat treatment at 450 to 650 ° C.

A method for producing a carbon nanotube using the supported catalyst according to any one of claims 4 to 7.

14. The method of claim 13,
Wherein the supported catalyst is charged into a furnace, and a carbon source is injected at 650 to 750 ° C to synthesize carbon nanotubes for 40 to 90 minutes.

15. The method of claim 14,
Wherein the carbon source is ethylene, methane, or LPG.

14. The method of claim 13,
Wherein the synthesis yield of the carbon nanotubes is 80 to 200 (g _CNT / g _catalyst ).