KR101357630B1 - Supported Catalyst for Synthesizing Carbon Nanotubes and Method for Preparing thereof - Google Patents

Supported Catalyst for Synthesizing Carbon Nanotubes and Method for Preparing thereof Download PDF

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KR101357630B1
KR101357630B1 KR1020100137580A KR20100137580A KR101357630B1 KR 101357630 B1 KR101357630 B1 KR 101357630B1 KR 1020100137580 A KR1020100137580 A KR 1020100137580A KR 20100137580 A KR20100137580 A KR 20100137580A KR 101357630 B1 KR101357630 B1 KR 101357630B1
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catalyst
method
fluidized bed
carbon nanotubes
supported catalyst
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KR20120075760A (en
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김병열
송이화
이윤택
장영규
배승용
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제일모직주식회사
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Abstract

The present invention provides a supported catalyst for synthesizing carbon nanotubes and a method of manufacturing the same. The supported catalyst is prepared by a fluidized bed spray coating method, and the supported catalyst has a density and size of Groups A to B of Geldart classification suitable for a fluidized bed reactor, and thus has no advantage of being scattered outside the fluidized bed. In addition, the supported catalyst prepared by the fluidized bed spray coating method of the present invention has excellent sphericity since it has a sphericity of 0.8 to 1. In addition, the fluidized bed spray drying method of the present invention can adjust the size and density of the catalyst according to the coating deposition time and the spray flow rate of the nozzle, so that the catalyst having a particle size and density in the range of Group A or Group B in the Geldart classification It is easy to manufacture.

Description

Supported catalyst for synthesizing carbon nanotubes and method for preparing}

The present invention relates to a supported catalyst for synthesizing carbon nanotubes, a method for preparing the same, and carbon nanotubes using the same. More specifically, the present invention relates to a supported catalyst for synthesizing carbon nanotubes capable of synthesizing a large amount of high-purity carbon nanotubes by increasing the sphericity and density of a catalyst using a fluidized bed spray coating method, and a method for preparing the same.

The carbon nanotubes, discovered by Dr. Iijima in 1991, are tube-shaped, carbon materials with diameters of several nanometers.

Single-walled carbon nanotubes are simply a single layer of graphite plate rolled and have a diameter of 0.5 to 3 nm, and double-walled carbon nanotubes have a concentric axis of two layers of single-walled carbon nanotubes. Nanotubes are materials with 3 to 15 layers of wall number and 5 to 100 nm in diameter.

Carbon nanotubes have very low resistance due to the one-dimensional structure and the inherent electrical structure of graphite.The resistance of single-walled carbon nanotubes is only 1/100 of copper, and the current carrying capacity is 1,000 times that of copper. Has unique electrical properties. In addition, the carbon-carbon sp 2 bond has a mechanical characteristic having a very high stiffness and strength, and has a double thermal conductivity of diamond and excellent thermal stability up to 750 ℃ in the atmosphere. In addition, the wound shape of the carbon nanotubes may have the properties of a conductor or a semiconductor, the energy band gap varies depending on the diameter and exhibits a unique quantum effect due to the one-dimensional structure. Due to the characteristics of carbon nanotubes, carbon nanotubes are actively being applied and researched in the field of display, memory devices, hydrogen storage materials, and nanocomposite materials.

Carbon nanotubes having the above characteristics may be synthesized through various methods such as electric discharge, laser deposition, plasma chemical vapor deposition, thermochemical vapor deposition, and gas phase synthesis. The electrodischarge method is obtained by discharging carbon clusters from the graphite rod used as the anode when they are discharged between the two electrodes to condense and collect on the low temperature cathode graphite electrode. The laser deposition method vaporizes graphite by irradiating a laser with a graphite as a target point in an oven at 1200 ° C. The vaporized graphite is obtained by adsorption and condensation on the collector. In the plasma chemical vapor deposition method, a substrate on which carbon nanotubes are to be grown (Si, SiO 2 , a catalyst metal deposited on a glass substrate) is placed on a lower electrode, a raw material gas is supplied from the upper electrode side, and RF glow discharge is applied on the substrate. Synthesize CNT. Thermochemical vapor deposition is a method of synthesizing carbon nanotubes by supplying hydrocarbon gas onto a substrate on which a metal catalyst is deposited in a reactor maintained at a synthesis temperature of carbon nanotubes.

Among the synthesis methods, the electric discharge method and the laser deposition method have advantages in that the principle is simple and easy to apply, but includes a lot of impurities in the synthesis and is not suitable for mass production. On the other hand, thermochemical vapor deposition is known as the most suitable method for synthesizing high purity carbon nanotubes in large quantities at low cost.

When synthesizing nanotubes through the thermochemical vapor deposition method, the catalyst plays a very important role. For example, the growth of carbon nanotubes depends on the type and composition ratio of the transition metal and the size of the metal particles. Fe, Co, Ni, etc. are used as the transition metal and synthesized by supporting it on a carrier. In the synthesis method, the catalyst material is uniformly dissolved in an aqueous solution, and the coprecipitation method or the dissolved solution which is supported on the carrier by controlling the pH is dried and then polished for uniform support of the metal catalyst and then again 700 ° C. The impregnation method which synthesize | combines by sintering (Calcination) for 6 to 10 hours at high temperature of -900 degreeC, etc. is mentioned. However, this method has a problem that it is time-consuming and the yield is not suitable for mass production.

In order to solve the problems of the conventional carbon nanotube synthesis method, the carbon nanotube synthesis method using a fluidized bed reactor is disclosed in Korea Patent Publication No. 2007-0141265, Korean Patent Publication No. 2007-0077714, Japanese Patent Publication No. 2006 The synthesis technology using the vertical CVD apparatus for the continuous process disclosed in US Patent Publication No. 2005-663451 has been recently highlighted because of the advantage of mass production of carbon nanotubes. However, in the case of the vertical CVD applied for mass production, there are disadvantages in that the residence time is quite short and it is difficult to control the residence time.

However, when synthesizing carbon nanotubes on the surface of the catalyst by flowing the catalyst as a gas used as a carbon source in the fluidized bed chamber, the residence time of the catalyst can be controlled, that is, the synthesis time of the carbon nanotubes can be controlled. It has the advantage that mass production is possible. Therefore, in the synthesis of carbon nanotubes in a fixed bed or fluidized bed reactor, especially a fluidized bed reactor, it is possible to mass-produce high-purity carbon nanotubes whether the supported catalyst has excellent fluidity or low density by having a density that meets the criteria. It can be said to be a key requirement for measuring whether there is.

An object of the present invention is to provide a supported catalyst having excellent fluidity for synthesizing carbon nanotubes.

Another object of the present invention is to provide a supported catalyst that can mass-produce carbon nanotubes.

Still another object of the present invention is to provide a supported catalyst capable of obtaining high purity carbon nanotubes.

Still another object of the present invention is to provide a supported catalyst that can be applied to both a fixed bed and a fluidized bed reactor when manufacturing carbon nanotubes.

Still another object of the present invention is to provide a new method for preparing a supported catalyst which can reduce time and cost and does not require a post-treatment process such as grinding or ball milling process or a separate purification process, and is effective for mass production.

These and other objects of the present invention can be achieved by the present invention which is described in detail.

In order to achieve the above technical problem, the present invention is a metal catalyst selected from one or more of Co, Ni, Fe is supported on the alumina, magnesium oxide, silica carrier, comprises a molybdenum-based activator, characterized in that it has the following molar ratio It provides a supported catalyst for the synthesis of carbon nanotubes, characterized in that the spherical degree is 0.8 to 1.

Metal catalyst [(Co, Ni) Fe]: Molybdenum-based activator [Mo]: Carrier [(Mg, Si) Al] = x: y: z

(Wherein 1 ≦ x ≦ 10, 0 ≦ y ≦ 5, and 2 ≦ z ≦ 70).

In one embodiment of the present invention, the supported catalyst may be a supported catalyst for synthesizing carbon nanotubes, which has a density of 0.5 to 2 g / cm 3 and a particle diameter of 100 to 500 μm.

In order to achieve the above another technical problem, the present invention comprises the step of coating the catalyst seed particles by continuously spray drying the catalyst aqueous solution to the catalyst seed particles charged in the fluidized bed reactor through a spray nozzle installed in the fluidized bed reactor Provided is a method for preparing a supported catalyst for synthesizing carbon nanotubes.

In one embodiment of the present invention, the catalyst seed may be filled with seed particles having a particle size of 50 to 100㎛ by spraying and drying the aqueous catalyst solution through a spray nozzle in a fluidized bed reactor.

The present invention provides a supported catalyst capable of mass-producing high purity carbon nanotubes when synthesizing carbon nanotubes in a fluidized bed reactor by increasing the density of the catalyst in a simple manner to prevent the catalyst from scattering and improving the fluidity of the catalyst by improving the sphericity. And it has the effect of providing the manufacturing method.

1 is a schematic view illustrating a process of a fluidized bed spray production method for preparing a supported catalyst for synthesizing carbon nanotubes according to the present invention.
FIG. 2 is a schematic view showing a process of growing seed particles by coating seed particles in a fluidized bed spray production method for preparing a supported catalyst for synthesizing carbon nanotubes according to the present invention.
Figure 3 (a) is a scanning electron microscope (SEM) photograph of the supported catalyst prepared in Comparative Example 1, (b) is a scanning electron of the carbon nanotubes synthesized using the supported catalyst prepared in Comparative Example 1 Micrograph (SEM).
Figure 4 (a) is a scanning electron microscope (SEM) photograph of the supported catalyst prepared in Example 1, (b) is a scanning electron microscope of carbon nanotubes synthesized using the supported catalyst prepared in Example 1 SEM) picture.

In order to synthesize carbon nanotubes using a fluidized bed reactor, the catalyst for synthesizing carbon nanotubes preferably has a form and density suitable for flowing. Generally, the particles can be classified into four types according to the Geldart classification method based on the particle size and density of the particles. Group A is a particle having a small particle size and low density (<1.4 g / cm 3 ), and a material which is easy to flow at a low flow rate, such as a FCC catalytic cracking catalyst. Group B is a sandy material with a particle diameter of 40 to 500 µm and a density of 1.4 to 4 g / cm 3 , which flows smoothly. Group C is a cohesive material that is difficult to flow, such as flour or starch. Group D is a material with a large or heavy particle size, such as coal, and has a material flowing in a low bed due to irregular flowability in a high flow bed. Therefore, in order to apply to the fluidized bed, it is preferable to use a catalyst of Group A or B type.

Currently, catalysts for synthesizing carbon nanotubes are generally manufactured by using an impregnation method. However, the supported catalyst prepared by the solution supporting method does not have a spherical shape, and thus has a limitation that is difficult to apply to a fluidized bed reactor. In addition, although a hollow catalyst having a wide reaction surface area is prepared by spray drying, the catalyst prepared by the spray drying has a low density and does not have suitable fluidity when used in a fluidized bed reactor.

Therefore, the inventor of the present invention has begun to develop a spherical catalyst having excellent fluidity and a method for producing the same having an appropriate density suitable for use in a fluidized bed reactor.

Hereinafter, the supported catalyst of the present invention and a manufacturing method thereof will be described in detail.

Supported catalyst

One aspect of the present invention relates to a supported catalyst for synthesizing carbon nanotubes. The catalyst has a metal catalyst selected from at least one selected from Co, Ni, and Fe on an alumina, magnesium oxide, or silica carrier, and has a surface area of 50 to 1000 m 2 / g.

In one embodiment of the present invention, the supported catalyst may have the following molar ratio.

(Co, Ni) Fe: Mo: (Mg, Si) Al = x: y: z

(Wherein 1 ≦ x ≦ 10, 0 ≦ y ≦ 5, and 2 ≦ z ≦ 70).

In a preferred embodiment, the supported catalyst may have the following molar ratio.

Fe: Mo: Al = x: y: z

(Wherein 1 ≦ x ≦ 10, 0 ≦ y ≦ 5, and 2 ≦ z ≦ 70).

In one embodiment of the present invention, the supported catalyst has a density of 0.5 to 2 g / cm 3 , and has a particle size of 100 to 500 ㎛ in order to show the optimum fluidity in the fluidity reactor. The catalyst prepared using the spray drying method disclosed in Korean Patent Laid-Open No. 2008-0104349 has a hollow type shape, which has the advantage of widening the reaction surface area of the catalyst, but has a considerably low density of about 0.4 g / cm 3 . Therefore, according to the Geldart classification has a lower density than the Group A particles, the flow conditions are difficult as an intermediate material of Group C and A and due to the low density is likely to be scattered when flowing in the fluidized bed reactor.

On the other hand, the supported catalyst prepared by the fluidized bed spray coating method of the present invention has a higher density than the catalyst prepared by the general spray drying method because the catalyst has a tighter form, and thus belongs to Group A of Geldart classification, so that the catalyst flows in the fluidized bed. This can be done smoothly.

In addition, in the fluidized bed reactor, high mobility and motility may cause a lot of friction, and as a result of the friction, the catalyst particles may be crushed and flowed out through the top of the bed. Therefore, the supported catalyst suitable for the fluidized bed reactor has a more perfect spherical shape, it is advantageous to improve the yield of carbon nanotubes. In this respect, the supported catalyst prepared by using the fluidized bed reactor of the present invention in order to improve the fluidity of the supported catalyst has a more complete spherical shape as shown in FIG. More specifically, the supported catalyst of the present invention has a sphericity of 0.8 to 1.

Of the supported catalyst  Manufacturing method

Another aspect of the invention provides a method for producing the supported catalyst. The method comprises spraying a catalyst aqueous solution mixed with a metal catalyst and a support through a spray nozzle in a fluidized bed reactor to form a catalyst seed, flowing the seed in a fluidized bed reactor, and continuously supplying a catalyst solution through the spray nozzle. The present invention relates to a method of coating a seed by spraying to increase the particle size and to produce a catalyst having a more complete spherical shape.

Referring to Figure 1 specifically described the fluidized bed spray coating method of the present invention.

Step 1-Metal Catalysts Support  Preparation of Mixed Catalyst Aqueous Solution

In embodiments, the metal catalyst may be Fe (NO 3 ) 3 , Ni (NO 3 ) 2 Co (NO 3 ) 2 , Fe (OAc) 2 , Ni (OAc) 2 or Co (OAc) 2, which may be used. It can be used individually or in mixture of 2 or more types. In embodiments, the metal catalyst may have the form of a hydrate. For example, it may be used in the form of Iron (III) nitrate nonahydrate, Nickle (II) nitrate hexahydrate, Cobalt nitrate hexahydrate.

The carrier may be used aluminum nitrate, magnesium nitrate, and the like, but is not necessarily limited thereto. These may be used alone or in combination of two or more. Preferably, aluminum nitrate nonahydrate may be used.

The metal catalyst and the carrier are dissolved in water and mixed in an aqueous solution.

In another embodiment of the present invention, a molybdenum-based activator such as Ammonium Molybdate tetrahydrate may be added to prevent agglomeration between nano-sized metal catalysts during sintering at high temperature. In another embodiment, an activator such as citric acid may be used.

The catalyst aqueous solution mixed with the metal catalyst and the support and optionally the molybdenum (Mo) -based active agent are completely dissociated by stirring.

Step 2-Seed Formation

The catalyst solution is sprayed through a nozzle located inside the fluidized bed reactor and dried in the fluidized bed to prepare an initial catalyst seed having a particle size of 50 to 100 μm to fill the inside of the fluidized bed reactor.

In addition to the method of forming the catalyst seed as described above, the catalyst seed particles prepared separately may be first introduced into a fluidized bed reactor and then coated with a catalyst solution sprayed through a spray nozzle.

The catalyst seed particles may be used without limitation as long as they are particles having the same composition as the sprayed catalyst solution or spherical particles having a particle diameter of 50 to 100 μm. For example, spherical alumina particles, spherical starch particles, spherical silica particles, and the like may be used as seed particles. At this time, when catalyst seed particles having a narrow particle size distribution are used, the particle size distribution of the final catalyst particles can also be narrowed.

In the seed forming step, the reactor internal temperature is preferably 100 ℃ to 300 ℃, the spray amount through the spray nozzle is preferably 0.1 to 10 ml / sec. In addition, in the case of the catalyst prepared through the present invention, since the catalyst size can be freely adjusted according to the residence time in the reactor, the residence time in the reactor is not limited.

Step 3-Fluidized Bed Spray Coating Step

The catalyst solution is continuously sprayed through a nozzle while flowing the catalyst seed to coat the outer circumferential surface of the seed. The spraying time and spraying speed of the spray nozzle are continuously made until a catalyst of a suitable size can be obtained. It is possible to control the particle diameter of the catalyst formed according to the spraying time and the spraying speed of the spray nozzle, it is easy to control the particle diameter of the catalyst formed.

In the process of growing the catalyst in the fluidized bed reactor, a flowing gas is introduced to facilitate the flow of the catalyst. The flowing gas is a gas for flowing the catalyst particles, and in general, air may be used, and in some cases, a gas, such as nitrogen, oxygen, hydrogen, etc., may be used to improve or flow the catalyst properties.

In addition, the production method of the present invention has an advantageous effect of producing a large amount of catalyst particles because it uses a fluidized bed spray drying apparatus in which the catalyst is continuously produced instead of a batch reactor.

The supported catalyst prepared by the above method has a perfect spherical shape, and the particle size of the supported catalyst can be adjusted according to the coating deposition time and the spray flow rate of the nozzle, so that the supported catalyst falls within the range of Group A or Group B of the Geldart classification. It is easy to prepare a catalyst having a particle diameter and density.

In the case of synthesizing carbon nanotubes by adding spherical catalyst particles prepared by the fluidized bed spray drying method to a fluidized bed reactor, high purity carbon nanotubes can be manufactured in large quantities due to the excellent flow characteristics of the catalyst.

Carbon nanotube

Another aspect of the present invention provides a carbon nanotube prepared using the supported catalyst. The supported catalyst of the present invention can be applied to either a fixed bed or a fluidized bed reactor, and is preferably a fluidized bed reactor.

In a specific embodiment, the carbon nanotubes may be prepared by adding hydrocarbon gas in the presence of a supported catalyst at a temperature of 600 to 1100 ° C., preferably 650 to 950 ° C. In one embodiment, the carbon nanotubes may be manufactured at 650 to 800 ° C. In another embodiment, carbon nanotubes may be manufactured at 800 to 990 ° C., and in another embodiment, carbon nanotubes may be manufactured at 980 to 1100 ° C. FIG. As the hydrocarbon gas, methane, ethylene, acetylene, LPG, or a mixed gas thereof may be used, but is not limited thereto. The supply time of the hydrocarbon gas is supplied for 15 to 120 minutes, preferably 30 to 60 minutes.

The productivity [{(weight of the synthesized carbon nanotubes-catalyst weight) / catalyst weight} X 100] of the carbon nanotubes prepared using the supported catalyst of the present invention is 1000% or more, preferably 1200% or more, More preferably 1500% or more. In embodiments it has a productivity of 1500 to 3000%.

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

Example 1

A catalyst solution comprising a metal catalyst (Fe, Co), a molybdenum activator (Mo) and a support (Al 2 O 3 ), wherein the molar ratio of Fe: Co: Mo: Al 2 O 3 = 0.24: 0.36: 0.02: 1.44 Prepare the aqueous catalyst solution. The prepared aqueous catalyst solution is sprayed into the fluidized bed reactor through a spray nozzle located in the fluidized bed reactor. The internal temperature of the fluidized bed reactor is 190 ℃, the spray amount of the aqueous catalyst solution is 2 ml / sec. After seed particles are manufactured by the fluidized bed spray drying method, the catalyst solution is continuously coated on the seed particles, and the spray drying process is continuously performed until the catalyst particle diameter reaches about 500 μm. The prepared catalyst has a density suitable for flowing as shown in FIG. 3 (a) and has a perfect spherical shape.

100 g of the supported catalyst synthesized by the above method was added to a fluidized bed thermochemical vapor deposition apparatus, and carbon nanotubes were synthesized for 45 minutes while flowing 100/100 sccm at a ratio of 1: 1 of ethylene and hydrogen at 700 ° C. Synthesized carbon nanotubes were taken by scanning electron micrograph (SEM) at 50 times magnification, and it is possible to manufacture spherical carbon nanotube bundles as shown in the SEM photograph of FIG. Has one advantage. C purity of the synthesized carbon nanotubes, TGA, productivity is shown in Table 1 by measuring the increased weight after synthesis. It is possible to produce up to about 16g of carbon nanotubes with 1 g of the catalyst, wherein the C purity was 93%.

Comparative Example 1

A catalyst preparation method was prepared under the same conditions as in Example 1, except that the preparation method of the catalyst was prepared by a general supporting method. The SEM photograph of the prepared catalyst is 100 times higher than that of the catalyst prepared by the general supporting method. Figure 4 (b) is a SEM picture of 100 times the magnification of the carbon nanotubes synthesized by adding the catalyst to the fluidized bed reactor.

Example 1 Comparative Example 1 Method for producing catalyst Fluidized Bed Spray Drying Method General supporting method C purity (%) 93 86 CNT Productivity (%) 1600 700

* Carbon Nanotube Productivity (%): {(Weight of Synthetic Carbon Nanotube-Catalyst Weight) / Catalyst Weight} X 100

As a result of preparing carbon nanotubes using the catalyst prepared by the fluidized bed spray drying method as shown in Table 1, the C purity was 93% and the productivity was 1600%. It can be seen that it has.

In addition, comparing with Figure 3 and Figure 4 can be confirmed that the catalyst prepared by the fluidized bed spray drying method has a more complete spherical shape than the catalyst prepared by the general supporting method, and even in the case of synthesized carbon nanotubes. .

Claims (10)

  1. delete
  2. delete
  3. Supporting the carbon nanotube synthesis comprising the step of filling the catalyst seed particles in a fluidized bed reactor and coating the catalyst seed particles by continuously spray drying the catalyst aqueous solution through a spray nozzle installed in the fluidized bed reactor Method for preparing a catalyst.
  4. The method of claim 3, wherein the spray drying is carried out at a temperature range of 100 to 300 ° C.
  5. The method for preparing a supported catalyst for synthesizing carbon nanotubes according to claim 3, wherein the spray amount of the sprayed aqueous catalyst solution is 0.1 to 10 ml / sec.
  6. The method of claim 3, wherein the catalyst seed filling step is carried out by spray drying the catalyst aqueous solution through a spray nozzle in a fluidized bed reactor to fill seed nanoparticles having a particle size of 50 to 100 µm. Method for preparing a catalyst.
  7. [Claim 4] The supported catalyst for synthesizing carbon nanotubes of claim 3, wherein the catalyst seed is a spherical particle having a particle size of 50 to 100 µm and comprises alumina particles, starch particles, silica particles, or a mixture thereof. Manufacturing method.
  8. 8. The method of claim 3, wherein the aqueous catalyst solution is a catalyst aqueous solution in which a metal catalyst and a support are mixed. 9.
  9. The metal catalyst of claim 8, wherein the metal catalyst is made of Fe (NO 3 ) 3 , Ni (NO 3 ) 2 , Co (NO 3 ) 2 , Fe (OAc) 2 , Ni (OAc) 2, and Co (OAc) 2 . A method for producing a supported catalyst for synthesizing carbon nanotubes, characterized in that at least one selected from the group.
  10. The method of claim 8, wherein the support is at least one selected from the group consisting of aluminum nitrate, magnesium nitrate, and silica.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030091496A1 (en) 2001-07-23 2003-05-15 Resasco Daniel E. Method and catalyst for producing single walled carbon nanotubes
US20050074392A1 (en) 2002-07-31 2005-04-07 Yuemei Yang Method for making single-wall carbon nanotubes using supported catalysts
KR20100045247A (en) * 2008-10-23 2010-05-03 제일모직주식회사 Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same
KR20100074002A (en) * 2008-12-22 2010-07-01 제일모직주식회사 Supported catalyst with solid sphere structure, method for preparing thereof and carbon nanotube using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030091496A1 (en) 2001-07-23 2003-05-15 Resasco Daniel E. Method and catalyst for producing single walled carbon nanotubes
US20050074392A1 (en) 2002-07-31 2005-04-07 Yuemei Yang Method for making single-wall carbon nanotubes using supported catalysts
KR20100045247A (en) * 2008-10-23 2010-05-03 제일모직주식회사 Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same
KR20100074002A (en) * 2008-12-22 2010-07-01 제일모직주식회사 Supported catalyst with solid sphere structure, method for preparing thereof and carbon nanotube using the same

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