WO2018160042A1 - Catalyst for mass production of multi-wall carbon nanotubes - Google Patents

Abstract

An embodiment of the present invention provides a catalyst for manufacturing multi-wall carbon nanotubes, the catalyst comprising metal components according to <Equation> Ma:Mb = x:y, and having a hollow structure with a thickness of 0.5-10 ㎛. In the above equation, Ma represents at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn, and Cu; Mb represents at least one metal selected from Mg, Al, Si, and Zr; x and y each represent the molar ratio of Ma and Mb; and x+y = 10, 2.0≤x≤7.5, and 2.5≤y≤8.0.

Description

Catalysts for Mass Production of Multi-walled Carbon Nanotubes

The present invention relates to a catalyst for mass production of multi-walled carbon nanotubes.

Carbon nanotube (carbon nanotube) is a hexagonal honeycomb tubular structure in which one carbon atom is bonded to three other carbon atoms, and its electrical, thermal, and mechanical properties are superior to other materials to be applied to various industrial fields. have.

Such carbon nanotubes are generally arc-discharge, pyrolysis, laser vaporization, chemical vapor deposition, plasma chemical vapor deposition, and thermochemistry. It is prepared by various methods such as thermal chemical vapor deposition, chemical vapor condensation, and the like.

Until now, catalysts for carbon nanotube production have been developed that have various metal components and physical properties, but most of them have been developed based on a fixed bed chemical vapor deposition reactor having low productivity and uniformity of synthesized carbon nanotubes. There is a problem with fluidized bed chemical vapor deposition reactors that are advantageous for the production of carbon nanotubes.

In addition, the production method of the catalyst is spray drying (spray dry) is made at a low temperature of 200 ~ 350 ℃, in order to form a hole in the catalyst, it is essential to use a water-soluble polymer as a pore-forming agent, making the catalyst in a form suitable for synthesis In order to have a separate firing process to 350 ~ 1,100 ℃, there is a problem that the catalyst prepared by the spray drying method is not suitable for the fluidized bed reactor due to the high apparent density.

The present invention is to solve the above problems of the prior art, an object of the present invention is to provide a catalyst suitable for the production process of multi-walled carbon nanotubes using a fluidized bed reactor.

One aspect of the present invention includes a metal component according to the following formula,

<Expression>

Ma: Mb = x: y

It provides a catalyst for producing multi-walled carbon nanotubes having a hollow structure of 0.5 ~ 10㎛ thickness.

Wherein Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu, Mb is at least one metal selected from Mg, Al, Si and Zr, x And y represent the mole fractions of Ma and Mb, respectively, x + y = 10, 2.0 ≦ x ≦ 7.5 and 2.5 ≦ y ≦ 8.0.

In one embodiment, the apparent density of the catalyst may be 0.05 ~ 0.70 g / mL.

In one embodiment, the thickness may be 1 ~ 8㎛.

In one embodiment, the hollow ratio of the hollow structure may be more than 50% by volume.

Another aspect of the present invention provides a carbon nanotube assembly including a bundle of carbon nanotubes consisting of a plurality of multi-walled carbon nanotubes grown on the catalyst for preparing the multi-walled carbon nanotubes.

In one embodiment, the average bundle diameter of the bundle-type carbon nanotubes may be 0.5 ~ 20㎛, the average bundle length (bundle length) may be 10 ~ 200㎛.

In one embodiment, the Raman spectral intensity ratio (I _G / I _D ) of the multi-walled carbon nanotubes may be 0.7 ~ 1.5.

In one embodiment, the average diameter of the multi-walled carbon nanotubes may be 5 ~ 50nm.

In one embodiment, the apparent density of the multi-walled carbon nanotubes may be 0.01 ~ 0.07g / mL.

According to an aspect of the present invention, a catalyst having a hollow structure, that is, a spherical or partially broken spherical sphere having a hollow structure, that is, a core-shell structure by spray pyrolysis of an aqueous catalyst solution in which all metal catalyst components are dissolved without using a separate carrier is used. It can be produced, by controlling the thickness of the shell, the hollow ratio, and the density of the catalyst constituting the hollow structure to a certain range to optimize the composition and structure of the catalyst in a fluidized bed reactor can produce a large amount of multi-walled carbon nanotubes.

It is to be understood that the effects of the present invention are not limited to the above effects, and include all effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is an SEM image of a catalyst for preparing multi-walled carbon nanotubes according to an embodiment of the present invention.

2 is an SEM image of a catalyst for preparing multi-walled carbon nanotubes according to a comparative example of the present invention.

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is "connected" to another part, it includes not only "directly connected" but also "indirectly connected" with another member in between. . In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

One aspect of the present invention includes a metal component according to the following formula,

<Expression>

Ma: Mb = x: y

It provides a catalyst for producing multi-walled carbon nanotubes having a hollow structure of 0.5 ~ 10㎛ thickness.

Wherein Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu, Mb is at least one metal selected from Mg, Al, Si and Zr, x And y represent the mole fractions of Ma and Mb, respectively, x + y = 10, 2.0 ≦ x ≦ 7.5 and 2.5 ≦ y ≦ 8.0.

The catalyst may be used in a gas phase synthesis method for synthesizing carbon nanotubes, wherein Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu, and Mb is Since it is at least one metal selected from Mg, Al, Si and Zr, it may contain at least three or more metals, preferably three to five metal components.

In particular, the Ma is a catalyst component and an active component in the catalyst, and compared to the case of using a single metal component as the catalyst component and the active component, impurities in the carbon nanotube synthesis process by using a mixture of two or more metal components Purity can be improved by suppressing production.

As used herein, the term "catalyst component" refers to a substance that substantially lowers the chemical reaction energy of the substance, i.e., the main catalyst, and "active component" refers to a substance that aids in the action of the catalyst component, i.e., a promoter. it means. When the catalyst component and the active component have a uniform distribution within a certain range, the synthesis yield of carbon nanotubes may be improved.

The mole fractions x and y of Ma and Mb may satisfy a relationship of 2.0 ≦ x ≦ 7.5 and 2.5 ≦ y ≦ 8.0, respectively. When x is less than 2.0, the activity of the catalyst and the synthesis yield of carbon nanotubes may be lowered. If the x is greater than 7.5, the content of Mb, which is a support component, is relatively low, resulting in a decrease in the durability of the catalyst. There is a problem that is difficult to apply to the continuous fluidized bed chemical vapor deposition method for.

The catalyst may have a hollow structure having a thickness of 0.5 to 10 μm, preferably 1 to 8 μm, and the hollow ratio may be 50% by volume or more. In addition, the apparent density of the catalyst may be 0.05 ~ 0.70 g / mL.

As used herein, the term “hollow structure” refers to a three-dimensional structure with an empty interior, for example, a spherical or polyhedral structure with an empty interior, wherein the hollow structure is a closed structure in which the entire hollow is closed. ), Some of the hollows may be interpreted to include an open structure, or a combination thereof.

In the case of the conventionally filled solid catalyst, its apparent density is higher than about 0.7 g / mL, making it difficult to apply to continuous fluidized bed chemical vapor deposition for mass production of carbon nanotubes, and only carbon nanoparticles on the outer surface of the catalyst. There is a problem that the tube is difficult to grow and improve the yield above a certain level.

On the other hand, since the catalyst has a hollow structure, the apparent density is lower than that of the conventional catalyst, so that the catalyst can be applied to a continuous fluidized bed chemical vapor deposition method, and carbon nanotubes can be grown outward from the outer surface of the hollow structure. In addition, it can also grow inward from the inner surface of the hollow structure can significantly improve the carbon nanotube synthesis yield.

Another aspect of the invention, (a) dissolving the metal precursor in a solvent to prepare a precursor solution; And (b) forming a catalyst by spraying the precursor solution into the reactor while pyrolysis to form a catalyst.

<Equation 1>

Ma: Mb = x: y

Wherein Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu, Mb is at least one metal selected from Mg, Al, Si and Zr, x And y represent the mole fractions of Ma and Mb, respectively, x + y = 10, 2.0 ≦ x ≦ 7.5 and 2.5 ≦ y ≦ 8.0.

In the step (a) it can be prepared a precursor solution of each metal element constituting the catalyst. The metal precursor may be one selected from the group consisting of nitrates, sulfates, alkoxides, chlorides, acetates, carbonates, and mixtures of two or more thereof, but is not limited thereto.

In the step (a), the solvent may be a polar solvent, and water, methanol, ethanol, propanol, isopropanol, butanol, or a mixed solvent of two or more thereof may be used as the polar solvent, preferably, water, more Preferably, deionized water can be used.

When dissolving each precursor for the preparation of the precursor solution, the use of deionized water as a solvent can minimize impurities in the precursor solution, thereby improving the purity of the final catalyst prepared. Improving the purity of the catalyst may mean improved purity of the carbon nanotubes as a result.

In the step (b), the precursor solution may be pyrolyzed while spraying into the reactor to form a catalyst. Step (b) may include: (i) spraying a precursor solution into the reactor by supplying air of 2 to 5 atmospheres as a carrier gas and introducing external air; And (ii) pyrolyzing the sprayed precursor solution at 600 to 1,200 ° C. to form a catalyst.

In step (i), the precursor solution may be sprayed into the reactor and converted into finer droplets in order to control the particle size, apparent density, and the like of the catalyst.

When spraying the precursor solution, the pressure can be adjusted in the range of 2 to 5 atm. If the spraying pressure is less than 2 atm, the particle size, apparent density, etc. of the catalyst may not be controlled within a predetermined range, thereby lowering the purity of the carbon nanotubes synthesized therethrough. On the other hand, when the spray pressure is more than 5 atm, the particle size of the droplets is excessively small, so that the catalysts obtained may aggregate with each other.

As the surface tension of the precursor solution is overcome and the inertia force is effectively transferred to the solution, the droplet size can be more precisely controlled, and thus the particle size, apparent density, etc. of the catalyst can be precisely controlled.

Accordingly, droplets may be formed by spraying a gas simultaneously with spraying the precursor solution, or spray droplets may be formed by spraying a gas after spraying the precursor solution.

However, when the spraying of the precursor solution and the gas is sequentially performed, the size of the droplet may be more precisely controlled, and thus the method of preparing the catalyst further includes spraying the gas into the reactor before the step (ii). It may include.

In this case, as the gas, air, nitrogen, argon or a mixed gas of two or more thereof may be used, and preferably air may be used. In addition, electrostatic attraction may be added to the gas spray to improve the efficiency of the droplet formation.

In the case of further spraying the gas after spraying the precursor solution, as in the case of spraying at the same time, the pressure of the spraying gas can be adjusted within the range of 2 to 5 atmospheres, and the effect of the case out of the above range is described above. It's like that.

In step (ii), the catalyst may be finally prepared by heating the droplets to evaporate the solvent and decomposing the precursor. At this time, the temperature of the reactor may be 600 ~ 1,200 ℃, preferably, 700 ~ 900 ℃.

When the temperature of the reactor is less than 600 ℃, the dry state of the catalyst is poor and requires an additional process is disadvantageous in terms of economics, through which the purity or physical properties of the carbon nanotubes manufactured may be reduced. In addition, if the temperature of the reactor is more than 1,200 ℃ excessive cost to build equipment or equipment not only causes economic losses, but also the performance of the catalyst may be degraded due to the formation of solid solution or modification of the crystal structure.

Another aspect of the present invention provides a carbon nanotube assembly including a bundle of carbon nanotubes consisting of a plurality of multi-walled carbon nanotubes grown on the catalyst for preparing the multi-walled carbon nanotubes.

The bundle type carbon nanotubes may basically exist in a form in which a plurality of carbon nanotubes, preferably, a plurality of multi-walled carbon nanotubes are aggregated with each other. Each carbon nanotube and the aggregate thereof may be straight, curved, or a mixture thereof.

An average bundle diameter of the bundled carbon nanotubes may be 0.5 to 20 μm, and an average bundle length may be 10 to 200 μm. In addition, the Raman spectral intensity ratio (I _G / I _D ) of the multi-walled carbon nanotubes may be 0.7 to 1.5, the average diameter may be 5 to 50nm, the apparent density may be 0.01 ~ 0.07g / mL. .

Hereinafter, embodiments of the present invention will be described in detail.

Examples and Comparative Examples

Fe (NO ₃ ) _{3 ·} 9H ₂ O, Co (NO ₃ ) _{3 ·} 6H ₂ O, (NH ₄ ) ₆ Mo ₇ O _{24 ·} 4H ₂ O, NH ₄ VO ₃ , (NH ₄ ) ₁₀ H ₂ (W ₂ 0 ₇ ) _{6 ·} 9H ₂ O, Al (NO ₃ ) _{3 ·} 9H ₂ O, Mg (NO ₃ ) _{2 ·} 6H ₂ O and ZrO (NO ₃ ) _{2 ·} 2H ₂ O in the catalyst composition of Table 1 below. Each required precursor was dissolved in deionized water to prepare a precursor solution. The precursor solution was pyrolyzed by spraying 3L per hour with air into the reactor to obtain a catalyst powder. At this time, the pyrolysis condition was that the air pressure is 3 atm, the reactor internal temperature is 750 ℃, and operated continuously for 120 minutes.

division	Catalyst composition	Ma (number of moles)					Mb (number of moles)			Ma total	Mb total	x (mole fraction)	y (mole fraction)
		Fe	Co	Mo	V	W	Al	Mg	Zr
Example 1	Fe / Al / Mg	71.6	-	-	-	-	148.2	82.3	-	71.6	230.5	2.37	7.63
Example 2	Fe / Mo / Al / Mg	88.6	-	5.2	-	-	183.5	4.1	-	93.8	187.6	3.33	6.67
Example 3	Co / V / Al / Mg	-	118.8	-	9.8	-	148.2	41.1	-	128.6	189.4	4.04	5.96
Example 4	Fe / Co / Mo / Al	47.0	14.8	5.2	-	-	185.3	-	-	67.1	185.3	2.66	7.34
Example 5	Fe / Co / Mo / Al	67.1	21.2	5.2	-	-	185.3	-	-	93.6	185.3	3.36	6.64
Example 6	Fe / Co / Mo / Al	94.0	29.7	5.2	-	-	185.3	-	-	128.9	185.3	4.10	5.90
Example 7	Fe / Co / Mo / Al / Mg	67.1	21.2	5.2	-	-	185.3	4.1	-	93.6	189.4	3.31	6.69
Example 8	Fe / Co / Mo / V / Al	134.3	42.4	5.2	0.6	-	185.3	-	-	182.5	185.3	4.96	5.04
Example 9	Co / V / W / Al	-	118.8	-	9.8	8.2	148.2	-	-	136.8	148.2	4.80	5.20
Example 10	Co / V / Al / Zr	-	237.6	-	17.7	-	74.1	-	21.9	255.2	96.0	7.27	2.73
Comparative Example 1	Fe / Al / Mg	53.7	-	-	-	-	148.2	82.3	-	53.7	230.5	1.89	8.11
Comparative Example 2	Fe / Co / Mo / Al	143.2	67.9	20.8	-	-	74.1	-	-	231.9	74.1	7.58	2.42
Comparative Example 3	Fe / Co / Mo	67.1	21.2	5.2	-	-	-	-	-	93.6	0.0	10.00	0.00
Comparative Example 4	Al / Mg	-	-	-	-	-	74.1	41.1	-	0.0	115.3	0.00	10.00
Comparative Example 5	Fe / Co / Mo / Al	67.1	21.2	5.2	-	-	185.3	-	-	93.6	185.3	3.36	6.64
Comparative Example 6	Fe / Co / Mo / Al	67.1	21.2	5.2	-	-	185.3	-	-	93.6	185.3	3.36	6.64
Comparative Example 7	Fe / Co / Mo / Al	67.1	21.2	5.2	-	-	185.3	-	-	93.6	185.3	3.36	6.64
Comparative Example 8	Fe / Co / Mo / Al	67.1	21.2	5.2	-	-	185.3	-	-	93.6	185.3	3.36	6.64

The catalyst of Comparative Example 5 is the same in composition and composition as the catalyst of Example 5, but the catalyst is prepared by spray drying, and Example 5 is different from the method of preparing the catalyst. Specifically, in the case of Comparative Example 5 compared to the spray pyrolysis method of Example 5 to prepare a catalyst powder by spraying the precursor solution in the reactor at a temperature of 200 ℃ relatively low, 700 ℃, 1 hour in an air atmosphere heat treatment furnace The solid catalyst powder of the solid shape was prepared by heat treatment for a while. The catalysts of Comparative Examples 6 and 7 were prepared by the co-precipitation method and the combustion method, respectively, and they each had a plate shape as shown in FIG. The catalyst of Comparative Example 8 is a catalyst prepared using alumina (Al ₂ O ₃ ) powder which is not dissolved in water as a precursor of Al in the catalyst component.

1 and 2 are SEM images of a catalyst for preparing multi-walled carbon nanotubes according to Examples and Comparative Examples, respectively.

Referring first to Figure 1, it can be seen that all the catalyst powder of Example 1 has a spherical or partially broken sphere of a core-shell structure, in particular, in the case of a partially broken sphere, at least 50% of the surface of the hollow structure It can be seen that the shell is made of a flake formed of a metal component in the region.

On the other hand, referring to Figure 2, the shape of the catalyst powder of Comparative Examples 6, 7 is very non-uniform compared to Example 1, the catalyst powder having a complete spherical core-shell structure was not observed at all, and also the shape of the flakes It can be seen that this plate-shaped or curved surface having a constant curvature does not have a substantially hollow structure.

Experimental Example

Carbon nanotubes were synthesized using catalyst powders according to Examples and Comparative Examples. Specifically, each catalyst powder was introduced into a fluidized bed chemical vapor deposition reactor having a diameter of 350 mm, and maintained at 700-800 ° C. in a nitrogen atmosphere. Thereafter, a mixture of nitrogen and ethylene was supplied at a rate of 150 L per minute for 40 minutes to synthesize carbon nanotubes grown on the respective catalyst powders.

The apparent density of the catalyst powder was obtained by measuring the weight by filling the catalyst powder in the mass cylinder, and dividing the measured weight by the volume of the mass cylinder. The apparent density of the carbon nanotubes was measured in the same manner. In addition, the synthesis yield of carbon nanotubes was calculated according to the formula "weight of synthesized carbon nanotubes (g)] / [weight of injected catalyst powder (g)] * 100". The measurement results are shown in Table 2 below.

division	Catalyst powder apparent density (g / mL)	Carbon Nanotube Synthesis Yield (%)	Carbon nanotube apparent density (g / mL)
Example 1	0.180	1,264	0.015
Example 2	0.060	1,490	0.022
Example 3	0.516	1,400	0.020
Example 4	0.077	1,354	0.020
Example 5	0.072	1,437	0.022
Example 6	0.084	2,600	0.023
Example 7	0.090	1,392	0.015
Example 8	0.215	4,282	0.027
Example 9	0.369	3,855	0.031
Example 10	0.662	4,030	0.034
Comparative Example 1	0.164	651	0.008
Comparative Example 2	0.470	967	0.029
Comparative Example 3	0.437	826	0.076
Comparative Example 4	0.906	0	-
Comparative Example 5	0.815	763	0.053
Comparative Example 6	0.726	582	0.013
Comparative Example 7	0.028	594	0.007
Comparative Example 8	1.056	742	0.012

Referring to Table 2, when synthesizing carbon nanotubes in a fluidized bed chemical vapor deposition reactor using the catalysts of Examples 1 to 10, a high synthesis yield of 1,200% or more can be obtained, which is suitable for mass production of carbon nanotubes. You can check it. However, when the catalyst of the comparative example is used, the synthesis yield of carbon nanotubes is less than 1,000%, which is not suitable for mass production. From these results, it can be seen that the catalyst of the comparative example is not a catalyst suitable for a fluidized bed chemical vapor deposition reactor. The catalysts of Comparative Examples 4, 5, 6, and 8 are difficult to float in the fluidized bed chemical vapor deposition method of synthesizing carbon nanotubes while floating the catalyst powder with the reaction gas with an apparent density of 0.70 g / mL or more. there is a problem.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the invention is indicated by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the invention.

Claims (9)

1. It contains a metal component according to the following formula,

   <Expression>

   Ma: Mb = x: y

   Catalyst for preparing multi-walled carbon nanotubes having a hollow structure with a thickness of 0.5 ~ 10㎛:

   Where

   Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu,

   Mb is at least one metal selected from Mg, Al, Si and Zr,

   x and y represent the mole fraction of Ma and Mb, respectively

   x + y = 10, 2.0 ≦ x ≦ 7.5, 2.5 ≦ y ≦ 8.0.
2. The method of claim 1,

   A catalyst for producing multi-walled carbon nanotubes having an apparent density of 0.05 to 0.70 g / mL.
3. The method of claim 1,

   Catalyst for producing multi-walled carbon nanotubes having a thickness of 1 ~ 8㎛.
4. The method of claim 1,

   Catalyst for producing multi-walled carbon nanotubes having a hollow ratio of the hollow structure is 50% by volume or more.
5. Carbon nanotube assembly comprising a bundle of carbon nanotubes made of a plurality of multi-walled carbon nanotubes grown on the catalyst for producing a multi-walled carbon nanotubes according to any one of claims 1 to 4.
6. The method of claim 5,

   An average bundle diameter of the bundle type carbon nanotubes (0.5 ~ 20㎛), the average bundle length (bundle length) 10 ~ 200㎛ carbon nanotube assembly.
7. The method of claim 5,

   Raman spectral intensity ratio (I _G / I _D ) of the multi-walled carbon nanotubes of the carbon nanotube assembly.
8. The method of claim 5,

   Carbon nanotube assembly having an average diameter of the multi-walled carbon nanotubes of 5 ~ 50nm.
9. The method of claim 5,

   Carbon nanotube assembly having an apparent density of the multi-walled carbon nanotubes 0.01 ~ 0.07g / mL.

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