KR20160084290A - Catalyst comprising cellulose based polymer for obtaining carbon nanotube, process for preparing same, and method for controlling diameter of carbon nanotubes using same - Google Patents
Catalyst comprising cellulose based polymer for obtaining carbon nanotube, process for preparing same, and method for controlling diameter of carbon nanotubes using same Download PDFInfo
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- KR20160084290A KR20160084290A KR1020150152931A KR20150152931A KR20160084290A KR 20160084290 A KR20160084290 A KR 20160084290A KR 1020150152931 A KR1020150152931 A KR 1020150152931A KR 20150152931 A KR20150152931 A KR 20150152931A KR 20160084290 A KR20160084290 A KR 20160084290A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C01B2202/00—Structure or properties of carbon nanotubes
Abstract
Description
TECHNICAL FIELD The present invention relates to a catalyst for synthesizing carbon nanotubes containing a cellulose-based polymer, a process for producing the same, and a CNT diameter controlling method using the same, and more particularly, to a cellulose polymer capable of synthesizing a large-diameter carbon nanotube without a high reaction temperature or an additional heat- Containing catalyst, a process for producing the same, and a CNT diameter control method using the same.
Generally, a carbon nanotube (hereinafter, referred to as CNT) has a cylindrical carbon tube having a diameter of about 3 to 150 nm, specifically about 3 to 100 nm, and a length several times the diameter, for example, 100 times or more Quot; These CNTs are composed of layers of ordered carbon atoms and have different types of cores. Such CNTs are also referred to as carbon fibrils or hollow carbon fibers, for example.
On the other hand, such CNTs are industrially important in the production of composites due to their size and specific physical properties, and have high utility in the fields of electronic materials, energy materials and various other fields.
The CNT can be generally manufactured by an arc discharge method, a laser evaporation method, a chemical vapor deposition method, or the like. Among them, the arc discharge method and the laser evaporation method are difficult to mass-produce, and there is a problem that economical efficiency is lowered due to an excessive cost of producing an arc or a cost of purchasing a laser apparatus.
The catalyst used in the chemical vapor deposition method may be an impregnation catalyst, a coprecipitation catalyst, or the like, the catalytically active component having an oxide form, a partially or fully reduced form, or a hydroxide form, and which can be generally used for producing CNTs. It is preferable to use a double impregnation catalyst because when the impregnated catalyst is used, the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst and unlike the coprecipitation catalyst, the attrition that can occur during the fluidization process is small It is possible to reduce the possibility of generation of a fine particle by the catalyst, and the mechanical strength of the catalyst itself is also excellent, so that the operation of the reactor can be stabilized.
Also, as a method for producing such impregnated catalyst, there is proposed a technique (impregnation method) for preparing a catalyst by mixing a metal aqueous solution and a support followed by coating-drying. Porous structure is mainly used as a support. In order to obtain large-diameter CNTs using such catalysts, a high reaction temperature and high temperature heat treatment are inevitably required. When the reaction temperature is high, there is a problem that a large amount of carbon impurities are generated in the reactor, and in the case of the high temperature heat treatment process, a high cost is additionally incurred, which leads to a problem that economical efficiency is lowered.
SUMMARY OF THE INVENTION [0006]
And is capable of easily controlling the diameter even at a low reaction temperature to obtain a CNT having a large diameter.
[0010] Another object of the present invention is to provide
And a method for producing the CNT synthesis catalyst.
[0010] Another object of the present invention is to provide a high-
And a method for producing CNT using the CNT synthesis catalyst.
[0010] Another object of the present invention is to provide a high-
And controlling the diameter of the CNT by controlling the composition ratio of the CNT synthesis catalyst.
According to an aspect of the present invention,
Wherein the metal catalyst is supported on a porous support made of a cellulose-based polymer.
According to another aspect of the present invention,
Mixing an aqueous metal solution containing a metal catalyst precursor with a cellulosic polymer to form an aqueous solution containing a catalyst precursor;
Removing the solvent component in the catalyst precursor-containing aqueous solution to obtain a gel material; And
And drying the gel material at a temperature of 150 to 250 ° C to obtain a particulate catalyst.
According to another aspect of the present invention,
Introducing a catalyst for synthesizing CNTs containing a cellulose-based polymer and a metal catalyst into a reactor;
Injecting a carbon source or a mixed gas of hydrogen and nitrogen into the reactor at a temperature of 700 ° C or lower; And
And growing the CNT through decomposition of the carbon source on the surface of the catalyst,
And controlling the diameter of the CNT by controlling the ratio of the first catalyst and the second catalyst, wherein the metal catalyst includes a first catalyst and a second catalyst.
The CNT synthesis catalyst according to the present invention enables production of large-diameter CNTs at a low reaction temperature without a high reaction temperature or high temperature heat treatment process. Particularly, the diameter of the CNT can be controlled by controlling the catalyst component.
Fig. 1 shows an SEM photograph of the catalyst obtained in Example 1. Fig.
Fig. 2 shows an enlarged photograph of the area A in Fig.
3 is an SEM photograph of the catalyst obtained in Comparative Example 1. Fig.
4 is a SEM photograph of the CNT obtained in Example 3. Fig.
5 is a SEM photograph of the CNT obtained in Example 4. Fig.
6 is an SEM photograph of the CNT obtained in Comparative Example 2. Fig.
The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor can properly define the concept of the term to describe its invention in the best possible way And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention.
Hereinafter, the present invention will be described in detail.
The catalyst for synthesizing CNT according to an embodiment includes a cellulosic polymer and a metal catalyst.
In the case of inorganic carriers that have been conventionally used, their diameters are limited in the CNT synthesis due to their porous structure, for example, pore size and distribution. The CNT synthesis catalyst according to the present invention can overcome the limitations of the inorganic support by providing a porous structure using a cellulose-based polymer without an inorganic carrier such as alumina as a porous structure.
The catalyst for synthesizing CNT according to the present invention comprises a cellulose-based polymer without an inorganic carrier and a metal catalyst of the above formula (1), and the cellulose-based polymer forms a porous structure adjacent to the metal catalyst particles, Thereby supporting the metal catalyst.
The cellulose-based polymer used in the catalyst is preferably soluble in a solvent, and for example, a water-soluble polymer may be used. More specifically, the cellulose-based polymer may have a repeating unit represented by the following formula (1).
≪ Formula 1 >
In Formula 1, each R is independently a hydrogen atom, a C1-10 alkyl, a hydroxy C1-10 alkyl, a carboxy C1-10 alkyl, or an alkali metal salt thereof.
According to one embodiment, at least one of hydroxymethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, carboxyethylcellulose, or an alkali metal salt thereof may be used as the cellulose-based polymer.
The metal catalyst particles contained in the catalyst have a composition represented by the following formula (2)
And metal catalyst particles of formula (2)
(2)
[Fe, Co, Ni] p [Al, Mg, Mn, Mo, V] q
Where p and q are the mole fractions of [Fe, Co, Ni] and [Al, Mg, Mn, Mo, V], where p + q = 1, 0.1? P? 0.9, 0.1? Q? 0.9,
[Fe, Co, Ni] is a first catalyst containing at least one of Fe, Co and Ni,
The above-mentioned [Al, Mg, Mn, Mo, V] is a second catalyst containing at least one of Al, Mg, Mn, Mo and V.
Preferably a first catalyst of Co and preferably a second catalyst of Al.
The cellulose-based polymer may be used in an amount of about 10 to 500 parts by weight based on 100 parts by weight of the metal catalyst particles, and a sufficient porous structure may be provided in the catalyst in this range.
The catalyst for synthesis of CNT according to the present invention may be any suitable size as a particle. For example, the catalyst may have a specific surface area as measured by the BET method, for example, from about 0.1 m 2 / g to about 10 m 2 / g.
In addition, the catalyst for synthesizing CNT according to the present invention does not contain an inorganic carrier having a porous structure, but may have a pore volume of 0.1 to 5 cm 3 / g, for example, as the cellulosic polymer structure has a porous structure.
The CNT synthesis catalyst of the present invention as described above can be produced by the following method.
According to one embodiment, a method for producing a catalyst for synthesizing CNT according to the present invention comprises:
(1) mixing an aqueous metal solution containing a metal catalyst precursor with a cellulose-based polymer to form an aqueous solution containing a catalyst precursor;
(2) removing the solvent component from the catalyst precursor-containing aqueous solution to obtain a gel material; And
(3) drying the gel material at a temperature of 150 ° C to 250 ° C at a high temperature to obtain a particulate catalyst.
In step (1), the aqueous solution containing a catalyst precursor is formed by mixing a metal-based catalyst precursor, preferably a first catalyst precursor and a second catalyst precursor, with a cellulose-based polymer .
The first catalyst precursor used in the process may include at least one selected from Fe, Co and Ni, and examples thereof include Fe salts, Fe oxides, Fe compounds, Co salts, Co oxides, Co compounds, (NO 3 ) 2 .6H 2 O, Fe (NO 3 ) 2 .9H 2 O, Ni (NO 3 ) 2 .6H 2 O and the like. O, Co (NO 3 ) 2 .6H 2 O, and the like.
The second catalyst precursor used in the above step may include at least one of Al, Mg, Mn, Mo, and V, and may include at least one of Al salt, Al oxide, Al compound, Mg salt, Mg And can be used by dissolving it in distilled water, and it can be used as an oxide, Mg compound, Mn salt, Mn oxide, Mn compound, Mo salt, Mo oxide, Mo compound, V salt, V oxide,
The first catalyst precursor and the second catalyst precursor can be used in an amount satisfying the composition of the metal catalyst particle of Formula 2 contained in the resultant catalyst, and sufficient CNT synthesis efficiency can be exhibited in such a range.
Examples of the cellulose-based polymer used in the above process include hydroxymethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, carboxyethylcellulose, and alkali metal salts thereof. More specifically, sodium carboxymethylcellulose Can be used.
Considering the reaction efficiency, it is more efficient to use the concentration of the metal aqueous solution used in the step (1) in the range of, for example, 0.1 to 0.5 g / ml, or 0.1 to 0.3 g / ml. The cellulosic polymer mixed in the metal aqueous solution may be used in an amount of about 10 to 500 parts by weight based on 100 parts by weight of the metal catalyst particles in the resultant catalyst.
In step (2) of the above production method, the solvent component, that is, water is removed from the catalyst precursor-containing aqueous solution to obtain a gel-like substance. Such a process can be carried out by rotary evaporation under vacuum, and can be carried out, for example, at 45 to 90 DEG C for 10 hours or for 1 minute to 5 hours.
In the vacuum drying described in this specification, the meaning of "vacuum" is not particularly limited when it corresponds to the vacuum range normally applied to vacuum drying.
In step (3) of the above-described method, the resultant product obtained in step (2) is dried at a high temperature to form the final catalyst of the present invention. Such a high-temperature drying is carried out at a temperature of about 150 to 250 ° C, Lt; 0 > C. The high-temperature drying time is not limited thereto, but can be performed within about 30 minutes to 5 hours.
The catalyst for synthesizing CNT of the present invention obtained according to the above production method comprises a metal catalyst particle of the following formula (2) and a cellulose-based polymer forming a porous structure adjacent to the metal catalyst particle.
(2)
[Fe, Co, Ni] p [Al, Mg, Mn, Mo, V] q
Where p and q are the mole fractions of [Fe, Co, Ni] and [Al, Mg, Mn, Mo, V], where p + q = 1, 0.1? P? 0.9, 0.1? Q? 0.9,
[Fe, Co, Ni] is a first catalyst containing at least one of Fe, Co and Ni,
The above-mentioned [Al, Mg, Mn, Mo, V] is a second catalyst containing at least one of Al, Mg, Mn, Mo and V.
The process for producing CNT from the CNT synthesis catalyst obtained by the above-mentioned method includes, but is not limited to, the following steps:
Introducing a carbon source for the CNT synthesis catalyst according to the present invention into the reactor at a temperature of about 750 ° C or less and injecting hydrogen gas, nitrogen gas or a mixture thereof into the reactor; And
And growing the CNT through decomposition of the carbon source injected on the catalyst surface.
According to one embodiment, the reactor may be a fixed bed reactor or a fluidized bed reactor without limitation.
In the CNT production method, when the reaction temperature is in the range of 750 ° C or lower, for example, 650 ° C to 750 ° C, the specific surface area of the produced CNT is decreased while using the catalyst obtained by the above- It becomes possible to manufacture the large diameter CNT by increasing the diameter of the CNT.
The CNT obtained by the above production method may have a specific surface area of 30 to 50 m 2 / g as measured by the BET method.
In addition, in the CNT production method, it is possible to control the diameters of the CNTs by adjusting the values of p and q in the formula (2). That is, it is possible to control the diameter of the CNT to a desired range by controlling the content of the first catalyst and the second catalyst contained in the catalyst.
The CNT of the present invention can be used as a raw material in an electric field, an electronic field, an energy field, and the like, and can also be used as a reinforcing material in a plastic field.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to be illustrative of the present invention and the scope of the invention as defined by the appended claims. It will be obvious that such variations and modifications are intended to fall within the scope of the appended claims.
Example 1: Preparation of catalyst for synthesis of CNT
0.2 g NH 4 VO 3 and 0.14 g citric acid were dissolved in 50 ml of deionized water and 2 g of Co (NO 3 ) 2 .6H 2 O and 6 g of Al (NO 3 ) 3 .9H 2 O were continuously added to obtain a metal salt aqueous solution . 30 g of carboxymethylcellulose sodium was added to this solution, and the mixture was stirred for 10 minutes to form an aqueous solution containing a catalyst precursor. This aqueous solution was rotary evaporated at 60 DEG C to obtain a gel-like material. The obtained gelled material was dried at 200 ° C for 3 hours at a high temperature to obtain a particulate solid catalyst. The molar% ratio of the metal used in the preparation of the catalyst was Co: Al = 1: 2.3, and the carboxymethyl cellulose sodium was used in a proportion of 181 parts by weight based on 100 parts by weight of the metal.
An SEM photograph of the resultant solid catalyst is shown in Fig. 1, and an enlarged photograph of the area A is shown in Fig. 1 and 2, it can be seen that the porous structure is formed on the surface of the metal particles.
Example 2: Preparation of catalyst for synthesis of CNT
0.2 g NH 4 VO 3 and 0.14 g citric acid were dissolved in 50 ml of deionized water and 2 g of Co (NO 3 ) 2 .6H 2 O and 2 g of Al (NO 3 ) 3 .9H 2 O were continuously added to obtain a metal salt aqueous solution . 30 g of sodium carboxymethylcellulose sodium solution (5% by weight) was added to this solution, and the mixture was stirred for 10 minutes to form a catalyst precursor-containing aqueous solution. This aqueous solution was rotary evaporated at 60 DEG C to obtain a gel-like material. The obtained gelled material was dried at 200 ° C for 3 hours at a high temperature to obtain a particulate solid catalyst. The molar ratio of the metal used in the preparation of the catalyst was Co: Al = 1.3: 1, and the carboxymethyl cellulose sodium was used in a proportion of 278 parts by weight based on 100 parts by weight of the metal.
Comparative Example 1
A particulate solid catalyst was obtained by carrying out the same process except that carboxymethylcellulose sodium was not used in Example 1 above. The molar% ratio of the metals used in the preparation of the catalyst was Co: Al = 1: 2.3.
An SEM photograph of the resultant solid catalyst is shown in FIG. As can be seen from Fig. 3, it did not contain any porous structure at all.
Example 3: CNT production example
Carbon nanotubes were synthesized in a laboratory scale fixed bed reactor using the CNT synthesis catalyst prepared in Example 1 above. Specifically, the catalyst for synthesizing CNTs prepared in Example 1 was attached to the middle portion of a quartz tube having an inner diameter of 55 mm, and then heated to 700 ° C in a nitrogen atmosphere and maintained. The ratio of nitrogen: hydrogen: Was synthesized at a ratio of 1: 1: 1 for 2 hours to synthesize a predetermined amount of carbon nanotube aggregates. The CNT yield at this time was 14 CNT g / g catalyst.
An SEM photograph of the obtained CNT is shown in Fig.
Example 4: CNT production example
The synthesis of carbon nanotubes was tested in a laboratory scale fixed bed reactor using the CNT synthesis catalyst prepared above. Specifically, the catalyst for synthesizing CNTs prepared in Example 1 was attached to the middle portion of a quartz tube having an inner diameter of 55 mm, and then heated to 700 ° C in a nitrogen atmosphere and maintained. The ratio of nitrogen: hydrogen: At a ratio of 1: 1: 1 was synthesized for 2 hours to synthesize a predetermined amount of carbon nanotube agglomerates. The CNT yield at this time was 5 CNT g / g of catalyst.
An SEM photograph of the obtained CNT is shown in Fig. As can be seen from FIG. 5, it can be seen that the diameter of the CNT was increased by increasing the metal content of the catalyst. Therefore, it was confirmed that the diameter of the CNT can be controlled by using the catalyst according to the present invention.
Comparative Example 2
The carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using the CNT synthesis catalyst prepared in Comparative Example 1. Specifically, the CNT synthesis catalyst prepared in Comparative Example 1 was attached to the middle portion of a quartz tube having an inner diameter of 55 mm, and then heated to 700 ° C in a nitrogen atmosphere and maintained. The ratio of nitrogen: hydrogen: Was synthesized at a ratio of 1: 1: 1 for 2 hours to synthesize a predetermined amount of carbon nanotube aggregates. The yield of CNT at this time was 43 CNT g / g of catalyst.
An SEM photograph of the obtained CNT is shown in Fig. As can be seen from FIG. 6, when the cellulosic polymer is not used, the CNT diameter is small.
Claims (16)
Wherein the cellulose-based polymer has a repeating unit represented by the following formula (1): < EMI ID =
≪ Formula 1 >
In Formula 2, each R is independently a hydrogen atom, a C1-10 alkyl, a hydroxy C1-10 alkyl, a carboxy C1-10 alkyl, or an alkali metal salt thereof.
Wherein the metal catalyst is represented by Formula 2:
(2)
[Fe, Co, Ni] p [Al, Mg, Mn, Mo, V] q
Where p and q are the mole fractions of [Fe, Co, Ni] and [Al, Mg, Mn, Mo, V], where p + q = 1, 0.1? P? 0.9, 0.1? Q? 0.9,
[Fe, Co, Ni] is a first catalyst containing at least one of Fe, Co and Ni,
The above-mentioned [Al, Mg, Mn, Mo, V] is a second catalyst containing at least one of Al, Mg, Mn, Mo and V.
Wherein the first catalyst is Co and the second catalyst is Al.
Wherein the cellulose-based polymer is present in an amount of about 10 to 500 parts by weight based on 100 parts by weight of the metal catalyst particles.
Wherein the catalyst has a specific surface area of about 0.1 m 2 / g to about 10 m 2 / g as measured by the BET method.
Wherein the catalyst has a pore volume of 0.1 to 5 cm < 3 > / g.
Removing the solvent component in the catalyst precursor-containing aqueous solution to obtain a gel material; And
And drying the gel material at a temperature of 150 to 250 ° C to obtain a particulate catalyst.
Wherein the metal catalyst is at least one of a salt, an oxide or a compound of Fe, Co or Ni and a second catalyst precursor which is at least one of a salt, an oxide or a compound of Al, Mg, Mn, Mo or V, By weight based on the total weight of the carbon nanotubes.
Wherein the concentration of the metal aqueous solution is 0.1 to 0.5 g / ml.
And growing a carbon nanotube through decomposition of a carbon source injected onto the surface of the catalyst.
Wherein the reactor is a fixed bed reactor or a fluidized bed reactor.
Wherein the reaction temperature is 650 ° C to 750 ° C.
Wherein the specific surface area of the carbon nanotubes is 10 to 80 m 2 / g as measured by the BET method.
And growing the carbon nanotubes through decomposition of the carbon source injected on the catalyst surface,
And controlling the diameter of the carbon nanotubes by controlling the molar ratio of the first catalyst and the second catalyst included in the catalyst to control the diameter of the carbon nanotubes.
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