JP2008093494A - Catalyst for producing nano-carbon material and method for manufacturing the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing a nano-carbon material, which makes it possible to mass-produce the high-purity single layer nano-carbon material continuously and to provide a catalyst fine particle, a method for manufacturing the catalyst for producing the nano-carbon material and a system for producing the nano-carbon material. <P>SOLUTION: The catalyst 10 for producing the nano-carbon material, which is used for producing the nano-carbon material from a raw carbon material, is manufactured by depositing an active metal 11 on the surface of a carrier 12 while interposing an agglomeration preventing material 15 for preventing the agglomeration of the active metal between the active metal and the surface of the carrier. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a catalyst for producing a nanocarbon material, catalyst fine particles, a method for producing a catalyst for producing a nanocarbon material, and a nanocarbon material production system that can produce a carbon material efficiently and with high purity.

  The carbon nanotube is a tubular carbon polyhedron having a structure in which a graphite (graphite) sheet is closed in a cylindrical shape. The carbon nanotube includes a multi-layer nanotube having a multilayer structure in which a graphite sheet is closed in a cylindrical shape, and a single-wall nanotube having a single-layer structure in which a graphite sheet is closed in a cylindrical shape.

  One multi-walled nanotube was discovered by Iijima in 1991. That is, it was discovered that multi-walled nanotubes exist in the carbon mass deposited on the cathode of the arc discharge method (Non-Patent Document 1). Since then, research on multi-walled nanotubes has been actively conducted, and in recent years, it has become possible to synthesize a large number of multi-walled nanotubes.

  In contrast, single-walled nanotubes have an inner diameter of approximately 0.4 to 10 nanometers (nm), and their synthesis was simultaneously reported in 1993 by a group of Iijima and IBM. The electronic state of single-walled nanotubes has been predicted theoretically, and it is thought that the electronic properties change from metallic properties to semiconducting properties depending on how the spiral is wound. Therefore, such single-walled nanotubes are considered promising as future electronic materials.

  Other applications of single-walled nanotubes include nanoelectronic materials, field electron emitters, highly directional radiation sources, soft X-ray sources, one-dimensional conducting materials, high thermal conducting materials, hydrogen storage materials, and the like. Further, it is considered that the use of single-walled nanotubes is further expanded by functionalization of the surface, metal coating, and inclusion of foreign substances.

Conventionally, the single-walled nanotubes described above are manufactured by mixing a metal such as iron, cobalt, nickel, or lanthanum into a carbon rod of an anode and performing arc discharge (Patent Document 1).
However, in this production method, in addition to single-walled nanotubes, multi-walled nanotubes, graphite, and amorphous carbon are mixed in the product, and not only the yield is low, but also the diameter and length of single-walled nanotubes vary. In addition, it was difficult to produce single-walled nanotubes with relatively uniform yarn diameter and yarn length in high yield.

  In addition to the arc method described above, a vapor phase pyrolysis method, a laser sublimation method, a condensed phase electrolysis method, and the like have been proposed as methods for producing carbon nanotubes (Patent Documents 2 to 4).

However, any of the production methods disclosed in these documents is a laboratory or small-scale production method, and there is a problem that the yield of the carbon material is low and the purity is particularly low.
In recent years, the use of carbon materials has expanded, and for this reason, the advent of an apparatus that can produce carbon materials with good purity while being able to be produced efficiently in large quantities is desired.

  Therefore, the present inventors have previously proposed that carbon nanofibers be produced in a fluidized bed (Patent Document 5).

S. Iijima, Nature, 354, 56 (1991) Japanese Patent Laid-Open No. 06-280116 Japanese Patent No. 3100962 JP-T-2001-520615 JP 2001-139317 A JP 2004-76197 A

  However, when a single layer carbon material is produced by the fluidized bed method of Patent Document 5, as shown in FIG. 15, when the catalyst in which the active metal 1 is supported on the carrier 2 is also used as a fluidizing agent, the catalyst There is a problem that the active metals 1 are aggregated and coarsened during production, and the selectivity between the single-layer nanocarbon tube 3 and the multi-layer nanocarbon tube 4 in the synthesis of the nanocarbon material is deteriorated. That is, there is a problem that the yield of the single-walled nanocarbon tube 3 is lowered because the proportion of growth of the multilayered nanocarbon tube 4 is increased from the agglomerated active metal.

  Further, in the production of the catalyst, even when the fine active metal 1 is dispersed and supported on the support 2, when the nanocarbon material is produced at a high temperature in the fluidized bed reactor, the aggregation of the active metals 1 proceeds, In addition, there is a problem in that the rate of growth of the multi-layer nanocarbon tube 4 increases, and the yield of the single-layer nanocarbon tube 3 decreases.

  Therefore, it is desired to industrially produce a high-purity single-layer nanocarbon material by, for example, a fluidized bed method.

  In view of the above circumstances, the present invention provides a catalyst for producing a nanocarbon material, a catalyst fine particle, and a catalyst for producing a nanocarbon material that can be continuously mass-produced and can produce a single-layer carbon material having a high purity. It is an object to provide a manufacturing method and a nanocarbon material manufacturing system.

  A first invention of the present invention for solving the above-mentioned problems is a catalyst for producing a nanocarbon material using a carbon raw material, and an active metal aggregation preventing material is interposed on the surface of the support. Thus, the present invention provides a catalyst for producing a nanocarbon material, wherein an active metal is supported.

  A second invention is the catalyst for producing a nanocarbon material according to the first invention, wherein the active metal aggregation preventing material is an alkaline earth metal or an alkali metal.

  According to a third invention, in the first or second invention, the active metal is any one of V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, or a combination thereof, and the carrier is alumina, silica , Sodium aluminate, alum, aluminum phosphate, calcium oxide, calcium carbonate, calcium sulfate, magnesium oxide, magnesium hydroxide, magnesium sulfate, calcium phosphate, or magnesium phosphate In production catalyst.

  A fourth invention is the catalyst for producing a nanocarbon material according to the third invention, wherein the active metal contains one or both promoters of Mo and W.

  A fifth invention is the catalyst for producing a nanocarbon material according to any one of the first to fourth inventions, wherein the nanocarbon material is a single-walled carbon nanotube.

  A sixth invention is a catalyst fine particle characterized in that the catalyst for producing a nanocarbon material according to any one of the first to fifth particles is granulated to form fine particles of 0.005 to 10 mm.

  In the seventh invention, the carrier material is immersed in a solvent in which the raw material salt for the active metal and the raw material salt for the active metal agglomeration preventing material are dissolved, then dried, and then subjected to an activation heat treatment, The method for producing a nanocarbon material production catalyst according to claim 1 is produced.

  According to an eighth invention, there is provided a catalyst for producing a nanocarbon material according to the seventh invention, wherein the support material is immersed, stirred, dried, granulated, then sized and then subjected to an activation heat treatment. In the manufacturing method.

  A ninth invention is the method for producing a catalyst for producing a nanocarbon material according to the seventh or eighth invention, wherein the activation heat treatment temperature is 500 to 1200 ° C.

  A tenth aspect of the invention is a manufacturing apparatus for manufacturing a nanocarbon material from a carbon raw material using any one of the first to fifth nanocarbon material manufacturing catalysts, a recovery apparatus for recovering the carbon material from the manufacturing apparatus, A nanocarbon material manufacturing system comprising a carbon material purification apparatus for separating a carrier from a recovered carbon material.

  An eleventh invention is the nanocarbon material production system according to the tenth invention, wherein the production apparatus for producing the nanocarbon material is a fluidized bed reaction apparatus.

  A twelfth invention is the nanocarbon material production system according to the eleventh invention, wherein the catalyst fine particles of the sixth invention are used to produce the nanocarbon material with a fluidized bed reactor.

  A thirteenth invention is the nanocarbon material manufacturing system according to any one of the tenth to twelfth inventions, wherein the nanocarbon material is a single-walled carbon nanotube.

  According to the present invention, since the aggregation of active metals is suppressed both in the production of the catalyst and in the production of the nanocarbon material, multilayer nanocarbon that is an impurity generated when the carbon material is produced is produced. Only a single-layer nanocarbon material can be produced without producing a material.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

A catalyst for producing a nanocarbon material according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view of a catalyst for producing a nanocarbon material according to an example.
As shown in FIG. 1, a catalyst 10 for producing a nanocarbon material according to the present embodiment is a catalyst for producing a nanocarbon material using a carbon raw material, and an active metal is formed on the surface of a support 12. The active metal 11 is supported by interposing an aggregation preventing material 15 for preventing aggregation.

  Here, the aggregation preventing material 15 is preferably, for example, an alkaline earth metal such as Mg or Ca, or one or a combination of two or more alkali metals such as Na and K. Among these, when the same or the same component as the carrier is included, the affinity between the carrier and the anti-aggregating material is further increased, and the anti-aggregation effect of the active metal can be improved.

  The agglomeration of the active metal 11 is suppressed by using the agglomeration preventing material 15 because the active metal anchor effect is obtained by performing an activation process in the catalyst production to produce a composite oxide of the active metal and the agglomeration preventing material. By demonstrating.

An example of the method for producing the catalyst for producing the carbon material is shown below.
For example, when using magnesium oxide as the carrier 12 and Fe as the active metal 11 and using Mg as the aggregation preventing material, first, iron nitrate and magnesium nitrate are dissolved in a solvent at a predetermined ratio. Magnesium oxide as the carrier 12 is added to this solution and dried with stirring. The solvent is then removed to obtain the catalyst. Further, if necessary, it is pulverized by a pulverizer such as a roll mill, and sized to fine particles having a predetermined particle size.

Next, the obtained catalyst is continuously heat-treated at a high temperature in an inert gas atmosphere in a reactor.
In this heat treatment, a composite oxide (MgFe ₂ O ₄ ) of the active metal and the aggregation preventing material or the carrier is partially formed.

  Here, the temperature of the heat treatment in the inert gas atmosphere is, for example, 500 to 1200 ° C., preferably about 800 ° C.

  FIG. 2 is a photograph of a TEM in which a nanocarbon material is produced using a catalyst that suppresses the aggregation of the active metal by the aggregation preventing material.

  At this time, the catalyst was Fe as an active metal, the aggregation preventing material was Mg, and the carrier was MgO. The activation process was performed at 800 ° C. for 13 minutes. Then, using the obtained catalyst, 1 g of the catalyst was put into a magnetic boat in a horizontal tubular furnace, and methane (20%) was used as a carbon raw material to produce a nanocarbon material at 800 ° C. for 15 minutes.

Moreover, FIGS. 3-1 and 3-2 are charts of Raman spectroscopic measurement results of the nanocarbon material obtained thereby, FIG. 3-1 is 1700 to 1300 cm ⁻¹ , and FIG. 3-2 is 300 to 100 cm ^−. The Raman signal intensity in ¹ is shown.
FIG. 4 is a photograph of a TEM produced with a nanocarbon material using a catalyst that does not suppress the aggregation of the active metal without using the anti-agglomeration material, and FIGS. 5-1 and 5-2 were obtained thereby. It is a chart of the Raman spectroscopic measurement result of nanocarbon material.
Confirmation was performed at 10 points. Note that the variation in peak height means that the existence ratio in the field of view is low and does not mean that the purity is poor.

Here, 1700～1300Cm ^-1 is for sure peaks from vibration modes within the graphite surface of the single-walled carbon nanotubes, 1580 cm ^-1 graphite: the peak of the (G crystalline), 1360 cm ^{- 1} is a broad peak of amorphous carbon (D: many defect structures). Moreover, 300-100 cm < ^-1 > originates in the tube structure (Radial Breathing Mode: RBM) of a single-walled carbon nanotube.

  G / D (average) obtained from the chart of the Raman spectroscopic measurement result of the nanocarbon material obtained by the catalyst of this example using the aggregation preventing material of FIGS. 3-1 and 3-2 is 10.0. , RBM / (G / D) was 6.6, confirming that the abundance of single-walled carbon nanotubes was large.

  On the other hand, G / D (average) obtained from the chart of the Raman spectroscopic measurement result of the nanocarbon material obtained by the conventional catalyst not using the aggregation preventing material of FIGS. 5-1 and 5-2 is 2.7. In addition, RBM / (G / D) was 0.012, and it was confirmed that the abundance of impurities such as multi-walled carbon nanotubes and amorphous carbon was large.

The result is shown in FIG. As shown in FIG. 6, it was confirmed that the abundance ratio of the single-walled carbon nanotubes was improved by preventing the aggregation of the active metal by using the aggregation preventing material.
That is, for example, by supporting an agglomeration preventing material together with an active metal such as Fe, the active metal is prevented from coarsening during the loading, and active even in a high temperature environment of, for example, 500 ° C. or higher such as during the synthesis of the carbon material T. It prevents the coarsening due to the aggregation on the surface of the metal carrier, and produces a single-layer nanocarbon material with high selectivity.

  Further, when Mo was added as a promoter, the produced carbon / catalyst increased from 3.97% to 10.7%.

  Further, the addition amount of the aggregation preventing material 15 is 10 to 1000%, preferably 50 to 200% with respect to an equimolar molar ratio when taking a composite form with respect to the active metal component. This is because if it is less than 10%, only a partial effect is exhibited, whereas if it exceeds 1000%, a further aggregation suppressing effect is not exhibited.

  Here, the active metal 11 constituting the catalyst for producing the nanocarbon material is not particularly limited. For example, any one of V, Cr, Mn, Fe, Co, Ni, Cu, and Zn is used. Or the combination of these can be mentioned.

  Examples of the carrier 12 carrying the active metal 11 include alumina, silica, sodium aluminate, alum, aluminum phosphate, calcium oxide, calcium carbonate, calcium sulfate, magnesium oxide, magnesium hydroxide, magnesium sulfate, calcium phosphate, or Any one of magnesium phosphate can be mentioned.

  Moreover, you may make it contain the promoter of either one or both of Mo or W in the said active metal. This is because by adding a small amount of the promoter such as Mo, the decomposition of the carbon raw material is promoted, the incorporation of carbon into an active metal such as iron is promoted, and the production of the carbon material is promoted.

  A method for producing a nanocarbon material using the catalyst for producing a nanocarbon material according to the present invention is not particularly limited. For example, as shown in FIG. A fluidized bed system in which a catalyst 10 for producing a nanocarbon material is added and fluidized, a raw material gas 103 is introduced from the lower part, and extracted from above is performed.

  As another manufacturing method, as shown in FIG. 8, the moving bed furnace 104 is filled with the catalyst 10, and the catalyst 10 for producing the nanocarbon material is gradually added and a part thereof is extracted, and the raw material gas 103 is used. A moving bed system in which the reaction is carried out from the bottom and extracted from above can be mentioned.

  As other manufacturing methods, as shown in FIG. 9, a fixed layer system in which a raw material gas 103 is put into a fixed bed furnace 105 from the lower part and extracted from above, or a gas phase reactor as shown in FIG. A gas flow layer system in which the catalyst 10 for producing the nanocarbon material is introduced together with the raw material gas 103 from one end of the 106, the reaction is performed, and the reactant is recovered at the other end can be exemplified.

  Here, the particle diameter of the catalyst fine particles for producing the nanocarbon material when used in the fluidized bed method as shown in FIG. 7 is not a fine catalyst, but is adjusted after granulating the fine catalyst. Thus, for example, a range of 0.05 to 10 mm, preferably 0.4 to 2.0 mm is preferable. This is because in the case of the fluidized bed reaction method, it is preferable to prevent the catalyst from being scattered by the fluidized gas.

Therefore, in the present invention, since the catalyst is extremely fine particles, the catalyst fine particles 16 having a predetermined diameter are adjusted by, for example, granulation.
In the case of the moving bed method, the fixed layer method, and the airflow layer method, it is preferable that the particle diameter is appropriately set appropriately.

Next, FIG. 11 shows an example of the production of the nanocarbon material production catalyst of the present example and a nanocarbon material production system using this nanocarbon material production catalyst.
The nanocarbon material manufacturing system 30 according to the present embodiment includes a stirring granulator 31 that supplies a support 12, a raw material salt for the active metal 11, a raw material salt for the aggregation preventing material 15, and the solvent 16; The pulverizing and granulating device 33 for pulverizing and sizing the supported granulating catalyst 32 obtained by the granulating device 31 and the activation treatment for activating the particle size control catalyst 34 whose particle size is adjusted by the pulverizing and granulating device 33. A device 35, a nanocarbon material production device 37 for producing a nanocarbon material by supplying an activation catalyst 36 and a raw material gas 38 activated by the activation treatment device 35, and the nanocarbon material production device 37. The catalyst removal purification apparatus 42 which removes the activated catalyst 36 from the nanocarbon material 39 with a catalyst manufactured in (1) to obtain a purified nanocarbon material 41 is provided.

In the stirring granulator 31, a raw material salt for the active metal 11 (iron nitrate) and a raw material salt for the aggregation preventing material 15 (magnesium nitrate) are dissolved in a solvent (ethanol) at a predetermined ratio. Thereafter, magnesium oxide (MgO) as a carrier is added to the solution, granulated while stirring, and dried under reduced pressure.
Thereafter, the lump obtained by evaporating ethanol to dryness is pulverized by a pulverizer (eg, a roll mill) 33 and sized to a particle size of 0.5 to 1.7 mm to obtain a particle size control catalyst 34.

  Next, the obtained particle size control catalyst 34 is heat-treated in the activation treatment device 35 by, for example, continuously heat-treating at 800 ° C. in nitrogen gas for a predetermined residence time.

The activated catalyst 36 that has been activated is put into a nanocarbon material production apparatus 37. In this nanocarbon material manufacturing apparatus 37, for example, the nanocarbon material grows on the activated catalyst by reacting at a source gas (CH ₄ = 20% (N ₂ balance)) at 800 ° C. for a predetermined residence time.

  The nanocarbon material 39 with catalyst obtained by growing the nanocarbon material on the catalyst obtained by the nanocarbon material production apparatus 37 is put into a hydrochloric acid solution of the catalyst removal and purification apparatus 42, and catalyst components and the like (Mg, Fe, etc.) are added. By dissolving and removing, a highly purified nanocarbon material purified product 41 can be obtained.

FIG. 12 is a system configuration diagram in which catalyst activity and nanocarbon material production are continuously performed using two fluidized bed reactors.
As shown in FIG. 12, in this embodiment, the upstream reactor is a fluidized bed reactor 51 for catalyst activation, and the downstream reactor is a fluidized bed reactor 52 for producing nanocarbon materials.
Then, the particle size control catalyst 34 having a controlled particle size is introduced into the catalyst activation fluidized bed reactor 51, the activation gas is supplied, and the activation treatment is performed at a predetermined temperature to obtain the activation catalyst 36. After that, the activated catalyst 36 is continuously supplied to the fluidized bed reactor 52 for producing the nanocarbon material to continuously produce the nanocarbon material. Then, after passing through a catalyst removal purification apparatus (not shown), the nanocarbon material product 41 is obtained.
In addition, you may make it perform the process according to a required quantity as a batch type instead of making it a continuous type.

  In addition, as shown in FIG. 13, the raw material may be partially oxidized by a partial oxidation device 54 and supplied as a high-temperature raw material gas 55 to a fluidized bed reactor 52 for producing a nanocarbon material. As a result, the high temperature source gas 55 is introduced, so that it can be used as a heat source for producing the carbon material, and external heating in the reaction can be eliminated or reduced.

Here, as the raw material 53, in addition to the flammable gas, a C-containing flammable solid material such as graphite and coal can be used in addition to the flammable liquid. Since the heat source is the source gas 55, the temperature uniformity of the reaction field is further increased, and as a result, the purity and yield of the carbon material can be improved.
Moreover, the heating at the time of scale-up becomes easy, and the equipment configuration can be simplified.

  Next, a specific example in which a fluidized bed reactor is used as the nanocarbon material production apparatus shown in FIG. 11 will be described with reference to FIG. In the present embodiment, the activated catalyst 36, which is activated by secondary particles having a predetermined particle diameter, is formed by compacting primary particles made of a carrier (magnesium oxide) in which an active metal (iron) is dispersed and supported by an aggregation preventing material. In addition, a fluid catalyst that combines a catalytic action and a fluid action is used.

As shown in FIG. 14, the fluidized bed reactor 52 for producing the nanocarbon material according to the present example includes a fluidized bed reaction unit 62-1 filled with an activated catalyst 36 that serves both as a catalyst and a fluidized material, A raw material supply device 63 for supplying a carbon gas 38 as a carbon source into the fluidized bed reaction unit 62-1, a fluidized catalyst supply device 64 for supplying an activation catalyst 36 into the fluidized bed reaction unit 62-1, A free board part 62-2 having a space in which the activated catalyst 36, which is a fluidized material in the fluidized bed reaction part 62-1, scatters and flows down, is introduced into the fluidized bed reaction part 62-1 and activated inside. A fluid gas supply device 66 for supplying a fluid gas 65 for fluidizing the catalyst 36, a heating unit 62-3 for heating the fluidized bed reaction unit 62-1 and the exhaust gas 22 discharged from the free board unit 62-2 are processed. Exhaust gas treatment device 67 and the front A recovery device 23 for recovering the catalyst with nano-carbon material 39 from the fluidized bed reaction unit 62-1 and drawn by recovery line 68 is for and a catalyst removal purification device 42 for purifying catalyst with nano-carbon material 39.
The fluidized bed reaction mode of the fluidized bed reaction section 62-1 includes a bubble type fluidized bed type and a jet type fluidized bed type, and any one may be used in the present invention.

  In the present embodiment, the fluidized bed reactor 62 is composed of the fluidized bed reaction section 62-1, the free board section 62-2, and the heating section 62-3. The free board section 62-2 preferably has a larger flow path cross-sectional area than the fluidized bed reaction section 62-1.

The carbon gas 38 which is the raw material gas supplied from the raw material supply device 63 may be any compound as long as it is a compound containing carbon. For example, in addition to CO, CO ₂ , methane, ethane, propane, hexane, etc. Alkanes, unsaturated organic compounds such as ethylene, propylene and acetylene, aromatic compounds such as benzene and toluene, organic compounds having oxygen-containing functional groups such as alcohols, ethers and carboxylic acids, polymers such as polyethylene and polypropylene Examples of the material include petroleum, coal (including coal conversion gas), and the like, but the present invention is not limited thereto. Further, in order to control the oxygen concentration, two or more oxygen-containing carbon sources CO, CO ₂ , alcohols, ethers, carboxylic acids and the like and a carbon source not containing oxygen can be supplied in combination.

  The carbon gas 38 is supplied in a gas state into the fluidized bed reaction section 62-1, and a uniform reaction is performed by stirring with the activation catalyst 36 that is a fluidized material, thereby growing the nanocarbon material. At this time, an inert gas is separately introduced into the fluidized bed reaction section 62-1 as the fluidized gas 65 by the fluidized gas supply device 66 so as to satisfy the predetermined fluidization conditions.

  And the inside of the fluidized bed reaction part 62-1 is made into the temperature range of 300 degreeC-1300 degreeC by the heating part 62-3, More preferably, it is the temperature range of 400 degreeC-1200 degreeC, and carbon gas 38, such as methane, is impurity carbon decomposition product Nanocarbon materials are synthesized by contacting the catalyst for a certain period of time in a coexisting environment.

  In addition to the cyclone, the recovery device 23 may be a known separation means such as a bag filter, a ceramic filter, or a sieve.

  Further, as described above, the catalyst-attached nanocarbon material 39 separated by the recovery device 23 is purified by dissolving the catalyst adhering to the catalyst removal and purification device 42, and nano-unit nanocarbon material (for example, carbon nanotube, Carbon nanofiber etc.).

  As described above, according to this example, when the nanocarbon material by the fluidized bed reaction mode is manufactured, the activation catalyst 36 in which the aggregation of the active metal is prevented is used, so that the multilayer nanocarbon material which is an impurity is used. Alternatively, a single-layer nanocarbon material can be obtained without producing an amorphous carbon material.

  As described above, the nanocarbon material production catalyst according to the present invention suppresses aggregation of active metals, and thus does not produce a multilayer nanocarbon material that is an impurity generated when producing a carbon material. Only the nano-carbon material of the layer can be manufactured, and mass production of a large-scale carbon material can be realized.

It is a schematic diagram of the catalyst for nanocarbon material manufacture which concerns on an Example. It is a transmission electron microscope (TEM) photograph of the nanocarbon material manufactured by this invention goods. It is a chart (1700-1300 cm < ^-1 >) of the Raman spectroscopic measurement result of the nanocarbon material manufactured by this invention goods. It is a chart (300-100cm < ^-1 >) of the Raman spectroscopy measurement result of the nanocarbon material manufactured by this invention goods. It is a transmission electron microscope (TEM) photograph of the nanocarbon material manufactured by the comparative product. It is a chart (1700-1300 cm < ^-1 >) of the Raman spectroscopic measurement result of the nanocarbon material manufactured by the comparative product. It is a chart (300-100cm < ^-1 >) of the Raman spectroscopic measurement result of the nanocarbon material manufactured by the comparative product. It is a graph which shows the ratio of the single layer carbon of the nanocarbon material manufactured by this invention product and the comparison product, and multilayer carbon. It is the schematic of the manufacturing apparatus of the nanocarbon material by the fluidized bed system concerning a present Example. It is the schematic of the moving bed reaction system concerning a present Example. It is the schematic of the fixed bed reaction system concerning a present Example. It is the schematic of the airflow layer reaction system concerning a present Example. It is the schematic of the manufacturing system of nanocarbon material. It is a system configuration schematic diagram in which the activity of a catalyst and the production of a nanocarbon material are continuously performed using two fluidized bed reactors. FIG. 5 is a schematic diagram of another system configuration in which catalyst activity and production of a nanocarbon material are successively performed using two fluidized bed reactors. It is the schematic of the fluidized bed reactor for nanocarbon material manufacture. It is a schematic diagram which shows a mode that the conventional active metal aggregates.

Explanation of symbols

10 Nanocarbon material production catalyst 11 Active metal 12 Support 15 Aggregation preventing material

Claims (13)

A catalyst for producing a nanocarbon material using a carbon raw material to produce a nanocarbon material,
A catalyst for producing a nanocarbon material, wherein an active metal is supported on the surface of a carrier with an active metal aggregation preventing material interposed therebetween. In claim 1,
The catalyst for producing a nanocarbon material, wherein the active metal aggregation preventing material is an alkaline earth metal or an alkali metal. In claim 1 or 2,
The active metal is any one of V, Cr, Mn, Fe, Co, Ni, Cu, Zn or a combination thereof;
The carrier is any one of alumina, silica, sodium aluminate, alum, aluminum phosphate, calcium oxide, calcium carbonate, calcium sulfate, magnesium oxide, magnesium hydroxide, magnesium sulfate, calcium phosphate, or magnesium phosphate. A catalyst for producing nano-carbon materials. In claim 3,
A catalyst for producing a nanocarbon material, wherein the active metal contains one or both promoters of Mo and W. In any one of Claims 1 thru | or 4,
A catalyst for producing a nanocarbon material, wherein the nanocarbon material is a single-walled carbon nanotube.   A catalyst fine particle obtained by granulating the catalyst for producing a nanocarbon material according to any one of claims 1 to 5 to obtain a fine particle of 0.005 to 10 mm. The carrier material is immersed in a solvent in which the raw material salt for the active metal and the raw material salt for the active metal aggregation preventing material are dissolved, and then dried.
Thereafter, an activation heat treatment is performed to produce the catalyst for producing a nanocarbon material according to claim 1, wherein the catalyst for producing a nanocarbon material is produced. In claim 7,
A method for producing a catalyst for producing a nanocarbon material, wherein the carrier material is immersed, stirred, dried, granulated, then sized, and then subjected to an activation heat treatment. In claim 7 or 8,
The method for producing a catalyst for producing a nanocarbon material, wherein the activation heat treatment temperature is 500 to 1200 ° C. A production apparatus for producing a nanocarbon material from a carbon raw material using the catalyst for producing a nanocarbon material according to any one of claims 1 to 5,
A recovery device for recovering the carbon material from a manufacturing device;
A system for producing a nanocarbon material, comprising: a carbon material purification apparatus that separates a carrier from the recovered carbon material. In claim 10,
A production system for producing a nanocarbon material, wherein the production apparatus for producing the nanocarbon material is a fluidized bed reactor. In claim 11,
A nanocarbon material production system, comprising using the catalyst fine particles of claim 6 and producing a nanocarbon material in a fluidized bed reactor. In any one of claims 10 to 12,
A nanocarbon material manufacturing system, wherein the nanocarbon material is a single-walled carbon nanotube.