KR100675992B1 - Carbon nano-rod and fibrous nano carbon, and method and apparatus for preparing fibrous nano carbon - Google Patents

Abstract

The carbon nanorods 12 are composed of carbon hexagonal net face 11 having a central axis extending in one direction, and the carbon nanorods 12 are three-dimensionally assembled to form fibrous nanocarbons.

Description

CARBON NANO-ROD AND FIBROUS NANO CARBON, AND METHOD AND APPARATUS FOR PREPARING FIBROUS NANO CARBON}

The present invention relates to a carbon nanorod, a fibrous nanocarbon, and a method for producing the fibrous nanocarbon, and an apparatus thereof.

Recently, as a carbon material in nano units (nm = 1 billionth of a meter), for example, carbon nanofibers (1983, United States, Hyperion Catalytic International, Japanese Patent Publication No. 1987-5000943, Multi-walled Nanotube, The number of walls varies , with 8 to 15 being typical.The outside diameter of the tube is approximately 10 to 15 nanometers.The inside diameter is approximately 5 nanometers.Nanotubes are typically tens of microns in length.Aspect ratios on the order of 100 to 1000), ( HP Boehm, Carbon, 11, 583 (1973), H. Murayama, T. Maeda, Nature, 245, 791, Rodriguez, NM 1993. J. Mater. Res. 8: 3233), and carbon nanotubes (S. Iijima) , Nature, 354, 56 (1991), S. Iijima) has been found to attract attention as a fine carbon material.

The outline of the conventional carbon nanofiber structure is shown in FIG. As shown in Fig. 49, in the conventional carbon nanofibers, three types of structures consisting of a plate-like laminate of carbon hexagonal reticulated surfaces have been proposed (Rodriguez, NM 1993. J. Mater. Res. 8: 3233). ). These carbon materials are three-dimensional structures, such as the platelet structure of FIG. 49 (a), the herringbone or fishbone structure of FIG. 49 (b), and the tube, ribbon or of FIG. 49 (c). It has been classified as a parallel structure. However, conventional carbon nanofibers have no variety due to the defined simple structure, and have not been provided as materials satisfying various functions at the same time.

In recent years, research on the use of carbon nanofibers has been conducted, and examples thereof include occlusion and adsorption and desorption of hydrogen and lithium, catalysis, adsorption of nitrogen oxides, and the like. However, although a high occlusion force on the target material of the carbon nanofibers for this use is required, the preferred carbon nanofibers have not yet appeared.

Accordingly, various carbon nanorods are arranged in various dimensions or shapes, and the emergence of fibrous nanocarbon materials capable of simultaneously giving various characteristics by systematically manufacturing fibrous nanocarbons having a wide variety of structures is strongly required. have.

In addition, in the production of conventional carbon nanofibers, a basic reactor as shown in FIG. 50 is used. As shown in Fig. 50, the conventional elementary reactor is made by contacting the raw material gas 01 as a carbon source with the catalyst 05 on the boat 04 in the reaction tube 03 with the heating means 02. It is a batch type for growing the carbon nanofibers (06) on the catalyst (05). Therefore, the conventional apparatus as shown in FIG. 50 has a problem that mass production cannot be performed.

Therefore, as shown in Fig. 51, for example, a gas phase flow method in which the raw material gas 01 is supplied into the gas phase reaction tube 03 and heated by the heating means 02 to produce carbon nanofibers is considered.

However, in the basic reactor as shown in FIG. 50 or the gas phase flow method as shown in FIG. 51, there is a problem that the inside of the reaction tube 03 tends to generate a temperature distribution and becomes uneven, while the grown product is a reaction tube. There exists a problem that it is easy to adhere to the inner wall surface of (03), and a product collection is difficult. As a result, there is a problem that scale up is difficult.

In view of the above circumstances, an object of the present invention is to provide a carbon nanorod capable of exhibiting a high ability in the storage and adsorption and desorption of hydrogen and lithium, the catalytic action and the adsorption of nitrogen oxides, and the fibrous nanos in which the carbon nanorods are arranged and assembled. The present invention provides a method for producing carbon and fibrous nanocarbon, and an apparatus thereof.

Summary of the Invention

The 1st invention for solving the said subject is a carbon nanorod characterized by consisting of the carbon hexagonal net surface which has the central axis extended in one direction.

2nd invention WHEREIN: 1st invention WHEREIN: The axial width (D) of the said carbon hexagonal net surface is 2.5 +/- 0.5 nm, and the length (L) of the carbon hexagonal net surface is 17 +/- 15 nm, The carbon nano It's a rod.

3rd invention is a carbon nanorod in which the said carbon hexagonal net surface is laminated | stacked by 2-12 layers in 1st or 2nd invention.

The fourth invention is a fibrous nanocarbon comprising a plurality of carbon nanorods of any one of the first to third inventions.

5th invention is fibrous nanocarbon in 4th invention in which the said carbon nanorod is laminated | stacked in the closest-packed state three-dimensionally.

6th invention is fibrous nanocarbon in 4th or 5th invention characterized by the said carbon nanorod being laminated | stacked in multiple numbers by making central axis | shaft parallel to each other, and forming a carbon nanorod group.

7th invention WHEREIN: In the 6th invention, the said carbon nanorod group consists of laminating | stacking the said carbon nanorod which consists of 2-12 layers of said carbon hexagonal nettles, and 2-12 layers of the said carbon hexagonal reticle nets. Between the carbon nanorods, it is a fibrous nanocarbon, characterized in that the three-dimensional lamination with nano-pores.

8th invention is fibrous nanocarbon in 4th invention which consists of carbon nanorods joining in series at an axial end part and forming a carbon nanorod group in an axial direction.

In the ninth invention, in the eighth invention, the shaft end portions of the carbon nanorods are bonded by heat treatment.

10th invention is a columnar column in 6th invention by arrange | positioning the said carbon nanorod group in the array angle of more than 0 degree and less than 20 degree with respect to the axis | shaft orthogonal to the fiber axis of the lamination direction of the said carbon nanorod. ) Is a fibrous nanocarbon characterized by forming a shape.

According to a sixth invention, in the sixth invention, the carbon nanorod group is arranged at an array angle of more than 20 degrees and less than 80 degrees with respect to an axis orthogonal to a fiber axis in the stacking direction of the carbon nanorods. ) Is a fibrous nanocarbon characterized by forming a shape.

A twelfth invention is the fibrous nanocarbon according to the tenth or eleventh invention, wherein the carbon nanorod group has a herringbone structure.

13th invention of claim 10 according to any of the eleventh invention, in the heat treatment conditions of below 700 ℃ nano-carbon fiber, characterized in that is less than the face-to-face distance (d ₀₀₂₎ between the hexagonal carbon mangmyeon 0.500㎚.

According to any one of the tenth to twelfth inventions, the fiber width of the aggregate of carbon nanorods is 8 to 500 nm, and the aspect ratio (fiber length / fiber width) of the fiber is 10 or more. Fibrous nanocarbon.

According to a fifteenth invention, in the eighth invention, the carbon nanorod group is arranged at an arrangement angle of 80 degrees to 88 degrees with respect to an axis orthogonal to a fiber axis in the stacking direction of the carbon nanorods, thereby forming a tubular shape. It is a fibrous nanocarbon characterized by the above-mentioned.

According to a fifteenth invention, in the fifteenth invention, the fiber width of the aggregate of carbon nanorods is 8 to 80 nm, and the aspect ratio (fiber length / fiber width) of the fiber is 30 or more.

17th invention is fibrous nanocarbon in any one of 10th-16th invention whose cross-sectional structure of the direction orthogonal to a fiber axis is a polygon.

18th invention is any one of 10th-17th invention, heat-processed at 1600 degreeC or more, the terminal of the said carbon nanorod on the surface is formed in loop shape two-dimensionally, and three-dimensionally The fibrous nanocarbon is characterized by being formed in a dome shape.

A nineteenth invention for solving the above-mentioned problems is a method for producing fibrous nanocarbon consisting of aggregates of carbon nanorods by reacting a carbon raw material in a high temperature fluidized bed using a catalyst, wherein a carrier carrying a metal catalyst is used as a binder. A carbon nanorod is produced in the presence of the metal catalyst of the catalyst mixed fluid using a first gas supplying step of supplying a reducing gas and supplying the carbonaceous gas in a gaseous state by using a catalyst mixed fluid formed by combining through a catalyst as a fluid. And a second gas supply step of supplying a carbon raw material supplying step and a gas not containing carbon to lose the flow function of the catalyst combined fluid.

20th invention is a manufacturing method of fibrous nanocarbon in 19th invention whose average particle diameter of the said catalyst combined fluid is 0.2-20 mm.

In a twenty-first aspect of the present invention, in the nineteenth aspect of the present invention, the catalyst-containing fluid is composed of one having the catalyst on the surface of the carrier or an aggregate thereof.

In a twenty-second aspect of the invention, in the nineteenth aspect of the invention, the carrier of the catalyst-compatible fluid is selected from carbon black, alumina, silica, silica sand, and aluminosilicate.

In a twenty-third aspect of the invention, in the nineteenth aspect, the metal catalyst of the fluid for both catalysts is one of Fe, Ni, Co, Cu, and Mo, or a mixture of two or more thereof. to be.

24th invention is a manufacturing method of the fibrous nanocarbon in 19th invention whose flow velocity in a fluidized bed is 0.02-2 m / s.

25th invention is a manufacturing method of the fibrous nanocarbon in 19th invention which controls each condition of the said 1st gas supply process, the said carbon raw material supply process, and the said 2nd gas supply process independently from each other. .

A twenty-sixth invention is the manufacturing method of fibrous nanocarbon in 25th invention whose said conditions are temperature, pressure, time, and a gas atmosphere.

In a twenty-ninth aspect of the invention, in the nineteenth aspect, the catalyst and the carbon raw material of the catalyst and the mixed fluid in the mixed gas of hydrogen and inert gas (hydrogen partial pressure 0% to 90%) under a pressure of 0.1 to 25 atm and 300 to It is a method for producing fibrous nanocarbon, characterized in that to produce a fibrous nanocarbon by contacting at a temperature of 1300 ℃ for a certain time.

In a twenty-eighth aspect of the present invention, in the nineteenth aspect, in the at least one of the first gas supply step and the carbon raw material supply step, the catalyst component of the fluid for mixed catalyst can be metallized by the reducing action of the reducing gas. At the same time, it is a method for producing fibrous nanocarbon, characterized in that the finer.

In a twenty-ninth invention, in the twenty-eighth invention, the diameter of the fibrous nanocarbon obtained is controlled by controlling the particle diameter of the metal catalyst when the metal catalyst of the fluid for dual catalysts is refined. Way.

In the thirtieth invention, in the nineteenth invention, the second gas supply process forms a region having a high flow velocity at a local portion of the fluidized bed, and the catalyst is formed by collision between the particles of the catalyst and the mixed fluid or collision between the particles and the wall surface. It is a method for producing fibrous nanocarbon, characterized by promoting the miniaturization and wear of the combined fluid.

A thirty-first invention is a method for producing fibrous nanocarbon according to the thirtieth invention, wherein a region having a high flow velocity in the fluidized bed is formed under the fluidized bed.

32nd invention is a manufacturing method of fibrous nanocarbon in 30th invention which forms a high flow velocity area | region by blowing a high speed gas into the said fluidized bed.

In a thirty-third aspect of the invention, in the thirty-second aspect of the present invention, there is provided a method for producing fibrous nanocarbon, wherein the particles scattered from the fluidized bed are supplied to the fluidized bed again with the high velocity gas.

A thirty-fourth invention is a method for producing fibrous nanocarbon according to the nineteenth invention, wherein the fibrous nanocarbon produced is separated from the carrier or the catalyst.

A thirty-fifth invention is a manufacturing apparatus used for carrying out the method for producing fibrous nanocarbon according to the nineteenth invention, comprising a fluidized bed reactor having a heating means for heating an interior of a fluid for mixing with a catalyst and the reducing gas in the fluidized bed reactor. First gas supply means for supplying gas, the carbon raw material supply means for supplying carbonaceous material into the fluidized bed reactor in a gas state, second gas supply means for supplying the gas containing no carbon into the fluidized bed reactor, and the fluidized bed An apparatus for producing fibrous nanocarbon, comprising a discharge line for discharging gas and fugitive particles from a reactor.

36th invention is a manufacturing apparatus of the fibrous nanocarbon in 35th invention which provided the collection | recovery means which collect | recovers the said scattering particle | grains in the said discharge line.

37th invention is a manufacturing apparatus of the fibrous nanocarbon in 35th invention whose fluidized-bed part of the said fluidized-bed reactor has a high speed flow part and a low speed fluid flow part.

38th invention is a manufacturing apparatus of the fibrous nanocarbon in 37th invention which has a collision part in the said high speed flow part.

In a thirty-ninth aspect of the present invention, there is provided a high-speed gas blowing means for blowing gas into the fluidized bed reactor at high speed.

40th invention is a manufacturing apparatus of the fibrous nanocarbon in 39th invention which accompanies collect | recovered particle | grains, when blowing in the said gas at high speed.

According to a thirty-first aspect of the present invention, in the thirty-fifth invention, the first, second, and third flow chambers in which the fluid is flowable are formed in the fluidized bed reactor, and the first gas supply means is connected to the first flow chamber. And the carbon raw material supply means is connected to the second flow chamber, and the second gas supply means is connected to the third flow chamber.

According to a thirty-fifth aspect of the invention, in the thirty-fifth invention, the first and second flow chambers in which the fluid is flowable are formed in the fluidized bed reactor, and a separate fluidized bed reactor different from the fluidized bed reactor is provided as the third fluidized bed. A transfer means for transferring a fluid from the second flow chamber to the third flow chamber, connecting the first gas supply means to the first flow chamber, and supplying the carbon raw material supply means to the second flow chamber. And connecting the second gas supply means to the third flow chamber.

A forty-fourth invention is a production apparatus for use in carrying out the method for producing fibrous nanocarbon according to the nineteenth invention, wherein the catalyst-coating fluid is filled therein, heating means for heating the inside, and supplying a reducing gas therein. A first fluidized bed reactor having a first gas supply means, a second fluidized bed reactor having a transport means for transporting the fluid from the first fluidized bed reactor and a carbon raw material supply means for supplying the carbon raw material in a gas state therein; A third fluidized bed reactor having transfer means for transferring the fluid and reaction product from a second fluidized bed reactor, and having a second gas supply means for supplying the gas containing no carbon therein, and a gas from the third fluidized bed reactor And a discharge line for discharging the scattering particles. .

A forty-fifth invention is a device for producing fibrous nanocarbon according to a forty-fourth invention, comprising a plurality of the first fluidized bed reactors.

A forty-fifth invention is a device for producing fibrous nanocarbon according to a forty-fourth invention, comprising a plurality of second fluidized bed reactors.

In a forty-fourth invention, a forty-ninth aspect of the invention is provided with a plurality of third fluidized bed reactors.

48th invention is the manufacturing apparatus of the fibrous nanocarbon in any one of 35th-47th invention whose average particle diameter of the said catalyst combined fluid is 0.2-20 mm.

49th invention is the manufacturing apparatus of the fibrous nanocarbon in any one of 35th-47th invention WHEREIN: The said catalyst combined fluid material consists of what carried the said catalyst on the surface of the said carrier, or its aggregate | aggregate. .

In a fifty-fifth invention, in any one of the thirty-fifth to seventy-ninth inventions, the carrier for the catalyst-compatible fluid is selected from carbon black, alumina, silica, silica sand, and aluminosilicate. Device.

In a fifty-ninth aspect of the invention, in any one of the thirty-fifth to seventy-ninth inventions, the metal catalyst of the mixed catalyst fluid is any one of Fe, Ni, Co, Cu, and Mo, or a mixture of two or more thereof. It is a manufacturing apparatus of fibrous nanocarbon.

A fifty-second invention is an apparatus for producing fibrous nanocarbon, according to any one of the thirty-ninth to seventy-ninth inventions, wherein the flow velocity in the fluidized bed is 0.02 to 2 m / s.

In the fifty-third aspect of the present invention, there is provided the catalyst of any one of the thirty-fifth to seventy-ninth inventions, wherein the catalyst and the catalyst in the mixed fluid of the catalyst and the fluid in a mixed gas of hydrogen and an inert gas (hydrogen partial pressure 0% to 90%) under a pressure of 0.1 to 25 atm. It is an apparatus for producing fibrous nanocarbon, characterized in that to produce a fibrous nanocarbon by contacting the carbon raw material at a temperature of 300 ℃ to 1300 ℃ for a certain time.

1 is a schematic diagram of carbon nanorods according to the present invention.

2 is a schematic diagram of a carbon nanorod group according to the present invention.

3 is a schematic diagram of carbon nanorods and fibrous nanocarbons according to the present invention.

4 is a schematic cross-sectional view of the carbon nanorods according to the present invention.

5 is a schematic view of the heat treatment of the carbon nanorods according to the present invention.

6 is a photomicrograph of the carbon nanorods as they were prepared and after the heat treatment.

7 is a high resolution transmission micrograph and scanning tunnel electron micrograph of carbon nanorods.

8 is a scanning tunnel electron micrograph and a schematic diagram thereof.

It is a schematic diagram which shows the shape which forms the carbon nanorod group.

10 is a high resolution transmission micrograph of a fibrous nanocarbon having a columnar structure.

It is a schematic diagram of various shapes of a carbon nanorod group.

It is a schematic diagram of the fibrous nanocarbon aggregate of columnar structure.

It is a schematic diagram of the fibrous nanocarbon aggregate of another columnar structure.

It is a cross-sectional schematic diagram of fibrous nanocarbon.

15 is a scanning tunnel electron micrograph of various shapes of carbon nanorods.

16 is a scanning tunnel electron micrograph of various shapes of carbon nanorods.

17 is a schematic diagram of a fibrous nanocarbon aggregate having a feather structure.

Fig. 18 is a high resolution transmission micrograph of fibrous nanocarbon having a flagged structure.

It is a schematic diagram of the fibrous nanocarbon aggregate of a tubular structure.

20 is a schematic diagram of heat treatment of carbon nanorods, and a schematic diagram of fibrous nanocarbons in which they are collected.

Fig. 21 shows the structure of the carbon nanorod group constituting the fibrous nanocarbon having a columnar structure after high temperature treatment at 2800 ° C. by varying the angle of the transmission electron beam of a high resolution transmission electron microscope (-30 degrees, 0 degrees, +30 degrees). One picture.

Fig. 22 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature treated product of the carbon nanorod group constituting the fibrous nanocarbon having a columnar structure.

FIG. 23 is a high resolution transmission electron micrograph (magnification: 600,000 times) of a 2800 ° C. high temperature processed product at an angle of −30 degrees in FIG. 21.

24 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature processed product at an angle of 0 degrees in FIG. 21.

25 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature treated product at an angle +30 degrees in FIG. 21.

FIG. 26 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature processed product at an angle of −30 degrees in FIG. 23.

FIG. 27 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature processed product at an angle of 0 degrees in FIG. 24.

28 is a high resolution transmission electron micrograph of a 2800 ° C. high temperature treated product at an angle +30 degrees in FIG. 25.

Fig. 29 is a high resolution transmission electron micrograph of fibrous nanocarbons having columnar, feathery, and tubular structures.

30 is a high resolution transmission electron micrograph of a group of carbon nanorods prepared in a state of forming fibrous nanocarbon having a columnar structure (prepared at 600 ° C. using an iron catalyst), and a structure after heat treatment at 2000 ° C. and 2800 ° C., respectively. to be.

Fig. 31 is a Raman scattering spectrum diagram before and after heat treatment of fibrous nanocarbons composed of carbon nanofiber groups having columnar structures.

32 is a schematic view of the first embodiment of the apparatus for producing carbon nanorods according to the present invention.

33 is a schematic view of a method of manufacturing carbon nanorods according to the present invention.

34 is a diagram illustrating an example of separation of fibrous nanocarbon.

35 is a diagram illustrating a relationship between the particle diameter and the flow velocity.

36 is a diagram illustrating a relationship between the particle diameter and the flow velocity.

37 is a schematic view of a second embodiment of the apparatus for producing carbon nanorods according to the present invention.

38 is a schematic view of a third embodiment of the apparatus for producing carbon nanorods according to the present invention.

39 is a schematic view of a fourth embodiment of an apparatus for producing carbon nanorods according to the present invention.

40 is a schematic diagram of carbon nanorods.

It is a schematic diagram of a carbon nanorod.

42 is a schematic view of a fifth embodiment of the apparatus for producing carbon nanorods according to the present invention.

43 is another schematic view of the fifth embodiment of the apparatus for manufacturing carbon nanorods according to the present invention.

44 is a schematic view of a sixth embodiment of an apparatus for producing carbon nanorods according to the present invention.

45 is another schematic view of the sixth embodiment of the apparatus for producing carbon nanorods according to the present invention.

46 is a micrograph of the fibrous nanocarbon obtained in Example 1. FIG.

47 is a micrograph of the fibrous nanocarbon obtained in Example 2. FIG.

48 is a micrograph of the fibrous nanocarbon obtained in Example 3. FIG.

49 is a model diagram of a conventional nanofiber.

50 is an explanatory diagram of a conventional basic reactor.

51 is an explanatory diagram of a conventional gas phase flow method.

Embodiments of the method for producing carbon nanorods, fibrous nanocarbons, and fibrous nanocarbons according to the present invention, and apparatuses thereof will be described below, but the present invention is not limited to these embodiments.

Carbon nanorods and fibrous nanocarbons

As a result of intensive research, the present inventors have found a new nanostructure unit of fibrous nanocarbon (so-called carbon nanofiber). A fibrous nanocarbon having a polygonal cross section that defines a fibrous nanocarbon composed of such structural units and exhibits a very high graphitization with an interplanar distance (d ₀₀₂ ) between carbon hexagonal reticules of 0.500 nm or less under relatively low temperature manufacturing conditions of 700 ° C or less. And also found that the structural unit of the fibrous nanocarbon is an aggregate of independent carbon nanorods.

In addition, it has been found that fibrous nanocarbons of polygonal cross section gather, for example, an average fiber width of 100 nm and an aspect ratio of 30 form a fibrous nanocarbon of polygonal cross section showing a surface area of 200 m 2 or more, as measured by nitrogen BET. .

Here, the fibrous nanocarbon laminated with carbon hexagonal reticulated surface (carbon hexagonal network), carbon nanorods that are nanoassemblies thereof, and carbon nanorods will be described based on FIGS. 1 and 2.

FIG. 1 is a schematic diagram of carbon nanorods composed of a plurality of carbon hexagonal meshes, and FIG. 2 is a schematic diagram illustrating an assembly state of carbon nanorods.

In the present embodiment, as shown in Figs. 1 and 2, the carbon nanorods 12 are constituted by the carbon hexagonal mesh 11 having a central axis extending in one direction. Although the carbon nanorod 12 becomes a basic structural unit even in one sheet (one layer), the carbon hexagonal net face 11 is normally laminated | stacked in 2-12 layers to form one structural unit.

In addition, the number of laminations is preferably 4 to 10. The reason why the carbon nanorods 12 constitute a unit by lamination of two to twelve layers is not yet clear, but it is thought that the carbon nanorods 12 are related to the crystal lattice structure of the metal catalyst used for synthesis.

FIG. 1 (a) is a schematic diagram in which the carbon hexagonal net surface 11 forms one structural unit of the carbon nanorods 12 by two layers. 1 (b) is a schematic diagram in which the carbon hexagonal net surface 11 forms one structural unit of the carbon nanorods 12 by eight layers. The carbon hexagonal reticle 11 constituting the carbon nanorods 12 has an axial width D of 2.5 ± 0.5 nm and a length L of 17 ± 15 nm. On the other hand, when this size is out of the said range, a favorable carbon nanorod 12 cannot be formed.

As shown in FIG. 2, the plurality of carbon nanorods 12 are most closely packed to form a carbon nanorod group 13, and thus the carbon nanorods 12 are formed along the axis (the X-axis direction in FIG. 2). There are a number of nanopores 14. The nano voids 14 become a space which receives atoms, such as hydrogen and lithium, for example. By the presence of many nano voids 14, the effect to a novel functional material, such as catalyst activity, storage and adsorption-and-desorption of a specific substance, can be expressed.

In FIG. 2A, the carbon nanorods 12 are in contact with each other, but the carbon nanorods 12 may be in contact with each other or may not be in contact with each other. When not in contact with each other, the nano voids 14 increase. In FIG.2 (b), the carbon nanorods 12 of a hexagonal cross section are aggregated with a little gap. The carbon nanorod group 13 composed of the carbon nanorods 12 is formed to form fibrous nanocarbons (so-called carbon nanofibers) 15 by aggregated three-dimensionally in the form of fibers as shown in FIG. 3. do.

Although the cross-sectional structure of the carbon nanorod 12 in the direction orthogonal to an axis | shaft is circular in FIG.2 (a) and hexagonal in FIG.2 (b), this invention is not limited to this. For example, as shown in FIG. 4, in addition to the circle (see FIG. 4 (a)) or hexagon (see FIG. 4 (b)), for example, octagon (see FIG. 4 (c)) or square (see FIG. 4 (d)). ) May be rectangular.

Representative structures of the fibrous nanocarbons 15 in which the carbon nanorod group 13 is three-dimensionally plurally aggregated include columnar structures, feather structures, and tubular structures (the details will be described later). . In this embodiment, it demonstrates centering on the fibrous nanocarbon 15 of columnar structure as an example.

Although the carbon nanorod 12 which concerns on this invention is a structural unit is not clear as it was manufactured, it becomes clear by heat-processing (or carbonizing) 1600 degreeC or more after manufacture. That is, by heat treatment at a high temperature of 1600 ° C. or higher, as shown in FIG. 5, the axial ends of the carbon nanorods 12 form a loop shape two-dimensionally, and the carbon network has a dome shape three-dimensionally. It is to constitute. As a result, it becomes clear that the carbon nanorods 12 are one structural unit.

In the following description, the carbon nanorods 12 whose ends are not formed in a loop as they are prepared are described as "manufactured states", and the carbon nanorods 12 heat-treated at a high temperature of 2800 ° C are referred to as "2800 ° C. Heat treatment state ".

6 is a photograph taken by a high resolution transmission electron microscope (HRTEM) of the carbon nanorods 12. FIG. 6 (a) is a photograph of an aggregate of carbon nanorods 12 obtained by a synthesis method described later, and FIG. 6 (b) is a carbon nanorod 12 having heat treatment at 2800 ° C. to be described later to improve the degree of carbonization. ) Is a picture of a collection. 6 shows the size of 10 nm.

7 is a photograph taken by an electron microscope of the carbon nanorod 12 (2800 ° C. heat treatment state). Figure 7 (a) is a high resolution transmission electron microscope (HRTEM) picture, Figure 7 (b) is a scanning tunnel electron microscope (STM) picture. Arrows in the picture indicate 20 nm size.

In FIG. 6 and FIG. 7, the lamination state of the carbon hexagonal netting surface 11 of 6 to 10 layers is shown together, and it can confirm that the carbon nanorod 12 is comprised by this. Therefore, it can be confirmed that the carbon nanorods 12 are formed in structural units, and these aggregate to form the fibrous nanocarbons 15. On the other hand, the scanning tunnel electron microscopy (STM) picture is taken with a high magnification that is not clear, and because of the principle of photographing, a clear picture can no longer be obtained at this point in time. However, it can be confirmed that the carbon nanorods 12 are one structural unit.

8 is another scanning tunnel electron micrograph (STM) of carbon nanorods 12 (at 2800 ° C. heat treatment). In FIG. 8, the right side is an enlarged view of the left side. 8, the network state of the loop is confirmed at the shaft end.

FIG. 9 is a schematic view showing how the carbon nanorods 12 shown on the right side of FIG. 8 aggregate to form the carbon nanorod group 13.

The carbon hexagonal netting surface (carbon hexagonal netting surface) according to the present embodiment is the same as the black material which occupies most of the current carbon materials, and is based on the hexagonal netting of carbon atoms as a basic unit. It is known that the properties of these carbon materials are basically determined by the integrity and size of the carbon hexagonal net face, the lamination thickness, the regularity of the lamination, and the manner and degree of selective orientation of the net face (Dictionary of Carbon Terminology, p. 226, The Carbon Society of Japan, Edited by the Dictionary of Carbon Terminology Edition Committe, Agne Shofu-Sha, Tokyo, 2000 ")

The carbon nanorods 12 of the present invention are formed of 95% or more carbon atoms based on the hexagonal net surface of carbon atoms. The carbon nanorods 12 are heat-treated at a high temperature of 2000 ° C. or higher to form 99% or more carbon atoms. In addition, the distance between the surface of the aggregate of carbon nano-hexagonal mangmyeon 11 of the carbon nano-rods (12) (d ₀₀₂₎ is less than 0.500㎚, the distance between the surface of pure graphite (d ₀₀₂₎ is a surface that approximates a 0.3354㎚ It is the gap between. Thereby, the carbon nanorod 12 according to the present invention has a high graphitization degree.

As shown in Table 1 below, the fibrous nanocarbon 15 having a columnar structure in the fibrous nanocarbon 15 composed of the closest packed laminate layer of only the carbon nanorods 12 was manufactured at 700 ° C. or less. It can be logically inferred that the interplanar distance d ₀₀₂ of the hexagonal reticle is less than 0.500 nm.

The fibrous nanocarbon 15 of the present invention is configured by closest filling of the carbon nanorods in a three-dimensional direction. The schematic diagram of lamination of the carbon nanorods 12 which is an example of the lamination state below is shown in FIG. The lamination shown in FIG. 3 is a columnar lamination structure, and a plurality of laminations are formed in a first direction (up and down direction of the sheet surface) with the central axis of the carbon nanorods 12 in parallel to form a carbon nanorod group 13 to form fibrous nanoparticles. It is made by forming carbon 15.

10 is a high resolution transmission electron micrograph of the fibrous nanocarbon 15 having a columnar structure heat-treated at 2800 ° C. As shown in FIG. 10, the carbon nanorods 12 having a loop shape at the tip are closest filled to form the carbon nanorod group 13, and form fibrous nanocarbons 15. 10A is an enlarged view (150,000 times magnification) of the fibrous nanocarbon 15. FIG. 10 (b) is an enlarged view of both ends (point A and point B of FIG. 10 (a)) in a direction orthogonal to the axial direction (left and right directions of FIG. 10 (a)) of the fibrous nanocarbon 15. FIG.

FIG. 10 (b) shows the fibrous nanocarbon 15 formed by the carbon nanorods 12 having the three-dimensional dome-shaped tip is most closely filled in the three-dimensional direction by heat treatment. Show formation. The collection aspect of the carbon nanorods 12 is various, and the carbon nanorod group 13 is laminated or aggregated in a direction orthogonal to the axis of the carbon nanorods 12, in the same direction or in a cross direction.

As a typical structure of the fibrous nanocarbon 15 which the carbon nanorod group 13 was plurally gathered three-dimensionally, the three types of structure of a columnar structure and a tubular structure other than columnar structure is mentioned, for example. Although the difference in these structures is not clear, it is guessed that the shape changes with the difference of a catalyst and manufacturing conditions.

FIG. 11 shows schematic diagrams of three forms of the carbon nanorod group 13.

The first embodiment is arranged at an angle α of more than 0 degrees and less than 20 degrees with respect to the axis X orthogonal to the axis Y in the stacking direction (fiber axial direction), and has a columnar fibrous nanocarbon group 13A. (See FIG. 11 (a)).

The second aspect is arranged at an angle α of more than 20 degrees and less than 80 degrees with respect to the axis X orthogonal to the axis Y perpendicular to the stacking direction (fiber axial direction), and has a feather-like fibrous nanocarbon group 13B. (See FIG. 11 (b)).

As can be seen from FIG. 11, the feather-like fibrous nanocarbon group 13B has a herringbone structure, but the opposing in this way is due to the relationship with the catalyst. Thus, the case of not facing may also be considered.

The third embodiment is arranged at an angle γ of 80 degrees to 88 degrees with respect to the axis X orthogonal to the axis Y in the stacking direction (fiber axial direction), and the tubular fibrous nanocarbon group 13C. This is referred to (see Fig. 11 (c)).

It is a schematic diagram which shows the example of columnar carbon nanorod group.

FIG. 12A shows that the carbon nanorod groups 13A are stacked in a direction orthogonal to the axial direction of the columnar carbon nanorods 12.

12 (b) and 12 (c) show a state in which at least one carbon nanorod group 13A is disposed in parallel and the central axis of the carbon nanorods 12 is parallel. That is, in FIG. 12 (b), the carbon nanorod group 13A is a parallel array of two rows in parallel. In Fig. 12 (c), the carbon nanorod group 13A is a parallel arrangement of four rows in parallel. As shown in Figs. 12 (b) and 12 (c), when the carbon nanorod groups 13A are disposed in parallel next to each other, the direction of the central axis of the carbon nanorods 12 becomes the same.

As shown in FIG. 12 (d), carbon nanorods 12 having various lengths in the axial direction are laminated to form a carbon nanorod group 13A, and the nanorods are stacked on the carbon nanorods 12. The voids 14 can be formed.

In addition, as shown in FIG. 13, a group of carbon nanorods in the form of tubes having nanopores 13 therein in a planar state (see FIG. 13A) and surrounded by carbon nanorods 12 above them. (13) can be formed. As shown in FIG. 14, the cross-sectional shape of the carbon nanorod group 13 in the direction orthogonal to the fiber axis is varied into hexagonal, octagonal, tetragonal, circular, and the like.

15 is a high resolution transmission microscope (HRTEM) photograph of the fibrous nanocarbon 15, and FIG. 16 is a scanning tunnel electron microscope (STM) photograph of the fibrous nanocarbon 15. From these photographs, it was confirmed that the shape of the fibrous nanocarbon 15 having three structures of columnar, feather and tube was almost hexagonal or pentagonal.

It can be seen that the carbon nanorod group 13A having a columnar structure has an axial width of about 15 to 20 nm, and the fibrous nanocarbon 15 having a columnar structure having four rows arranged in parallel has a fiber width of 60 to 80 nm. As a result, ten or more rows of fibrous nanocarbons 15 having a columnar structure having a fiber width of 200 nm are arranged in parallel.

The fibrous nanocarbon 15 is carbon monoxide or methane in a temperature range of 400 ° C. to 1200 ° C. using a single or alloy of pure transition metals represented by iron (Fe), cobalt (Co), and nickel (Ni) as a catalyst. Hydrocarbons, such as (CH ₄ ), ethylene (C ₂ H ₆ ), propane (C ₃ H ₈ ), and the like, are synthesized by contacting the catalyst for a predetermined time in a mixed gas with hydrogen (0% to 90% hydrogen partial pressure).

Preferable production examples relating to the production of the fibrous nanocarbon 15 having a columnar structure are as follows.

First, using iron nitrate, the precipitation method (Best, RJ Russell, WW, J. Amer. Soc. 76, 838 (1954), Sinfelt, JH, Carter, JL, and Yates, DJC, J. Catal. 24, 283 (1972) ") to prepare the iron catalyst.

The manufactured 30 mg iron catalyst was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (external value)) and mixed gas of hydrogen and helium (quartz partial pressure: 20%) in a quartz tube having an inner diameter of 4.5 cm. ) Is reduced at 500 ° C. for 0.5 to 10 hours while flowing at 100 sccm. Thereafter, a mixture of carbon monoxide and hydrogen (hydrogen partial pressure: 10% to 90%) was allowed to react at a temperature of 450 ° C to 620 ° C for 0.25 to 3 hours while flowing at 100 to 200sccm to provide a predetermined amount (2mg to 1500mg). The fibrous nanocarbon 15 of columnar structure is manufactured.

Next, FIG. 17 shows an example of fibrous nanocarbons in the form of flags in which the carbon nanorods 12 are closest-filled in a three-dimensional direction to have a predetermined angle with respect to an axis to constitute the carbon nanorod group 13B. As shown in FIG. 17, the carbon nanorod group 13B has a herringbone structure in which the carbon nanorods 12 are opposed to each other at a predetermined angle, and as shown in FIG. 17A, for example, between them. It has a space | gap 14 and takes the structure which cross | intersects each other as shown to FIG. 17 (b).

As described above, the fibrous nanocarbon 15 of the flagged structure is arranged at an angle β of more than 20 degrees and less than 80 degrees with respect to the axis X orthogonal to the axis Y in the stacking direction (fiber axial direction). It has a structure (see FIG. 11 (b)). The carbon nanorods 12 of the carbon nanorod group 13B having such a flagged structure have an axial width of 2.5 ± 0.5 nm and an axial length of 4 ± 2 nm in the synthesized step. This is because the angle of the carbon nanorods 12 becomes an acute angle than the fibrous nanocarbon group 13A of columnar structure, and the axial length L of the carbon nanorods 12 which is a structural unit becomes shorter.

The carbon hexagonal reticle 11 of the carbon nanorods 12 of the carbon nanorod group 13B has an interplanar spacing d _{002 of} less than 0.500 nm and a size of pure graphite interplanar spacing d ₀₀₂ (0.3354). It is a value approximating to nm). Therefore, the carbon nanorods 12 have a high graphitization degree.

This is based on the high-resolution transmission electron micrograph of the fibrous nanocarbon 15 having a flagged structure shown in FIG. 18. It can be inferred from the fact that the axial width of) and the number of constituents of the carbon hexagonal reticle 11 and the two-dimensional width of the nano-assembly consisting of these are almost identical.

The specific manufacture example regarding manufacture of fibrous nanocarbon of flagship structure is as follows.

In the production of the fibrous nanocarbon group 13B having a flagged structure, in the production of the fibrous nanocarbon having a columnar structure, nickel nitrate or a mixture of nickel nitrate and iron nitrate is used instead of iron nitrate, and nickel or nickel and An alloy catalyst of iron (nickel content: 70% to 90% by weight) was prepared.

Next, using the same method and apparatus as the above experiment, the mixed gas of hydrogen and helium (hydrogen partial pressure: 20%) with respect to the catalyst is reduced at 500 ° C. for 0.5 to 10 hours while flowing at 100 sccm. Thereafter, a predetermined amount (2 mg to 5400 mg) was caused by reacting a mixed gas of ethylene and hydrogen (hydrogen partial pressure: 10% to 90%) at a temperature of 450 ° C to 620 ° C for 0.25 to 3 hours while flowing at 100 to 200 sccm. To prepare a fibrous nano-carbon (15) of the herringbone structure of.

Next, an example of the fibrous nanocarbon 15 having a tubular structure in which the carbon nanorods 12 are joined to each other at both ends to have a predetermined number of knots in the axial direction to form the carbon nanorod group 13C is shown in FIG. 19. Shown in As shown in Fig. 19, in the carbon nanorod group 13C having a tubular structure, the carbon nanorods 12 are bonded to each other at both ends in the axial direction.

As described above, the fibrous nanocarbon group 13C having a tubular structure is formed at an angle γ of 80 degrees to 88 degrees with respect to the axis X orthogonal to the axis Y in the stacking direction (fiber axial direction). It is arranged in an arrangement (see Fig. 11 (c)). In the step of synthesizing, the carbon nanorods 12 constituting the tubular structure have an axis width of 2.5 ± 0.5 nm and an axis length of 13 ± 10 nm.

FIG. 19 (a) shows the axial ends of the carbon nanorods 12 connected in a straight line (column) to form a fibrous nanocarbon group 13C having a tubular structure, and FIG. 19 (b) shows pairs of carbon nanorods ( The shaft end of 12) is joined to overlap with the shaft end of one carbon nanorod 12 to form a fibrous nanocarbon group 13C having a tubular structure, and FIG. 19 (c) shows the shaft end of the carbon nanorod 12. By joining so that the parts overlap, the fibrous nanocarbon group 13C of a tubular structure is comprised. Although the joining form is not limited to these, joining is performed at both ends of the shaft, so that the carbon nanorod group 13C is formed with a knot.

Further, between the surface of the carbon nano-rods 12 of the carbon nano-rod group (13) spacing (d ₀₀₂₎ is less than the carbon hexagonal 0.3400㎚ mangmyeon 11 distance between the surface of pure graphite (d ₀₀₂₎ of 0.3354㎚ This is an approximation to. Thus, the carbon nanorods 12 have a high graphitization degree.

As shown in Table 1, the carbon in the step (fibrous heat treatment at 700 ° C. or less) of the fibrous nanocarbon 15 of the tubular structure was produced among the fibrous nanocarbons 15 formed of the closest packed lamination of the carbon nanorods 12 only. It can be logically deduced that the interplanar distance d ₀₀₂ of the nanoassembly composed of the hexagonal reticle 11 is less than 0.3400 nm.

Specific embodiments of the production of the fibrous nanocarbon 15 having a tubular structure are as follows.

First, using iron nitrate or a mixture of nickel nitrate and iron nitrate, an iron or nickel and iron alloy catalyst (nickel content ratio: 30% to 70% (weight ratio)) was produced by the same precipitation method as in the above-described experiment. do. Using the same method and apparatus as the above experiment, the produced catalyst was reduced at 500 ° C. for 0.5 to 10 hours while flowing a mixed gas of hydrogen and helium (hydrogen partial pressure: 20%) at 100 sccm. Thereafter, a mixed gas (hydrogen partial pressure: 10% to 90%) of carbon monoxide and hydrogen was reacted at a temperature range of 620 ° C to 655 ° C for 0.25 to 3 hours while flowing at 100 to 200 sccm, and a predetermined amount (2 to 1500 mg) was obtained. A fibrous nanocarbon 15 having a tubular structure of was prepared.

Next, the case where the fibrous nanocarbon 15 which consists of carbon nanorod group 13A of columnar structure is heat-treated at the temperature of 1600 degreeC or more in the atmosphere of vacuum or an inert gas is demonstrated.

As shown in Table 1, the fibrous nanocarbon 15 made of the carbon nanorod group 13 of the present invention has a high degree of graphitization even in a state of being manufactured while taking a columnar structure or a tube structure. Although it possesses sufficient characteristics as a graphite-based high functional material, it has a high graphitization degree while taking all structures including a herringbone structure when graphitization treatment of 2000 degreeC or more is carried out.

As heat processing conditions, it is preferable to set it as the temperature of 1600 degreeC or more, Preferably it heat-processes 2000 degreeC or more, More preferably, it is 2800 degreeC or more. If the heat treatment temperature is less than 1600 ° C, the degree of graphitization is low.

By heat treatment, the ends of the carbon nanorods 12 of the carbon hexagonal reticle 11 of the surface portion of the fibrous nanocarbon 15 are joined in a loop shape in two dimensions, or circular or hexagonal in three dimensions. It joins in a dome shape and comprises one unit.

20 is a schematic view of the heat treatment of the carbon nanorods 12. As shown in FIG. 20, the carbon nanorods 12 which consist of eight layers of carbon hexagonal netting 11 become one unit, and one unit of this carbon nanorods 12 is high temperature (1600 degreeC or more). By heat treatment, the cross section of the carbon nanorods 12 constituting the carbon hexagonal reticle 11 is joined to form a dome-shaped graphitized carbon nanorod group 13. A plurality of graphitized carbon nanorod groups 13 are stacked to form fibrous nanocarbons 15.

From the above-mentioned FIG. 10 which shows the photograph of the high-resolution transmission electron microscope (HRTEM) of the fibrous nanocarbon 15 of columnar structure before and after graphitization treatment, the cross section (edge surface) of the carbon hexagonal reticle 11 before high temperature treatment is high temperature. It can be confirmed that the process is bonded in a loop shape in two dimensions.

FIG. 21 shows that after the high temperature treatment of the carbon nanorod group 13A constituting the fibrous nanocarbon 15 having a columnar structure at 2800 ° C., the angle of the transmission electron beam of the high-resolution transmission electron microscope is changed (-30 degrees, 0 degrees, + 30 degrees).

23 to 25 show changes in the angle of the transmission electron beam of the high-resolution transmission electron microscope of the fibrous nanocarbon 15 shown in FIG. 22 (150,000 times magnification) (-30 degrees (FIG. 23), 0 degrees (FIG. 24), + 30 degrees (FIG. 25)) It is a photograph (magnification 600,000 times). 26 to 28 are enlarged photographs (magnification 3.2 million times) of FIGS. 23 to 25, and FIG. 26 shows -30 degrees, FIG. 27 is 0 degrees, and FIG. 28 is +30 degrees.

From these drawings, it was confirmed that changing the angle changes the position of the loop-like end of the tip portion. As a result, it was confirmed that the ends of the carbon nanorods 12 made of the carbon hexagonal reticle 11 were joined to form a loop-shaped cross section two-dimensionally. It is clear that the carbon nanorods 12 are constituted from the unit of.

29 is a high resolution scanning tunnel electron microscope (STM) photograph of three kinds of fibrous nanocarbons 15 before and after high temperature heat treatment. Since the (10) plane (that is, the 100 plane and the 110 plane) made of the carbon hexagonal reticulated plane 11 cannot theoretically be observed by a scanning tunnel electron microscope, a high magnification cross section cannot be observed. However, carbon nanorods 12 are observed from all photographs of the fibrous nanocarbons 15 before the three kinds of heat treatments, and furthermore, it can be confirmed that the fibrous nanocarbons 15 are formed by the three-dimensional closest packing lamination. .

30 shows the carbon nanorod group 13A in the state of being manufactured (produced at 600 ° C using an iron catalyst) constituting the fibrous nanocarbon 15 having a columnar structure, and treated at high temperatures of 2000 ° C and 2800 ° C, respectively. It is a photograph of the high resolution transmission electron microscope of a later structure.

FIG. 31 is a Raman scattering spectrum before and after heat treatment of the fibrous nanocarbon 15 made of the carbon nanorod group 13A having a columnar structure. According to a recent study, the peak of 1350 cm ^-1 in the Raman scattering spectrum of carbon not only quantifies amorphous carbon, but also shows the quantitative sensitivity of the cross section (edge face; 10 face) of the carbon hexagonal reticle 11. It turns out.

As shown in Table 1, the fibrous nanocarbon 15 having a columnar structure does not show a large difference compared with before and after graphitization. However, as can be seen from the transmission electron micrograph of FIG. 31 and the Raman spectrum of FIG. 32, it can be confirmed that the peak near 1350 cm ⁻¹ is significantly reduced by heat treatment of 2000 ° C. or higher.

The edge surface (surface 10) of the carbon hexagonal reticle 11 of the carbon nanorod group 13A constituting the fibrous nanocarbon 15 having a columnar structure by heat treatment at 2000 ° C. or higher is formed by bonding at the end. All of them clearly indicate that the dome-shaped base surface (plane 002) is three-dimensional. Moreover, from this result, the fibrous nanocarbon 15 of columnar structure before heat processing contains a large amount of the edge face (10 faces) of the carbon hexagonal reticle 11 which hardly exists as a normal high graphitization carbon other than HOPG. I could confirm that I was doing.

As described above, the fibrous nanocarbon 15 made of the carbon nanorods 12 according to the present invention has a high graphitization degree while taking a columnar structure or a tubular structure, and is preferable as a highly conductive (thermal, electrical) filler. As an application utilizing a high degree of graphitization, the application may be expected also as an electrode material of a lithium secondary battery, an electromagnetic shielding material, or a catalyst carrier for an organic reaction for a fuel cell. Since it is a feather-like structure with a large surface area, it can be expected to be used as an electrode material for a supercapacitor, a storage material of methane and hydrogen, a desulfurization material such as SOx, and a denitration material such as NOx.

<Method for producing fibrous nanocarbon and apparatus thereof>

32 is a schematic view of the first embodiment of the apparatus for producing fibrous nanocarbon.

As shown in FIG. 32, the apparatus 100 for manufacturing fibrous nanocarbon according to the present invention is an apparatus for manufacturing fibrous nanocarbon 15 by reacting a carbon raw material 106 in a high temperature fluidized bed using a catalyst. A fluidized bed reactor (103) having a heating means (102) for filling a catalyst mixed fluid (101) formed by bonding a carrier on which a catalyst is supported by a binder to form a fluidized bed, and for heating the inside thereof; First gas supply means (105) for supplying reducing gas (H ₂ or inert gas comprising H ₂ , or CO) 104 into the fluidized bed reactor (103); Carbon raw material supply means (107) for supplying a carbon raw material (106) contacting with a catalyst fluid (101) to produce fibrous nanocarbon (15) into the fluidized bed reactor (103) in a gaseous state; Second gas supply means 109 for supplying an inert gas 108 containing no carbon into the fluidized bed reactor 103; And a discharge line 111 for discharging the scattering particles 110 containing the gas G and the obtained fibrous nanocarbon 15 from the fluidized bed reactor 103.

The fluidized bed reactor 103 is formed of a fluidized bed part 103A forming a fluidized bed, and a free board part 103B communicating with an upper portion of the fluidized bed part 103A. The fluidized bed reaction types are bubble type fluidized bed type and jet type fluidized bed type. Any one can be used in the present invention. The free board portion 103B preferably has a larger flow path cross-sectional area than the fluidized bed portion 103A.

In this embodiment, the particle recovery means 112 for recovering the scattering particles 110 in the gas discharge line 111 is interposed. Examples of the recovery means 112 include means for collecting or recovering particles such as a cyclone or a filter. The cyclone separates the scattering particles 110 included in the gas G by using a centrifugal force, and the scattering particles 110 including the separated fibrous nanocarbon 15 may be recovered from the bottom of the cyclone.

In the present embodiment, as the fluid forming the fluidized bed, a catalyst-compatible fluid 101 is used instead of a general fluid such as silica sand or alumina. In this embodiment, the combined catalyst fluid 101 forms a fluidized bed, supplies the carbon raw material 106 to produce fibrous nanocarbon 15, and then, as described later, micronizes the fluid to lose its function as a fluid. In this way, recovery of the fibrous nanocarbon 15 grown on the catalyst can be facilitated.

As a result, in the case of manufacturing the fibrous nanocarbon 15, the mixed catalyst fluid 101 (catalyst) is uniformly present in the fluidized bed reactor 103, so that the contact efficiency with the carbon raw material 106 becomes good and uniform. At the same time, the recovery of the fibrous nanocarbons 15 grown on the catalyst is carried out, and the fibrous nanocarbons grown on the respective catalysts can be formed by subdividing the catalyst-coupled fluid 101 into constituent units or aggregates thereof. The separation efficiency of 15) can be improved, and uniform fibrous nanocarbon 15 can be easily obtained.

FIG. 33 is a schematic diagram of a process for producing a catalyst-compatible fluid 101 and providing fibrous nanocarbon 15 from a carbon raw material 106 using the fluid 101.

In the method for producing fibrous nanocarbon 15 according to the present invention, a catalyst-compatible fluid 101 formed by bonding a carrier 122 carrying a metal catalyst 121 through a binder 123 is used as a fluid. 1) a first gas supply step of supplying a reducing gas 104, (2) supplying a carbon raw material 106 in a gaseous state and in the presence of the catalyst 121 of the catalyst-compatible fluid 101 ), And (2) a second gas supply step of supplying an inert gas 108 containing no carbon and losing the flow function of the catalyst-compatible fluid 101.

First, the catalyst mixed fluid 101 of the present invention is formed by combining a carrier 122 carrying a catalyst 121 with a binder 123, as shown in FIGS. 33A and 33B. will be. 33 (e) to 33 (e), the catalyst dual fluid 101 shows only the contour.

In the catalyst mixed fluid 101, when the catalyst 121 is supported on the carrier 122, the catalyst 121 is supported on the carrier 122 in a more minute state to see the fiber diameter of the fibrous nanocarbon 15. The fine catalyst 121 can be supported on the carrier by controlling various conditions such as the concentration of the nitrate of the catalyst metal, the kind of the surfactant added, the drying conditions, and the like, for example.

In addition, in the miniaturization process of the catalyst 121 using the reducing gas 104, which will be described later, the smaller the initial particle size, the finer the degree of progression becomes, and the finer the catalyst 121 when supported on the carrier 122 becomes important. .

For example, when the particle size of the initially supported catalyst 121 is 1000 nm, the fineness is 10 nm, and when the particle size of the initially supported catalyst is 100 nm, the fineness can be 1 nm.

Next, as shown in Fig. 33 (c), the obtained catalyst-compatible fluid 101 is charged into the fluidized bed reactor 103, and H ₂ as the reducing gas 104 from the first gas supply means 105 or An inert gas containing H ₂ is supplied. By supplying the reducing gas 104 such as H ₂ , the catalyst 121 supported on the carrier 122 is made into a metal from the form of nitrate, thereby exhibiting a function as a catalyst.

As shown in FIG. 33 (d), the carbon raw material 106 is supplied in a gas state to grow the fibrous nanocarbon 15 on the catalyst 121. At this time, the inert gas 108 is separately introduced into the fluidized bed reactor 103 so as to have a predetermined flow condition.

The carbon raw material 106 may be any compound as long as it contains a carbon. Examples thereof include unsaturated organic compounds such as alkanes such as methane, ethane, propane and hexane, unsaturated organic compounds such as ethylene, propylene and acetylene, benzene, toluene and the like. Aromatic compounds or petroleum, coal (including coal conversion gas) and the like, but the present invention is not limited to these.

The fibrous nano-carbon 15 is produced by starting from the catalyst 121 of the catalyst fluid fluid 101. Therefore, to obtain a thinner fibrous nano-carbon (15), the first gas supply step, in at least one of a carbon-supplying step, the fibrous nano-carbon production process, hydrogen in the atmosphere (H _2), carbon monoxide (CO), etc. It is preferable to make the catalyst 121 finer when metallizing the catalyst 121 supported on the carrier 122 by the reducing action of the reducing gas 104.

For example, when the catalyst 121 in an initial state is about 100 nm, it can refine | miniaturize to about 1 nm by refinement | miniaturization. Therefore, in each of the above steps (first gas supply step, carbon supply step, and fibrous nanocarbon production step), the fiber diameter of the fibrous nanocarbon 15 produced by adjusting various conditions such as the reducing gas 104 and temperature, etc. And fiber structure.

Then, at the end of the reaction, as shown in FIG. 33 (e), the inert gas 108 containing no carbon is supplied and the inside of the fluidized bed reactor 103 is heated to a higher temperature than the reaction temperature by the heating means 102. As a result, the binder 123 forming the catalyst-compatible fluid 101 is decomposed by pyrolysis or the like, and the particle size of the fluid 101 is made small to be refined to lose its function as a fluid.

The fluid having lost the flow function becomes an aggregate of the carrier 122 or a combination thereof, which is refined to form gas (from the discharge line 111 through the free board portion 103B of the fluidized bed reactor 103 as the scattering particles 110). It discharges to the outside with G), and is collect | recovered by the particle | grain recovery means 112 (refer FIG. 32). Thereafter, the fibrous nanocarbon 15 is separated from the recovered scattering particles 110, whereby the fibrous nanocarbon 15 as a product can be obtained. On the other hand, the fibrous nanocarbon 15 produced in the catalyst 121 is also separated in the fluidized bed reactor 103.

The fibrous nanocarbon 15 can be separated from the catalyst 121 or the carrier 122 by, for example, disappearing the catalyst 121 or the carrier 122 of the grown root portion. A separation example is shown in FIG.

As it is shown in Figure 34, a method of supplying a method for gasifying the carrier 112, such as at the base of the fiber-shaped nano-carbon (15) with H _2, or water vapor (H ₂ O) and CO ₂ as a gas agent and By controlling the temperature to promote gasification, the carrier 122 and the like at the root portion of the fibrous nanocarbon 15 are lost. By this method, the fibrous nanocarbon 15 grown from the catalyst 121 can be separated from the carrier 122 or the unused catalyst 121 remaining in the carrier 122. This separation can be carried out at the same time as at least after recovery from the fluidized bed reactor 103 or in the fluidized bed reactor 103.

The catalyst combined fluid 101 has an average particle diameter of 0.2 to 20 nm so as to exhibit a good flow function in the fluidized bed reactor 103. This is because the inside of the fluidized bed reactor 103 can be stirred vigorously by setting the average particle diameter of the catalyst combined fluid 101 to the above range, and as a result, a uniform reaction field can be formed.

The catalyst combined fluid 101 is a known granulation method (e.g., a rotating fan granulation method, a rotary drum granulation method, a fluidized bed granulation method such as a fluidized bed granulation method, or a compression granulation method, or extrusion). Forced granulation method) such as a mold granulation method).

In addition, the flow velocity of the fluidized bed reactor 103 is preferably 0.02 to 0.2 m / s when the particle size of the combined fluid fluid 101 for a catalyst is 0.2 mm. As shown in FIGS. 35 and 36, when the flow rate is less than 0.02 m / s, fluidization of the combined catalyst fluid 101 does not occur and does not function as a fluidized bed, and when the flow rate is more than 0.2 m / s, the fluid 101 Is not preferable because it can not be controlled outside the fluidized bed reactor 103 to control the reaction time.

On the other hand, the air column velocity of the fluidized bed can be set by selecting different optimum values within a range of 2 to 8 times the fluidization start rate Umf of the fluid medium to be used, depending on various conditions such as raw materials and additives to be used. That is, the tower speed is set to a gas flow rate 2 to 8 times higher than the fluidization start rate. This air column speed is mainly maintained by controlling the amount of gas supplied from the inert gas supply means and the like.

Moreover, the contact reaction temperature of the catalyst 121 and the carbon raw material 106 of the catalyst mixed fluid 101 in the fluidized bed reactor 103 is preferably 300 ° C to 1300 ° C, and the pressure is preferably 0.1 to 25 atmospheres. . This is because good fibrous nanocarbon 15 cannot be produced if the temperature and pressure are outside the above ranges.

In the reaction, the fibrous nanocarbon 15 is obtained by contacting the carbon raw material 106 with the catalyst 121 of the mixed fluid 101 for a predetermined time in a reducing gas 104 having a hydrogen partial pressure of 0% to 90%. do. The supply of H ₂ in this reaction is for further promoting the growth of the fibrous nanocarbon 15 that grows on the catalyst 121 of the mixed fluid fluid 101. On the other hand, as the H ₂ source, it can be used for hydrogen in the carbon source (106) for feeding.

In addition, various conditions such as the temperature, pressure, time, and gas atmosphere of each of the first reducing gas supplying step, the carbon raw material supplying step, and the second gas supplying step can be independently controlled. Specifically, for example, when reducing and miniaturizing the catalyst 121 in the first reducing gas supply process, the temperature may be lower than the manufacturing conditions of the fibrous nanocarbon 15 in the carbon raw material supply process.

As shown in FIG. 33 (a), the catalyst mixed fluid 101 is formed of a catalyst 121 supported on the surface of the carrier 122 or an aggregate thereof. The carrier 122 has a diameter of about 40 nm, but is not limited thereto. The agglomerate refers to a number of these carriers 122 self-aggregating to an average particle diameter of about 100 to 200 nm.

Examples of the material of the carrier 122 include carbon black (CB), alumina (Al ₂ O ₃ ), silica (Si), silica sand (SiO ₂ ), aluminosilicate, and the like. Any thing can be used as long as it has a function to carry, but it is not limited to these.

It is preferable that the average particle diameter of the said carrier 122 is 200 micrometers or less. A catalyst 121 is supported on the surface of the carrier 122 or an aggregate thereof is used to form a binder using the binder 123 to form a catalyst-compatible fluid 101 having an average particle diameter of 0.2 to 20 mm.

Examples of the catalyst 121 include Fe, Ni, Co, Cu, Mo or a mixture of at least two or more thereof, but the present invention is not limited thereto. For example, when Fe is used as the catalyst 121 and carbon black is used as the carrier 122, it is preferable to add carbon black to an aqueous solution of iron nitrate or iron acetate so that Fe is supported on the surface of the carbon black. Do. As a result, as shown in the enlarged view of FIG. 33A, the catalyst 121 is supported on the surface 122a and the pores 122b of the carrier 122.

As said binder 123, a polymeric adhesive agent, an inorganic adhesive agent, the material which has another bonding effect, etc. are mentioned, for example.

Examples of the polymer adhesive include thermosetting polymer materials such as phenolic resin (maximum use temperature: about 360 ° C), urea resin (maximum use temperature: about 288 ° C), epoxy resin (maximum use temperature: about 288 ° C). It is preferable to use the binder which consists of polyimide-type resin (maximum use temperature: about 349 degreeC). This is because, as will be described later, the fibrous nanocarbon 15 is produced by supplying the carbon raw material 106 at a high temperature (300 ° C. or higher) in the fluidized bed, so that reflowing (melting) is performed in the high temperature state. It can be suppressed.

Examples of the inorganic adhesive include, but are not limited to, SiO ₂ and Al ₂ O ₃ .

Examples of the bonding material having another bonding action include tar or heavy oil, but the present invention is not limited thereto.

In the present invention, as shown in the following examples, the fibrous nanocarbon 15 is produced at about 480 ° C., and then, the inert gas 108 containing no carbon is supplied, and the heating means 102 is used for The binder 123 is thermally decomposed by heating at about 800 ° C. to subdivide the catalyst combined fluid 101 to the carrier 122 unit.

On the other hand, it is considered that pyrolysis proceeds somewhat even under the condition of 480 ° C, but it is also considered that sintering of carbon proceeds by caulking simultaneously with pyrolysis under conditions without oxygen. If in this case, unless the gasification or carbon nano fiber 15 due to H ₂ combustion above 800 ℃, as described above, it is preferable that the combustion process.

Meanwhile, the tar may be gasified by H ₂ , CO, or the like at a temperature of 800 ° C. or higher.

37 is a schematic view of the second embodiment of the apparatus for producing fibrous nanocarbon. As shown in FIG. 37, the apparatus 200 for manufacturing fibrous nanocarbon according to the present embodiment includes the inside of the fluidized bed portion 103A of the fluidized bed reactor 103 such that the fluid 101 may be continuously flown in the apparatus of FIG. 1. Is divided into three to form a first flow chamber 203A-1, a second flow chamber 203A-2, and a third flow chamber 203A-3, and the first flow chamber 203A-1 includes a reducing gas ( First gas supply means 105 for supplying 104 is provided, and carbon raw material supply means 107 for supplying carbon raw material 106 is provided in the second flow chamber 203A-2, and the third flow chamber is provided. The second gas supply means 109 for supplying the inert gas 108 containing no carbon is provided in 203A-3.

The same code | symbol is used about the member same as 1st Embodiment, and the description is abbreviate | omitted.

In the present embodiment, the interior is divided while forming the fluidized bed by providing a plurality of boundary plates 202 so as to alternately hang up and down in the vertical axial direction in the fluidized bed reactor 103, and the first in order from the left in the drawing. The first flow chamber 201A-1 is constituted by the subsidiary chamber 203A-11, the second subsidiary chamber 203A-12 and the third subsidiary chamber 203A-13, and the fourth subsidiary chamber 203A-24 and the fifth subsidiary chamber. (203A-25), the sixth sub chamber 203A-26, and the seventh sub chamber 203A-7 constitute a second flow chamber 203A-2, and the eighth sub chamber 203A-38 and the ninth sub chamber ( The third flow chamber 203A-3 is constituted by 203A-39, but the present invention is not limited to this arrangement. On the other hand, the free board part 103B is common with the 1st, 2nd, and 3rd flow chamber.

In this embodiment, the fluid supply means 204 which supplies the catalyst combined fluid 101 to the 1st flow chamber 203A-1 is provided, and the catalyst combined fluid 101 is sequentially supplied. This allows for continuous production.

For example, in the case where the entire fluidized bed reactor 103 is reacted for 9 hours, 7 hours of residence in the first fluid chamber 203A-1, 1 hour of residence in the second fluid chamber 203A-2, and the third In order to allow 1 hour of residence in the flow chamber 203A-3, the position of the boundary plate 202 and the volume of each chamber are adjusted so that the catalyst-flowing fluid 101 can remain in each room for an arbitrary time. To help.

In the first flow chamber 203A-1, the reducing gas 106 is supplied to exhibit the catalytic function of the fluid for mixing catalyst 101, and the carbon source gas 106 is supplied in the second flow chamber 203A-2. The fibrous nanocarbon 15 having high efficiency was produced by contacting with the catalyst fluidized material 101 having a catalytic function, and the inert gas 108 containing no carbon was supplied from the third flow chamber 203A-3. At the same time, by making the temperature higher than the reaction temperature, the catalyst function of the combined catalyst fluid 101 is lost and refined to make the scattering particles 101 having a particle size of 40 to 100 nm scatter with the gas C to be recovered. On the other hand, the catalyst mixed fluid 101 which is not scattered is separately collected by the recovery means.

As another example of this embodiment, it is also possible to have a fluidized bed reactor 103 comprising a fluidized bed section with a first fluid chamber and a second fluidized chamber, and a fluidized bed reactor comprising a fluidized bed section with the third fluid chamber.

38 is a schematic diagram of a third embodiment of an apparatus for producing fibrous nanocarbon. In this embodiment, as shown in FIG. 38, the fluidized bed reactor 103 is configured to have each independent function to enable continuous production.

As shown in FIG. 38, the apparatus 300 for producing fibrous nanocarbon according to the present embodiment is an apparatus for producing fibrous nanocarbon 15 by reacting a carbon raw material 106 in a high temperature fluidized bed using a catalyst. A first fluidized bed having a heating means 102 for filling the catalyst-coupled fluid 101 therein and for heating the inside, and having a first gas supply means 105 for supplying a reducing gas (H ₂ or CO). Reactor 301; And a transfer means 302 for transferring the mixed catalyst fluid 101 from the first fluidized bed reactor 301, and at the same time, a carbon raw material 106 for contacting the mixed catalyst fluid 101 to generate the fibrous nanocarbon 15. Second fluidized bed reactor (303) having carbon raw material supply means (107) for supplying gas in a gaseous state; A third fluidized bed having a conveying means 304 for conveying the reaction product and the fluid from the second fluidized bed reactor 303 and having a second gas supply means 109 for supplying an inert gas 108 containing no carbon. Reactor 305; And a discharge line 111 for discharging the gas G and the scattering particles 110 from the third fluidized bed reactor 305.

The first fluidized bed reactor 301, the second fluidized bed reactor 303, and the third fluidized bed reactor 305 are the fluidized bed parts 301A, 303A, and 305A and the free board parts 301B, 303B, and 305B as in the first embodiment. Are each provided.

In the first fluidized bed reactor 301, the reducing gas 106 can be supplied to exhibit the catalytic function of the catalyst-coupled fluid 101. Next, it supplies to the 2nd fluidized bed reactor 303 by the conveying means 302, such as airflow conveyance. In the second fluidized bed reactor 303, the carbon source gas 106 is supplied and brought into contact with the catalyst combined fluid 101 that exhibits a catalytic function to produce highly efficient fibrous nanocarbon 15. Then, it supplies to the 3rd fluidized bed reactor 305 by the conveying means 304, such as airflow conveyance. In the third fluidized bed reactor 305, the inert gas 108 containing no carbon is supplied, and at a temperature higher than the reaction temperature, thereby losing the catalytic function of the catalyst / coating fluid 101, thereby miniaturizing the grain size, and having a particle size of 40. It is to be recovered by scattering together with the gas (G) as the scattering particles 110 to 100nm. By this method, the fibrous nanocarbon 15 can be manufactured continuously. In addition, the catalyst combined fluid 101 which does not scatter is separately collected by a recovery means.

The conveying means 302, 304 may include means by cutting-off conveying using a filter in addition to the air flow conveying and the like mentioned above. However, the conveying means 302, 304 is not limited to these means as long as the fluid member 101 can be conveyed.

Depending on the residence time of the fluid 101 in each reactor 310, 303, and 305, the volume of the reactor 310, 303, 305 can be varied. For example, when the average residence time is 7 hours in the first fluidized bed reactor 301 and 1 hour in the second fluidized bed reactor 303 and the third fluidized bed reactor 305, respectively, The reaction conditions can be adjusted by making the volume seven times the volume of the second and third fluidized bed reactors.

Further, the first to third fluidized bed reactors 301, 303, and 305 may all have the same volume, and seven first fluidized bed reactors 301 may be connected in series.

In addition, as necessary, the first fluidized bed reactor 301 may be provided with a plurality of controllers to adjust the throughput. Similarly, the second fluidized bed reactor 303 may be provided with a plurality of controllers to adjust throughput. Similarly, the third fluidized bed reactor 305 may be provided with a plurality of controllers to adjust throughput.

39 is a schematic view of the fourth embodiment of the apparatus for producing fibrous nanocarbon. As shown in Fig. 39, the present embodiment makes it possible to prepare two second fluidized bed reactors 303 in the third embodiment to produce different reaction conditions.

As shown in FIG. 39, the apparatus 400 for producing fibrous nanocarbon according to the present embodiment is an apparatus for producing fibrous nanocarbon 15 by reacting a carbon raw material 106 in a high temperature fluidized bed using a catalyst. The first gas supply means 105 is provided with a heating means 102 for heating the inside of the catalyst and the fluid fluid 101, and for supplying a reducing gas (H ₂ or CO) 104. Having a first fluidized bed reactor 301 and a conveying means 402-1 for transferring the mixed catalyst fluid 101 from the first fluidized bed reactor 301, and in contact with the mixed catalyst fluid 101, fibrous nanocarbon A first second fluidized bed reactor 403-1 having carbon raw material supply means 107 for supplying the carbon raw material 106 for producing (15) therein in a gaseous state; It has a conveying means 402-2 which transfers the catalyst combined fluid 101 from the 1st 2 fluid bed reactor 403-1, and makes contact with the catalyst combined fluid 101, and produces fibrous nanocarbon 15. A second second fluidized bed reactor 403-2 having a carbon raw material supply means 107 for supplying the carbon raw material 106 therein in a gas state therein; Second gas supply means having a conveying means 304 for conveying the reaction product and the fluid from the second second fluidized bed reactor 403-2, and at the same time supplying an inert gas 108 containing no carbon therein; A third fluidized bed reactor 305 having 109; And a discharge line 111 for discharging the gas G and the scattering particles 110 from the third fluidized bed reactor 305.

For example, the temperature condition of the heating means 102 of the second second fluidized bed reactor 403-2 is compared with the temperature condition of the heating means 102 of the first second fluidized bed reactor 403-1. The feather structure on the catalyst 121 of the mixed fluid fluid 101 is changed by changing (for example, the temperature is 100 ° C. or more) and, for example, by setting the reaction temperature in the first fluidized bed reactor 403-1 in the first stage to 480 ° C. After growing the carbon nanorod group 13B of the carbon nanorod group 13B (see FIG. 40), the reaction temperature in the second fluidized bed reactor 403-2 of the second stage was set to 630 ° C. ), A complex in which the carbon nanorod group 13A having a tubular structure is grown can be prepared (see FIG. 41).

42 is a schematic diagram of a fifth embodiment of the apparatus for producing fibrous nanocarbon. As shown in FIG. 42, in the apparatus 500 for manufacturing fibrous nanocarbon according to the present embodiment, the fluidized bed part 103A of the fluidized bed reactor 103 includes the high speed side fluidized bed part 503A-1 and the low speed side fluidized bed part. Composed of (503A-2), and in the second gas supplying step after the production of the fibrous nanocarbon 15, the catalyst-containing fluid 101 in the high-speed side fluidized bed 503A-1 is vigorously stirred to provide a fluid 101 ), It is possible to promote the miniaturization by miniaturization due to abrasion and reduction of the bonding force of the binder 123.

Specifically, for example, when the diameter of the catalyst-compatible fluid 101 is set to 0.5 mm, the low-speed fluidized bed part 503A-2 at the top of the fluidized bed part 103A controls the flow rate to about 0.1 m / s to prevent scattering. The flow velocity of the high speed side fluidized bed portion 503A-1 at the lower portion of the fluidized bed portion 103A is set to about 0.2 to 1.0 m / s, and the catalyst and mixed fluid 101 is vigorously stirred to refine by wear of the fluid 101. Can be tried.

As shown in FIG. 43, the collision member 501 is further arrange | positioned in the high speed side fluidized-bed part 503A-1, and the catalyst combined fluid material 101 is actively collided with the said collision member 501, and refinement | miniaturization is added. Can be promoted.

44 is a schematic view of the sixth embodiment of an apparatus for producing fibrous nanocarbon. As shown in FIG. 44, in the manufacturing apparatus 600 of fibrous nanocarbon which concerns on this invention, the high-speed gas blowing means 602 which injects the high-speed gas 601 from the side wall in the fluidized-bed reactor 103 is provided, By violently stirring the catalyst-flowing fluid 101 by the high-speed gas 601 blown in the second gas supplying step after the production of the fibrous nanocarbon 15, the fineness due to the abrasion of the fluid 101 and the binder 123 are obtained. It is possible to promote the miniaturization by lowering the bonding force.

Specifically, by blowing N ₂ gas or inert gas from the high speed gas blowing means 602 at a flow rate of 10 m / s as the high speed gas 601, the mixed fluid 101 is stirred vigorously to abrasion of the fluid 101 It can be miniaturized by.

In addition, as shown in FIG. 45, when the crude fly particles 110b separated by the particle recovery means 112a are fed back into the fluidized bed reactor 103, the mixing means 603 is supplied to the high velocity gas 601. By mixing and blowing the coarse scattering particles 110b together with the high-speed gas 601, the physical breakdown force is improved, resulting from the miniaturization caused by the wear of the catalyst-coupled fluid 101 and the decrease of the bonding force of the binder 123. It can promote micronization. At this time, the fine scattering particles 110a containing the fibrous nanocarbon 15 can be separated and recovered by the downstream separating means 112b.

That is, the fifth and sixth embodiments form a localized high velocity region in the catalyst fluidized fluid 101 in the fluidized bed reactor 103 in the second gas supply process, thereby causing mutual collisions of the fluidized material 101, fluidized material 101. ) And collision between the wall surface or the collision member 503 of the reactor 103 or the blowing of the high-speed gas 601, etc., facilitates the miniaturization due to the wear and break of the catalyst mixed fluid 101 and the fibrous nanocarbon (15). ) To improve the recovery efficiency.

Thus obtained fibrous nanocarbon 15 is a transparent conductive material (conductive ink, conductive film, conductive plastic), ITO replacement material, transparent electromagnetic wave blocking material, antistatic material (solar cell, mirror, etc.), transparent ultraviolet blocking material (e.g., Cosmetic applications, automotive glass coating applications, etc.), high-grade electrical and thermal conductive materials (printer rolls, fax millimeters, etc.), high-quality conductive and heat-radiating devices, ceramic mixtures, carbon-carbon composites, battery conductive materials, and the like Adsorption or storage material, hydrogen storage material, hydrogen separation material, separation material such as butane, capacitor electrode material, electric desalination electrode material, seawater decomposition (electrolyte cell) oxygen electrode material, battery material (lithium secondary battery, NaS battery, Air secondary battery, long life alkaline battery conductive material), FED material, nano-lithography semiconductor, lead wire, MLUDI (genetic detection, diagnostic material), nano brain wave probe, biocompatible material, high selectivity catalyst carrier, high activity catalyst Carriers, graphite catalyst substitutes, Active catalyst carriers (e.g., Pt, Pt-Rh), thin film separators, air pollutants (SOx, NOx, ozone) adsorbents, water pollutant adsorbents, desalination purification electrode materials, various gas sensors, various materials such as conductive paper, gas It is preferable to use for an adsorption material, a biomaterial, etc.

Therefore, according to the present invention, the first gas supply process of using a catalyst mixed fluid formed by bonding a metal catalyst supporting carrier through a binder as a fluid and supplying a reducing gas, and supplying a carbon raw material in a gas state and a catalyst of a catalyst mixed fluid And a second gas supply step of supplying an inert gas containing no carbon and losing the flow function of the catalyst fluid, in which the catalyst is uniformly provided in the fluidized bed. In the presence of the catalyst, the contact efficiency between the catalyst and the raw material is improved, uniform reaction is carried out, and in the recovery of the fibrous nanocarbon growing on the catalyst, the fluidized material having a catalyst function is refined and the structural unit of the carrier or By making the aggregate, the separation efficiency of the fibrous nanocarbon growing on each catalyst It can be improved to obtain a catalyst having uniform properties.

Carbon nanorods and fibrous nanocarbons

Preferred examples of carbon nanorods and fibrous nanocarbons according to the present invention are described below, but the present invention is not limited by these examples.

Example 1

Example 1 is fibrous nanocarbon of columnar structure.

Using iron nitrate, precipitation method (Best, RJ Russell, WW, J. Amer. Soc. 76, 838 (1954), Sinfelt, JH, Carter, JL, and Yates, DJC, J. Catal. 24, 283 ( 1972)) to produce an iron catalyst.

Specifically, 29.54 g of iron nitrate (made by Wako Pure Chemicals, Reagent Grade 1, FeNO ₃ .9H ₂ O) was added to 200 ml of pure water to prepare a 4 g iron catalyst, and stirred slowly to prepare a solution. Ammonia hydrogen carbonate (NH ₄ HCO ₃ ; reagent grade 1, manufactured by Junsei Chemical Co., Ltd.) is added to the solution while stirring until a precipitate (FeCO ₃ · xH ₂ O) is formed. The precipitate is filtered and purified until pure ammonia is removed. The purified precipitate was vacuum dried at 80 ° C. for 8 hours, and then Fe ₂ O ₃ was obtained by heat-treating at 450 ° C. for 5 hours in an air atmosphere using a horizontal carbonaceous furnace.

The manufactured Fe ₂ O ₃ was placed in an alumina boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and mixed gas of hydrogen and helium (10% hydrogen partial pressure) in an alumina tube (inner diameter 10 cm). ), 4.02 g of an iron catalyst was obtained by reducing the mixture at 100 sccm for 48 hours at 480 ° C.

Subsequently, 50 mg of the iron catalyst prepared by the above method was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and a mixed gas of hydrogen and helium in a quartz tube having an inner diameter of 4.5 cm ( 20% hydrogen partial pressure) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixed gas (hydrogen partial pressure: 20%) of carbon monoxide and hydrogen was allowed to react at a temperature of 580 ° C. for 60 minutes while flowing at 100 sccm to produce a predetermined amount (1252 mg) of fibrous nanocarbon.

Example 2

This embodiment is an example of the case where the fibrous nanocarbon of Example 1 is heat-treated at high temperature.

That is, the fibrous nanocarbon prepared in Example 1 was heat-treated for 10 minutes at 2000 ℃ and 2800 ℃ in an argon atmosphere.

Example 3

This embodiment is a fibrous nanocarbon having a feather structure.

A nickel catalyst was prepared by using nickel nitrate and by the precipitation method of Example 1.

Specifically, in order to prepare a 4 g nickel catalyst, 19.82 g of nickel nitrate (NiNO ₃ xH ₂ O, reagent grade 1, manufactured by Wako Pure Chemical Co., Ltd.) was added to 200 ml of pure water, and the mixture was stirred slowly to prepare a solution. To this solution, hydrogen ammonia carbonate (NH ₄ HCO ₃ ; reagent grade 1, manufactured by Junsei Yuku Hinkyo Co., Ltd.) is added while stirring until a precipitate (NiCO ₃ · xH ₂ O) is formed. The precipitate is then filtered and purified with pure water until there is no ammonia hydrogen carbonate. The purified precipitate was vacuum dried at 80 ° C. for 8 hours, and then heated to 450 ° C. for 5 hours in an air atmosphere using a horizontal carbon dioxide furnace to obtain nickel oxide.

The prepared nickel oxide was placed in an alumina boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and a mixed gas of hydrogen and helium (hydrogen partial pressure: 10%) was carried out in an alumina tube having an inner diameter of 10 cm. 4.01 g of iron catalyst was obtained by reducing for 48 hours at 480 degreeC, flowing at 100 sccm.

Thereafter, 50 mg of the nickel catalyst prepared by the above method was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and hydrogen and helium mixed in a quartz tube having an inner diameter of 4.5 cm. The gas (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixed gas of ethylene and hydrogen (hydrogen partial pressure: 20%) was reacted at 580 ° C. for 60 minutes while flowing at 100 sccm, thereby preparing a predetermined amount (60 mg) of fibrous nanocarbon.

Example 4

This example is a high-temperature heat treatment of the fibrous nanocarbon of Example 3.

That is, the fibrous nanocarbon prepared in Example 3 was heat-treated at 2000 ° C. and 2800 ° C. for 10 minutes under argon atmosphere.

Example 5

This embodiment is a fibrous nanocarbon having a tubular structure.

An iron nickel alloy catalyst was prepared by the precipitation method of Example 1 using iron nitrate and nickel nitrate.

Specifically, to prepare 4 g of iron-nickel catalyst, 11.90 g of nickel nitrate (NiNO ₃ xH ₂ O, reagent grade 1, Wako Pure Chemical Co., Ltd.) and iron nitrate (FeNO ₃ · 9H ₂ O, 11.80 g of reagent 1, Waco Pure Chemical Co., Ltd.) was added, and stirred slowly to prepare a solution. To the solution, ammonia hydrogen carbonate (NH ₄ HCO ₃ , reagent grade 1, manufactured by Jusei Yuka Hinkyo Co., Ltd.) is added while stirring until a precipitate (NiCO ₃ · xH ₂ O) is formed. The precipitate is then filtered and purified with pure water until the ammonia of hydrogen carbonate is gone. The purified precipitate was vacuum dried at 80 deg. C for 8 hours, and then iron oxide-nickel was obtained by treatment at 450 deg. C for 5 hours in an air atmosphere using a horizontal carbonaceous furnace.

The manufactured iron oxide-nickel was placed in an alumina boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)) and mixed gas of hydrogen and helium (hydrogen partial pressure: 10%) in an alumina tube having an inner diameter of 10 cm. 4.05 g of iron-nickel catalyst was obtained by reducing the product at 480 ° C. for 48 hours while flowing 100 sccm.

Thereafter, 50 mg of the iron-nickel catalyst prepared by the above method was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and hydrogen and helium in a quartz tube having an inner diameter of 4.5 cm. Of mixed gas (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixed gas (hydrogen partial pressure: 80%) of carbon monoxide and hydrogen was allowed to react at a temperature of 630 ° C for 60 minutes while flowing at 200 sccm, thereby preparing a predetermined amount (432 mg) of fibrous nanocarbon.

Example 6

This example is a heat treatment of the fibrous nanocarbon of Example 5 at a high temperature.

Specifically, the fibrous nanocarbon prepared in Example 5 was heat-treated for 10 minutes at 2000 ℃ and 2800 ℃ in argon atmosphere.

<X-ray diffraction measurement>

The fibrous nanocarbons (150 mg) obtained in Examples 1 to 6 were mixed with 15 mg of standard silicon, respectively, and diffracted (CuKα ray at 5 degrees to 90 degrees using a wide-angle X-ray diffractometer (manufactured by Rigaku Corporation). , 40 kV, 30 mA, stepwise method) to obtain a rotation pattern.

From the obtained X-ray pattern, the interplanar distance (d ₀₀₂ ), the laminate size (Lc ₀₀₂ ), and the crystal size (La ₁₁₀ ) were calculated by the Gakusin method. The results are shown in Table 1 above.

<Observation by electric field scanning transmission electron microscope>

In order to investigate the fiber diameter and the structure of the fibrous nanocarbon obtained in Examples 1-4, it observed with the field scanning transmission electron microscope of JEM-2010F.

Specifically, a small amount of the fibrous nanocarbon obtained in Examples 1 to 4 in n-butanol to completely disperse until the appearance of light transparency by ultrasonic dispersion, the dispersion is 1 to 2 drops in the micro network sample cell After the addition, the sample cell was dried in air at room temperature for one day and observed.

The results are shown in FIGS. 6 (Examples 1 and 2) and 18 (Examples 3 and 4). FIG. 6 is an enlarged photograph (8 times) observed at 400,000 times magnification, FIG. 18 is a photograph observed at 400,000 times magnification, and FIG. 18 (c) further enlarges 8 times (FIG. 18 (b)) (3 million times magnification). One picture.

Observation by Scanning Tunnel Electron Microscopy

The fibrous nanocarbons obtained in Examples 1 to 6 were observed under a scanning tunnel electron microscope (Nanoscope III (DI, U.S.A.).

Specifically, the fibrous nanocarbon obtained in Examples 1 to 6 is placed in a small amount in ethanol and completely dispersed by ultrasonic waves. One drop of the resulting dispersion was added to HOPG and observed by drying in air for 8 hours (tunneling voltage 1V, tunnel current 3.0 nA).

The results are shown in FIG. 30 (Examples 1 and 2), FIG. 7B (Example 2), FIG. 15 (Examples 1 to 6), and FIG. 29 (Examples 1 to 6). 30 (a) is a photograph of the fibrous nanocarbon of Example 1, Figure 30 (b) and 30 (c) is a photograph of the fibrous nanocarbon of Example 2, Figure 7 (b) is a figure A photograph of the fibrous nanocarbon at an angle different from that of 30 (c), FIG. 15 is a photograph of the fibrous nanocarbon at low magnification, and FIG. 29 is a photograph of the fibrous nanocarbon at high magnification.

Next, a comparative example is given.

Comparative Example 1

The iron catalyst (50 mg) prepared by the precipitation method of Example 1 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and in a quartz tube having an inner diameter of 4.5 cm, hydrogen The mixture gas of helium and hydrogen partial pressure (20%) is reduced at 500 ° C. for 0.3 hour while flowing at 100 sccm. Thereafter, a mixture of carbon monoxide and hydrogen (hydrogen partial pressure: 20%) was reacted at a temperature of 580 ° C. for 60 minutes while flowing at 100 sccm, but fibrous nanocarbon was not produced.

Comparative Example 2

The iron catalyst (50 mg) prepared by the precipitation method of Example 1 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and in a quartz tube having an inner diameter of 4.5 cm, hydrogen And a mixture of helium (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, the reaction was performed for 60 minutes at a temperature of 580 ° C while flowing carbon monoxide gas at 100 sccm, but no fibrous nanocarbon was produced.

Comparative Example 3

The nickel catalyst (50 mg) prepared by the precipitation method of Example 1 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and hydrogen in a 4.5 cm inner diameter quartz tube. And a mixture of helium (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixture of carbon monoxide and hydrogen (hydrogen partial pressure: 20%) was reacted at a temperature of 580 ° C. for 60 minutes while flowing at 100 sccm, but fibrous nanocarbon was not produced.

Comparative Example 4

The nickel catalyst (50 mg) prepared by the precipitation method of Example 1 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and hydrogen in a 4.5 cm inner diameter quartz tube. And a mixture of helium (hydrogen partial pressure: 20%) was reduced at 450 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixture of carbon monoxide and hydrogen (hydrogen partial pressure: 20%) was reacted at a temperature of 580 ° C. for 60 minutes while flowing at 100 sccm, but fibrous nanocarbon was not produced.

Comparative Example 5

The nickel catalyst (50 mg) prepared by the precipitation method of Example 1 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and hydrogen in a 4.5 cm inner diameter quartz tube. And a mixture of helium (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixture gas of carbon monoxide and hydrogen (hydrogen partial pressure: 20%) was reacted at a temperature of 680 ° C. for 60 minutes while flowing at 100 sccm, but fibrous nanocarbon was not produced.

Comparative Example 6

The iron-nickel catalyst (50 mg) prepared by the method of Example 5 was placed in a quartz boat (length 10 mm, width 2.5 mm, depth 1.5 mm (outer surface value)), and in a quartz tube having an inner diameter of 4.5 cm, A mixed gas of hydrogen and helium (hydrogen partial pressure: 20%) was reduced at 500 ° C. for 2 hours while flowing at 100 sccm. Thereafter, a mixture of carbon monoxide and hydrogen (hydrogen partial pressure: 80%) was reacted at a temperature of 700 ° C. for 60 minutes while flowing at 200 sccm. A predetermined amount (20 mg) of nanocarbon was obtained and observed under a transmission electron microscope. As a result, no fibrous structure was observed.

<Method for producing fibrous nanocarbon and apparatus thereof>

Although the preferable example of the manufacturing method and apparatus of fibrous nanocarbon which concerns on this invention is described below, this invention is not limited by these Examples.

Example 1

Fe-Ni (2/8) was used as a catalyst and carbon black ("MS-3050B" (trade name), manufactured by Mitsubishi Gas Chemical Co., Ltd., BET = 43 m 2 / g, particle size = 40 nm) was used as a carrier. (5%) was supported on the carrier. A catalyst-compatible fluid was granulated using a phenolic resin-based polymer adhesive (maximum use temperature: about 360 ° C.) as a binder.

Using this catalyst mixed fluid, fibrous nanocarbon was produced using the apparatus of the first embodiment shown in FIG.

To activate the catalyst by the first gas supply, pretreatment was performed for 7 hours using H ₂ / He (20/80). Next, ethylene (C ₂ H ₄ ) was used as a carbon raw material, C ₂ H ₄ / H ₂ (4/1) was supplied, and reacted for 1 hour in a fluidized bed reactor at 480 ° C. to prepare fibrous nanocarbon. . After the preparation of the fibrous nanocarbon, the temperature was raised in an atmosphere of H ₂ / He (20/80) to thermally decompose the binder, and the catalyst-coating fluid was granulated and scattered to recover by a recovery means.

The micrograph of the obtained fibrous nanocarbon is shown in FIG. Fig. 46 (a) is a 10,000-fold photograph and the unit is 1 mu m. Fig. 46 (b) is a 100,000-fold photograph and the unit is 1 nm.

Example 2

Fibrous nanocarbon was prepared in the same manner as in Example 1 except that Ni-Mo (2/8) was used as a catalyst, titanium oxide (TiO ₂ ) was used as a support, and the reaction temperature was set to 560 ° C.

The micrograph of the obtained fibrous nanocarbon is shown in FIG. 47. Fig. 47 (a) is a 10,000-fold photograph and the unit is 1 mu m. Fig. 47 (b) is a 50,000-fold photograph and the unit is 100 nm.

Example 3

Fibrous nanocarbon was produced in the same manner as in Example 1 except that the catalyst was made of Fe-Ni (8/2).

The micrograph of the obtained fibrous nanocarbon is shown in FIG. 48 (a) is a 10,000-fold photograph and the unit is 1 μm. Fig. 48 (b) is a 100,000-fold photograph and the unit is 1 nm.

Carbon nanorods and fibrous nanocarbons according to the present invention have a high graphitization degree and a high surface area, and are used as high functional materials (resin, metal, ceramic and carbon reinforcing material, heat dissipating material, catalyst carrier, gas adsorption, biocomposite, etc.). It is desirable to. Particularly high capacities of hydrogen storage, adsorption and desorption, lithium storage, adsorption and desorption, catalysis and adsorption of nitrogen oxides are exhibited.

Claims (53)

Carbon nanorods comprising a carbon hexagonal net surface having a central axis extending in one direction. The method of claim 1, An axial width (D) of the carbon hexagonal net surface is 2.5 ± 0.5 nm, carbon nanorods characterized in that the length (L) of the carbon hexagonal net surface is 17 ± 15 nm. The method according to claim 1 or 2, Carbon nanorods, characterized in that the carbon hexagonal net surface is laminated in 2 to 12 layers. A fibrous nanocarbon, comprising a plurality of carbon nanorods according to claim 1 or 2 assembled. The method of claim 4, wherein A fibrous nanocarbon, characterized in that the carbon nanorods are laminated in a three-dimensional close-packed state (closest). The method of claim 4, wherein Fibrous nanocarbon, characterized in that the carbon nanorods are stacked in plural with the central axis parallel to each other to form a carbon nanorod group. The method of claim 6, The carbon nanorod group has a nano void between the carbon nanorod formed by laminating 2 to 12 layers of the carbon hexagonal network and the carbon nanorod formed by laminating 2 to 12 layers of the carbon hexagonal network. While fibrous nano-carbon, characterized in that laminated three-dimensionally. The method of claim 4, wherein Fibrous nanocarbon, characterized in that the carbon nanorods are bonded in series at the shaft end to form a carbon nanorod group in the axial direction. The method of claim 8, The shaft end portion of the carbon nanorods are bonded by heat treatment. The method of claim 6, The carbon nanorod group has a columnar shape by being arranged at an array angle of more than 0 degrees and less than 20 degrees with respect to an axis orthogonal to the fiber axis in the stacking direction of the carbon nanorods. carbon. The method of claim 6, The carbon nanorod group is formed in a feather shape by being arranged at an array angle of more than 20 degrees and less than 80 degrees with respect to an axis orthogonal to the fiber axis in the stacking direction of the carbon nanorods. carbon. The method of claim 10 or 11, The carbon nanorod group is a fibrous nanocarbon, characterized in that the herringbone (herring-bone) structure. The method of claim 10 or 11, Fibrous nanocarbon, characterized in that the interplanar distance (d ₀₀₂ ) between the carbon hexagonal net surface under a heat treatment condition of 700 ℃ or less. The method of claim 10 or 11, The fiber width of the aggregate of the carbon nanorods is 8 to 500nm, the fiber-shaped nanocarbon, characterized in that the aspect ratio (fiber length / fiber width) of the fiber is 10 or more. The method of claim 8, The carbon nanorod group is formed in a tubular shape by being arranged at an array angle of 80 degrees to 88 degrees with respect to an axis orthogonal to a fiber axis in the stacking direction of the carbon nanorods. The method of claim 15, A fibrous nanocarbon, wherein the fiber width of the aggregate of carbon nanorods is 8 to 80 nm, and the aspect ratio (fiber length / fiber width) of the fiber is 30 or more. The method of claim 10 or 11, Fibrous nanocarbon, characterized in that the cross-sectional structure in the direction perpendicular to the fiber axis is a polygon. The method of claim 10 or 11, A fibrous nanocarbon, which is heat-treated at 1600 ° C. or higher, so that the ends of the carbon nanorods on the surface are formed in a loop shape in two dimensions and in a dome shape in three dimensions. A method of producing fibrous nanocarbon consisting of aggregates of carbon nanorods by reacting a carbon raw material in a high temperature fluidized bed using a catalyst, A catalyst mixed fluid formed by bonding a carrier carrying a metal catalyst through a binder is used as a fluid. A first gas supply process for supplying a reducing gas, A carbon raw material supply step of supplying the carbon raw material in a gas state to produce carbon nanorods in the presence of the metal catalyst of the mixed catalyst fluid; A method for producing fibrous nanocarbon, characterized in that for carrying out a second gas supply step of supplying a gas containing no carbon to lose the flow function of the catalyst combined fluid. The method of claim 19, Method for producing fibrous nanocarbon, characterized in that the average particle diameter of the catalyst combined fluid material is 0.2 to 20mm. The method of claim 19, A method for producing fibrous nanocarbon, wherein the catalyst-compatible fluid includes the catalyst on the surface of the carrier or aggregates thereof. The method of claim 19, The carrier of the mixed catalyst fluid is a method for producing fibrous nanocarbon, characterized in that selected from carbon black, alumina, silica, silica sand and aluminosilicate. The method of claim 19, A method for producing fibrous nanocarbon, characterized in that the metal catalyst of the mixed catalyst fluid is any one of Fe, Ni, Co, Cu, and Mo, or a mixture of two or more thereof. The method of claim 19, A flow rate in the fluidized bed is 0.02 to 2 m / s, characterized in that the manufacturing method of the fibrous nano-carbon. The method of claim 19, A method for producing fibrous nanocarbon, characterized in that the respective conditions of the first gas supplying step, the carbon raw material supplying step, and the second gas supplying step are controlled independently of each other. The method of claim 25, The condition is a temperature, pressure, time, and a gas atmosphere, characterized in that the manufacturing method of the fibrous nanocarbon. The method of claim 19, Fibrous nano by contacting the catalyst and the carbon raw material at a temperature of 300 ° C to 1300 ° C for a predetermined time in a mixed gas of hydrogen and inert gas (hydrogen partial pressure 0% to 90%) under a pressure of 0.1 to 25 atmospheres. Method for producing fibrous nanocarbon, characterized in that to produce carbon. The method of claim 19, In at least one of the first gas supplying step and the carbon raw material supplying step, the catalytic component of the fluid for both catalysts is simultaneously metallized and refined by the reducing action of the reducing gas. Manufacturing method. The method of claim 28, A method for producing fibrous nanocarbon, characterized in that the diameter of the fibrous nanocarbon obtained is controlled by controlling the particle diameter of the metal catalyst when the metal catalyst of the catalyst mixed fluid is made fine. The method of claim 19, The second gas supply process forms a region having a high flow velocity at a local portion of the fluidized bed, and promotes miniaturization and wear of the catalyst mixed fluid by collision between the catalyst mixed fluid particles or collision of the particles with the wall surface. Method for producing fibrous nanocarbon. The method of claim 30, A method of producing fibrous nanocarbon, characterized by forming a region having a high flow rate in the fluidized bed below the fluidized bed. The method of claim 30, A method for producing fibrous nanocarbon, characterized by forming a region having a high flow rate by blowing a high velocity gas into the fluidized bed. The method of claim 32, And dispersing the particles scattered from the fluidized bed into the fluidized gas and supplying the particles into the fluidized bed again. The method of claim 19, Method for producing fibrous nanocarbon, characterized in that the separated fibrous nanocarbon from the carrier or the catalyst. A manufacturing apparatus used for carrying out the method for producing fibrous nanocarbon according to claim 19, A fluidized bed reactor filled with the combined catalyst fluid material and having a heating means for heating the interior thereof; First gas supply means for supplying the reducing gas into the fluidized bed reactor, Carbon raw material supply means for supplying the carbon raw material in a gas state into the fluidized bed reactor; Second gas supply means for supplying the gas containing no carbon into the fluidized bed reactor, and A discharge line for discharging gas and fugitive particles from the fluidized bed reactor, The fluidized bed portion of the fluidized bed reactor has a high speed flow portion and a low speed flow portion, Apparatus for producing fibrous nanocarbon, characterized in that the impingement portion in the high-speed flow portion. 36. The method of claim 35 wherein And a recovery means for recovering the scattering particles in the discharge line. delete delete 36. The method of claim 35 wherein An apparatus for producing fibrous nanocarbon, characterized in that a high speed gas blowing means is provided in the fluidized bed reactor to blow gas at high speed. The method of claim 39, An apparatus for producing fibrous nanocarbon, characterized in that the recovered particles are accompanied when the gas is blown at high speed. A manufacturing apparatus used for carrying out the method for producing fibrous nanocarbon according to claim 19, A fluidized bed reactor filled with the combined catalyst fluid material and having a heating means for heating the interior thereof; First gas supply means for supplying the reducing gas into the fluidized bed reactor, Carbon raw material supply means for supplying the carbon raw material in a gas state into the fluidized bed reactor; Second gas supply means for supplying the gas containing no carbon into the fluidized bed reactor, and A discharge line for discharging gas and fugitive particles from the fluidized bed reactor, In addition to forming first, second and third flow chambers in which the fluid can flow, the fluidized bed reactor, Connecting the first gas supply means to the first flow chamber, Connecting the carbon raw material supply means to the second flow chamber, Apparatus for producing fibrous nanocarbon, characterized in that for connecting the second gas supply means to the third flow chamber. A manufacturing apparatus used for carrying out the method for producing fibrous nanocarbon according to claim 19, A fluidized bed reactor filled with the combined catalyst fluid material and having a heating means for heating the interior thereof; First gas supply means for supplying the reducing gas into the fluidized bed reactor, Carbon raw material supply means for supplying the carbon raw material in a gas state into the fluidized bed reactor; Second gas supply means for supplying the gas containing no carbon into the fluidized bed reactor, and A discharge line for discharging gas and fugitive particles from the fluidized bed reactor, In addition to forming the first and second flow chambers in which the fluid can flow, the fluidized bed reactor, Install a separate fluidized bed reactor different from the fluidized bed reactor as a third fluidized chamber, A transfer means for transferring a fluid from the second flow chamber to the third flow chamber, Connecting the first gas supply means to the first flow chamber, Connecting the carbon raw material supply means to the second flow chamber, Apparatus for producing fibrous nanocarbon, characterized in that for connecting the second gas supply means to the third flow chamber. A manufacturing apparatus used for carrying out the method for producing fibrous nanocarbon according to claim 19, A first fluidized bed reactor having the catalyst mixed fluid filled therein and having heating means for heating the interior and first gas supply means for supplying a reducing gas therein, A second fluidized bed reactor having a conveying means for conveying the fluid from the first fluidized bed reactor and having a carbon raw material supply means for supplying the carbon raw material in a gas state therein; A third fluidized bed reactor having conveying means for conveying the fluid and the reaction product from the second fluidized bed reactor, and having a second gas supply means for supplying the gas containing no carbon therein, and Apparatus for producing fibrous nanocarbon, characterized in that it comprises a discharge line for discharging gas and fugitive particles from the third fluidized bed reactor. The method of claim 43, Apparatus for producing fibrous nanocarbon, comprising a plurality of the first fluidized bed reactor. The method of claim 43, Apparatus for producing fibrous nanocarbon, comprising a plurality of the second fluidized bed reactor. The method of claim 43, Apparatus for producing fibrous nanocarbon, comprising a plurality of the third fluidized bed reactor. The method according to any one of claims 35, 36 and 39-46, Apparatus for producing fibrous nanocarbon, characterized in that the average particle diameter of the combined catalyst fluid is 0.2 to 20 mm. The method according to any one of claims 35, 36 and 39-46, An apparatus for producing fibrous nanocarbon, wherein the catalyst-compatible fluid includes the catalyst on the surface of the carrier or aggregates thereof. The method according to any one of claims 35, 36 and 39-46, Apparatus for producing fibrous nanocarbon, characterized in that the carrier of the mixed catalyst fluid is selected from carbon black, alumina, silica, silica sand and aluminosilicate. The method according to any one of claims 35, 36 and 39-46, An apparatus for producing fibrous nanocarbon, wherein the metal catalyst of the mixed catalyst fluid is any one of Fe, Ni, Co, Cu, and Mo, or a mixture of two or more thereof. The method according to any one of claims 35, 36 and 39-46, The flow rate in the fluidized bed is 0.02 to 2m / s device for producing fibrous nanocarbon, characterized in that. The method according to any one of claims 35, 36 and 39-46, Fibrous nano by contacting the catalyst and the carbon raw material at a temperature of 300 ° C to 1300 ° C for a predetermined time in a mixed gas of hydrogen and an inert gas (hydrogen partial pressure 0% to 90%) under a pressure of 0.1 to 25 atmospheres. Apparatus for producing fibrous nanocarbon, characterized in that to produce carbon. delete

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