JP4175182B2 - Carbonaceous fine fiber - Google Patents

Carbonaceous fine fiber Download PDF

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Publication number
JP4175182B2
JP4175182B2 JP2003158233A JP2003158233A JP4175182B2 JP 4175182 B2 JP4175182 B2 JP 4175182B2 JP 2003158233 A JP2003158233 A JP 2003158233A JP 2003158233 A JP2003158233 A JP 2003158233A JP 4175182 B2 JP4175182 B2 JP 4175182B2
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Prior art keywords
carbonaceous fine
fiber
fine fibrous
diameter
fibrous body
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JP2004360099A (en
Inventor
修七 吉村
猛 柏木
秀彦 秋元
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三菱化学エンジニアリング株式会社
三菱化学株式会社
株式会社島津製作所
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a carbonaceous fine fibrous body, and more particularly to a fishbone-shaped carbonaceous fine fibrous body. Specifically, the present invention relates to a carbonaceous fine fibrous body that can be produced by reacting a carbon source gas in the presence of a catalyst.
[0002]
[Prior art]
Conventionally, exhaust gas such as carbon dioxide, hydrogen, and biogas (gas mainly composed of carbon dioxide (CO 2 ) and methane (CH 4 )) is collected, and this is reacted as a carbon source in the presence of a catalyst. Thus, there is known a method for immobilizing the carbonaceous product (Japanese Patent Laid-Open Nos. 11-29314 and 11-322315). According to this method, it has been confirmed that a carbonaceous fine hollow fiber body called a carbon nanotube can be obtained as a carbonaceous product. Carbon nanotubes are also known to be obtained by subjecting a carbon source material such as hydrocarbons to a gas phase reaction in the presence of a catalyst at a high temperature (Japanese Patent Publication No. 3-64606, Japanese Patent Publication No. 3-77288). Issue gazette).
[0003]
The carbonaceous fine fibrous material represented by carbon nanotubes produced in this way has attracted particular attention as a new material in recent years due to its excellent properties such as extremely high conductivity compared to conventional carbon materials. ing.
[0004]
A fishbone type is known as one type of carbonaceous fine fiber. When this fishbone type carbonaceous fine fiber is observed with a transmission electron microscope (TEM), it is observed as an image as shown in FIG. This carbonaceous fine fibrous body 61 is formed by coaxially connecting a large number of hollow cone-shaped bone tips 62 made of truncated tapered graphite as shown in FIG. 1 (b) as shown in FIG. 1 (c). . The diameter D of the fishbone type carbonaceous fine fibrous body 61 is the same as the maximum diameter D of the bone tip 62. The minimum diameter d of the bone tip 62 corresponds to the minimum inner diameter (diameter) of the inner diameter of the carbonaceous fine fibrous body 1. The surface interval t (002) between the bone tips 62 and 62 can also be measured by X-ray diffraction (XRD), and the interval is usually 3.4 to 3.6 angstroms (Å). The opening angle of the bone tip 62 (the crossing angle θ between the central axis of the carbonaceous fine fibrous body 1 and the side peripheral surface of the bone tip 62) can be measured by TEM.
[0005]
As a conventionally known fishbone type carbonaceous fine fibrous material, for example, D is about 50 to 200 nm and d / D is about 0.6 to 0.7 nm (GSI Creos Technology Co., Ltd.). (According to material).
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 11-29314 [Patent Document 2]
JP 11-322315 A [Patent Document 3]
Japanese Patent Publication No. 3-64606 [Patent Document 4]
Japanese Examined Patent Publication No. 3-77288 [0007]
[Problems to be solved by the invention]
An object of this invention is to provide the carbonaceous fine fiber body which is excellent in kneadability with resin, and is excellent in electroconductivity.
[0008]
[Means for Solving the Problems]
The carbonaceous fine fibrous body of the present invention (Claim 1) has a carbonaceous fine fibrous structure in which the crystal structure of graphite has a fishbone (fishbone-like) arrangement structure in the fiber axis direction in a transmission electron microscope (TEM) image. A fibrous body having an angle of 5 to 80 degrees with respect to the fiber axis, and the inner diameter of the hollow cavity (the diameter of the smallest diameter of the cavity observed by TEM). ) The ratio d / D between d and the diameter D of the fiber observed by TEM is 0.05 to 0.3 .
[0009]
The reason why the carbonaceous fine fibrous body of the present invention is excellent in kneadability with resin and electrical conductivity is that the unevenness formed by the joint interval between bone tips on the side surface of the fibrous body, This is probably because the surface spacing has a positive effect.
The carbonaceous fine fibrous body according to the present invention (Claim 12) has a carbonaceous fine fibrous structure in which the crystal structure of graphite has a fishbone (fishbone-like) arrangement structure in the fiber axis direction in a transmission electron microscope (TEM) image. A fibrous body having an angle of 5 to 80 ° with respect to the fiber axis, and the innermost diameter of the hollow cavity (the diameter of the smallest diameter of the cavity observed by TEM) ) The ratio d / D between d and the diameter D of the fiber observed by TEM is 0.5 or less, and is produced using a carbon source gas composed of methane and carbon dioxide as a raw material in the presence of a catalyst. It is characterized by.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0011]
The carbonaceous fine fibrous material of the present invention is of the fishbone type shown in FIG.
[0012]
The bone tip 62 of the fishbone type carbonaceous fine fibrous body is usually a hollow truncated taper as described above, and the carbonaceous fine fibrous body is hollow having a through-hole penetrating in the longitudinal direction. . However, in the present invention, the bone tip 62 may have a non-truncated cone shape (Jinkasa shape). That is, d = 0 may be used in FIGS. In this case, the carbonaceous fine fibrous body does not have a through hole.
[0013]
In the present invention, the angle θ of FIG. 1C measured by the TEM image, that is, the crossing angle between the axial direction A of the fibrous body and the side peripheral surface of the tapered bone tip 62 is preferably 5 to 80 °. 10 to 75 °, particularly preferably 20 to 60 °. The side peripheral surface of the bone tip 62 is made of a graphite surface. It is considered that when the angle θ is 5 to 80 °, moderate irregularities are formed on the outer peripheral surface of the fibrous body, and the kneadability between the fibrous body and the resin is improved. In addition, when the angle θ is 5 to 80 °, it is considered that the gap between the bone tips 62 is moderately open toward the outer peripheral surface, and the familiarity with the resin is improved. In addition, the effect of improving the occlusion of hydrogen or lithium ions can be expected by opening the gap between the bone tips 62 to the side peripheral surface of the fibrous body. When the angle θ is 5 to 80 °, it is considered that the bonding strength between the bone tips is sufficiently high and the strength of the carbonaceous fine fibrous body is also large.
[0014]
If the distance between the surfaces is out of this range, it means that there is a defect in the graphite laminated structure of the tube, and the above characteristics may be impaired.
[0015]
In the carbonaceous fine fibrous body of the present invention, the ratio d / D between the innermost diameter d and the outer diameter D is 0.5 or less, preferably 0.01 to 0.5, particularly preferably 0.05 to 0.3. It is. When D is the same, the smaller the d / D, the smaller the carbonaceous fine fibrous body has the smaller inner diameter d of the bone tip 62, and the larger the amount of carbon per bone tip 62 is. .
[0016]
Therefore, the value of d / D is considered to have an influence on the balance between the strength and conductivity of the carbonaceous fine fibrous material. Further, when storing hydrogen and lithium, the stored amount per tube, and hence the product unit. This indicates the possibility that the amount of occlusion per volume increases.
[0017]
The outer diameter D of the carbonaceous fine fibrous body is preferably 10 to 200 nm, particularly preferably 15 to 100 nm. If D is less than 10 nm, the kneadability of the carbonaceous fine fibrous material to a resin or the like may be lowered, and production at a low cost becomes very difficult. On the other hand, if D is larger than 200 nm, the effect of improving the conductivity and strength of the carbonaceous fine fibrous body may be reduced.
[0018]
The carbonaceous fine fibrous material of the present invention is not particularly limited with respect to the production method, but is preferably produced by a gas phase reaction method in the presence of a catalyst. There is no particular limitation on the reactor for the gas phase reaction method, and the reactor can be manufactured by a reactor such as a fixed bed reactor or a fluidized bed reactor, but more preferably in the spouted bed reactor in terms of manufacturing efficiency. Introducing catalyst particles and a carbon source gas to form a spouted bed, producing a fine granular aggregate having an average particle size of 10 to 200 μm of carbonaceous fine fibrous material, and carbon in the fluidized bed reactor Introducing the source gas and the particulate aggregates taken out from the spouted bed reactor to grow the aggregates while forming a fluidized bed of the particulate aggregates. Can do.
[0019]
According to this manufacturing method, when the carbon source gas is reacted at a high temperature in the presence of the catalyst particles, a fine carbonaceous fibrous body is generated using the catalyst particles as a starting point for the reaction and grows into a fibrous form. A fine-grained aggregate in which fine fibrous bodies are formed is obtained.
[0020]
When the carbonaceous fine fibrous body is grown in a state where the aggregate particles are separated from each other by jet stirring, the carbonaceous fine fibrous body grows so as to surround the growth reaction portion.
[0021]
In this production method, in the initial stage of the growth reaction of the carbonaceous fine fibrous body in which the aggregate particles tend to solidify, the carbonaceous fine fibrous body is in a state where the aggregated particles are vigorously stirred and released from each other in the spouted bed. Grow.
[0022]
After that, the fine granular aggregates thus grown to a certain size in the spouted bed are transferred to the fluidized bed to further grow the particles, thereby efficiently growing the carbonaceous fine fibrous body. Can do.
[0023]
In the above production method, it is preferable to grow aggregate particles (hereinafter sometimes referred to as “primary particles”) in the spouted bed to an average particle size of 10 to 200 μm. When the average particle diameter of the primary particles is less than 10 μm, the primary particles are easily solidified when introduced into the fluidized bed and reacted. Performing the reaction in the spouted bed until the average particle size of the primary particles exceeds 200 μm is not preferable in terms of production efficiency because the amount of carbonaceous fine fibrous body produced per unit volume of the reactor is reduced. In the spouted bed, primary particles are grown to an average particle size of 10 to 200 μm and introduced into the fluidized bed to prevent solidification in the fluidized bed and to produce an efficient carbonaceous fine fibrous body. Can do.
[0024]
FIG. 2 is a system diagram showing an example of a method for producing the carbonaceous fine fibrous body.
[0025]
A raw material gas such as biogas is supplied to the pipe 1 and, if necessary, carbon dioxide (CO 2 ) gas is added and mixed from the pipe 2 so that methane and carbon dioxide gas have an approximately equimolar ratio. After this raw material gas is sent to the heat recovery heat exchanger 5 through the pipe 4 by the blower 3 and heated, it is further sent to the heating furnace 7 through the pipe 6 to be heated, and to the reactor through the pipe 8. Sent out. This pipe 8 is branched into three pipes 9, 10 and 11. The piping 9 is connected to the spouted bed reactor 30, the piping 10 is connected to the fluidized bed reactor 40, and the piping 11 is connected to the fluidized bed reactor 50. A pipe 12 for adding a catalyst is connected to the pipe 9.
[0026]
In the spouted bed reactor 30, the raw material gas introduced from the pipe 9 is jetted upward to form a spouted bed. The spouted bed reactor 30 is provided with a stirrer 13a for stirring the spouted bed.
[0027]
Particles (carbon fine powder, scattering catalyst, etc.) that have jumped out of the spouted bed in the spouted bed reactor 30 are guided together with the gas from the pipe 14 to the cyclone 15 and collected, and returned to the spouted bed reactor 30 through the pipe 16. It is. The fine particles that have passed through the cyclone 15 are introduced into the bag filter 18 from the pipe 17 together with the gas and collected. The particles collected by the bag filter 18 are returned to the spouted bed reactor 30 through a return pipe (not shown).
[0028]
The gas removed from the dust by the bag filter 18 is guided to the heat recovery heat exchanger 5 through the pipe 19, and is cooled by exchanging heat with the raw material gas. The gas cooled in this way is led from the pipe 20 to the condenser 21 and cooled. Thereby, water vapor in the gas is condensed and separated into water, and is discharged from the discharge line 22. The gas that has passed through the condenser 21 is led to the raw material supply pipe 1 through the pipe 23 and mixed with the raw material gas as a circulation return gas.
[0029]
A pipe 24 for separating the gas is branched from the pipe 23 and a part of the gas is led to the heating furnace 7 as a heating fuel gas. The pipe 24 functions as a purge line for taking out part of the gas flowing in the pipe 23 out of the system and preventing nitrogen from accumulating in the circulating gas.
[0030]
In order to cover the amount of heat necessary for heating, a part of the raw material gas is introduced into the heating furnace 7 through the pipe 25 and used as fuel gas. Reference numeral 26 denotes an air introduction pipe.
[0031]
A hydrogen separator 28 is connected to the pipe 4 on the downstream side of the blower 3 through a pipe 27. This hydrogen separator 28 is for preventing excessive accumulation of H 2 in the circulating gas.
[0032]
A valve 13 c is provided at the outlet 13 b at the top of the spouted bed reactor 30. A pipe 29 for transporting aggregate particles is connected to the outlet 13b. A gas supply pipe 31 branched from the pipe 6 is connected to the middle of the pipe 29, and the aggregate particles are air-flowed through the pipe 29 and guided to the cyclone 32.
[0033]
Aggregate particles collected in the cyclone 32 are introduced into the first fluidized bed reactor 40 via the pipe 33. A raw material gas is introduced from the pipe 10 into the lower part of the first fluidized bed reactor 40, and a fluidized bed of aggregate particles is formed in the reactor 40.
[0034]
Aggregate particles from the spouted bed reactor 30 react and grow in the fluidized bed. The grown particles are taken out by a screw type take-out machine 41 provided at the lower part of the reactor 40 and sent to the second fluidized bed reactor 50 through a pipe 42. The gas containing scattered particles from the first fluidized bed reactor 40 is guided to the cyclone 32 via the pipe 43 and collected, and returned to the reactor 40. The gas that has passed through the cyclone 32 is sent to the bag filter 18 through the pipe 44.
[0035]
In the second fluidized bed reactor 50, a raw material gas is supplied to the lower part thereof via the pipe 11, and a fluidized bed of aggregate particles is formed in the reactor 50.
[0036]
Aggregate particles from the first fluidized bed reactor 40 grow further by reaction in this fluidized bed, and the grown particles are taken out by a screw type take-out machine 51 provided at the lower part of the reactor 50 to obtain a product. Is discharged outside the system.
[0037]
The gas containing scattered particles from the second fluidized bed reactor 50 is guided to the cyclone 53 through the pipe 52 and collected, and returned to the reactor 50 through the pipe 54. The gas that has passed through the cyclone 53 is sent to the bag filter 18 through the pipe 55.
[0038]
In the present invention, in producing the carbonaceous fine fibrous body in this way, in the spouted bed reactor 30, fine aggregated particles (primary particles) of carbonaceous fine fibrous bodies having an average particle size of 10 to 200 μm. The primary particles having an average particle diameter of 10 to 200 μm are introduced into the fluidized bed reactor 40 and further grown.
[0039]
As described above, if the average particle size of the primary particles is less than 10 μm, solidification of the aggregate particles cannot be effectively prevented, and if it exceeds 200 μm, the production efficiency is lowered. The average particle size of primary particles produced in the spouted bed reactor 30 is particularly preferably 30 to 100 μm.
[0040]
The average particle diameter of the primary particles can be controlled by adjusting the reaction time (residence time) in the spouted bed reactor 30, the feed gas supply rate, the reaction temperature, and the like.
[0041]
The primary particles produced in the spouted bed reactor 30 are further grown in the first fluidized bed reactor 40 and the second fluidized bed reactor 50. The operating condition of the fluidized bed is that the average particle size of the secondary particles obtained by growing the primary particles in the fluidized bed in this way is not more than twice the average particle size of the primary particles, particularly 1.2 to 2 times. It is preferable to set the degree to be a standard. If the ratio between the average particle size of the secondary particles and the primary particles is less than 1.2, the growth of the secondary particles may be insufficient. If the ratio is more than 2 times, the residence time in the fluidized bed becomes excessively long. In addition, there is a possibility that a lump may be generated and the reaction efficiency may be reduced.
[0042]
In FIG. 2, the first fluidized bed reactor 40 and the second fluidized bed reactor 50 are provided in two stages as the fluidized bed reactor, but the fluidized bed reactor may be only one stage. Moreover, you may provide in three steps or more. By providing fluidized bed reactors in two or more stages and controlling the reaction conditions for each reactor, the production efficiency per unit volume of the reactor is increased, and the shape and physical properties of the obtained carbonaceous fine fiber are obtained. Can be easily adjusted to a desired range.
[0043]
The carbon source gas used in the reaction is not particularly limited as long as it is a carbon compound that can be introduced into the reaction system in the form of a gas. Preferably, a gas containing hydrocarbon and / or hydrogen and carbon oxide is used. Used. In particular, recovering and using process exhaust gas such as carbon dioxide, hydrogen, biogas, etc. as the carbon source gas is effective not only for reducing the manufacturing cost but also for maintaining the environment. When carbon dioxide and methane are used as the carbon source gas, if both are equimolar, methane and carbon dioxide can be immobilized as a carbonaceous product according to the following reaction formula.
CH 4 → C + 2H 2
2H 2 + CO 2 → C + 2H 2 O
[0044]
When a carbon oxide gas such as carbon dioxide or carbon monoxide is used as the carbon source gas, a reducing gas is used as the gas used for the reaction at the same time. The reducing gas as used herein refers to a gas that itself has reducing properties, or that gas decomposes in the reaction system to generate such reducing gases. In the above reaction formula, methane gas is a carbon source gas, and at the same time, it decomposes to generate hydrogen having reducibility, so it is a reducing gas. Examples of such reducing gas include hydrogen gas, and various hydrocarbon gases, that is, compounds such as methane, ethane, propane, and butane.
[0045]
On the other hand, the catalyst is not particularly limited in chemical composition and shape as long as it can efficiently generate a carbonaceous fine fibrous body from a carbon source gas. The compound is preferably used. As the catalyst, metal catalysts such as nickel, cobalt, and iron are particularly preferable. These metals may be used individually by 1 type, or may be used in combination of 2 or more types as appropriate. These metals can be used in the elemental state or in compounds such as oxides, hydroxides and carbonates. Further, these catalyst components may be supported on a carrier such as silica. In this case, the amount of the catalyst component supported on the support is preferably about 1 to 90% by weight with respect to the weight of the support. The particle shape of the catalyst is not particularly limited, and may be a generally known shape such as a spherical shape. In addition, when the particle size is, for example, a spherical shape, a particle having a diameter of about 1 to 20 μm is usually preferably used.
[0046]
The amount of such catalyst particles used is not particularly limited, but is such an amount that the carbon source gas introduced into the spouted bed reactor 30 is about 10 to 60 L / g · hr with respect to the amount of the catalyst active component. It is preferable that
[0047]
Moreover, reaction conditions are reaction temperature 400-800 degreeC normally for both the spouted bed reactor 30 and the fluidized bed reactors 40 and 50, Preferably they are 500 degreeC or more and less than 600 degreeC. If the reaction temperature is lower than this range, a sufficient reaction rate cannot be obtained, which is disadvantageous in terms of production efficiency of the carbonaceous fine fibrous body. If the reaction temperature is higher than this range, the once produced carbon and the reaction atmosphere gas Reaction may occur and the yield of the carbonaceous fine fibrous body may decrease, which is not preferable.
[0048]
The reaction pressure is not particularly limited as long as the carbon source gas as a raw material reacts efficiently, and preferably has a gauge pressure of 1 to 200 kPa, more preferably a gauge pressure of 3 to 50 kPa.
[0049]
The spouted bed reactor introduces catalyst particles and a carbon source gas from the bottom, and grows carbonaceous fine fibrous bodies while forming spouted beds of aggregate particles and catalyst particles in the reactor. It has a jet dispersion mechanism that allows the aggregated particles having a predetermined average particle diameter to grow as the carbonaceous fine fibrous body grows.
[0050]
Such a reaction using a spouted bed reactor and a fluidized bed reactor may be carried out continuously or batchwise. For example, both the spouted bed reactor and the fluidized bed reactor may be operated continuously, one of the spouted bed reactor and the fluidized bed reactor may be a continuous type, and the other may be a batch type. Both the reactor and the fluidized bed reactor may be operated in batch mode.
[0051]
Whether these reactors are batch-type or continuous-type depends on the reaction conditions (residence time, etc.) and the desired characteristics of the carbonaceous fine fiber (length and diameter of the carbonaceous fine fiber) In order to control the aggregate particle size, etc., it can be selected as appropriate, which is to produce a carbonaceous fine fibrous material having various characteristics by selecting an operation method in the same equipment. Means that you can.
[0052]
As shown in FIG. 2, the exhaust gas from the spouted bed reactor 30 and the fluidized bed reactors 40 and 50 collects fine powders such as carbon fines and catalyst particles by means of fine powder collecting means such as cyclones and bag filters. It can be mixed and mixed with the carbon source gas of the raw material, and the collected fine powder is preferably returned to the reactor. In this way, the exhaust gas is recovered and recycled for use as a carbonaceous fine fiber. The yield of the body can be increased.
[0053]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
[0054]
Example 1
According to the present invention, a carbonaceous fine fiber was produced according to the method shown in FIG. However, the second fluidized bed reactor 50 was not used, and the aggregate particles obtained in the first fluidized bed reactor 40 were used as products.
[0055]
As a raw material gas, a 1: 1 (molar ratio) mixed gas of carbon dioxide and methane is used, heated in the heat recovery heat exchanger 5 together with the circulating return gas from the pipe 23, and then heated in the heating furnace 7 to 600 ° C. The temperature was raised to.
[0056]
The heated gas is supplied to the spouted bed reactor 30 together with the supported catalyst particles, and while the spouted bed is formed in the spouted bed reactor 30, the aggregated particles of the carbonaceous fine fibrous body are grown. Aggregate particles were periodically taken out from the inside and introduced into the fluidized bed reactor 40. The average particle size of the primary particles was 45 μm. The reaction conditions in the spouted bed reactor 30 are a temperature of 550 ° C. and a gauge pressure of 40 kPa. The raw material gas (including the circulation return gas) was introduced at a rate of 30 L / g · hr with respect to the amount of the active catalyst component introduced into the spouted bed reactor 30.
[0057]
The primary particles having an average particle diameter of 45 μm obtained in the spouted bed reactor 30 are then further granulated and grown in contact with the raw material gas in the first fluidized bed reactor 40. The aggregated particles in the fluidized bed were taken out and cooled to obtain a product.
[0058]
The reaction conditions of the fluidized bed reactor 40 were a temperature of 550 ° C. and a gauge pressure of 40 kPa, and the raw material gas was introduced at a rate of 30 L / g · hr with respect to the amount of active catalyst components. Moreover, the average particle diameter of the secondary particles taken out from the fluidized bed reactor 40 was 65 μm.
[0059]
Table 1 shows the result of measuring the characteristics of the carbonaceous fine fibrous material thus produced by TEM.
[0060]
Further, 0.9 g of this carbonaceous fine fibrous body and 44.1 g of polycarbonate (Mitsubishi Engineering Plastics 7025A) as a synthetic resin (2% by weight of the carbonaceous fine fibrous body) were mixed with a kneading apparatus (Toyo Seiki). Kneading at 260 ° C. for 15 minutes. The obtained mixture was press-molded to obtain a plate-like molded body of 100 mm × 100 mm × 2 mm. Table 1 shows the measurement results of the conductivity (volume resistivity) of this molded product.
[0061]
Example 2
In Example 1, a carbonaceous fine fibrous material was produced in the same manner except that the reaction temperature was 500 ° C., and the same test was performed. The results are shown in Table 1.
[0062]
Example 3
In Example 1, except that the ratio of the raw material gas was 15 L / g · hr, a carbonaceous fine fibrous body was produced in the same manner, and the same test was performed. The results are shown in Table 1.
[0063]
Comparative Example 1
A similar test was performed on commercially available multi-walled carbon nanotubes. The results are shown in Table 1.
[0064]
[Table 1]
[0065]
【The invention's effect】
As described in detail above, according to the present invention, an inexpensive carbonaceous fine fibrous body excellent in kneadability, dispersibility, workability, and function development is provided.
[0066]
The carbonaceous fine fibrous material of the present invention is excellent in processability as compared with conventional carbon nanotubes, and can be kneaded in the same manner as conventional carbon black, and can be used in similar applications such as resins and rubbers. In addition, it can be industrially advantageously used as an additive for imparting functionality such as reinforcement of an elastomer or the like, coloring, imparting electrical conductivity, etc., and as a compounding component of pigment, ink, toner, etc. as a functional pigment.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of a carbonaceous fine fibrous body of the present invention.
FIG. 2 is a system diagram showing an example of a method for producing a carbonaceous fine fibrous body of the present invention.
[Explanation of symbols]
30 spouted bed reactor 40 first fluidized bed reactor 50 second fluidized bed reactor 61 carbonaceous fine fibrous body 62 bone chip

Claims (13)

  1. In the transmission electron microscope (TEM) image, the crystal structure of graphite is a carbonaceous fine fibrous body having a fishbone (fishbone-like) arrangement structure in the fiber axis direction,
    The angle of the graphite surface is 5 to 80 ° with respect to the fiber axis,
    The ratio d / D between the innermost diameter of the hollow cavity (the diameter of the smallest diameter of the cavity observed by TEM) d and the diameter D of the fiber observed by TEM is 0.05 to 0.3 . A carbonaceous fine fibrous material characterized by being.
  2.   2. The carbonaceous fine fiber body according to claim 1, wherein an angle of the graphite surface is 10 to 75 [deg.] With respect to the fiber axis.
  3.   3. The carbonaceous fine fiber body according to claim 2, wherein the angle of the graphite surface is 20 to 60 [deg.] With respect to the fiber axis.
  4. The carbonaceous fine fibrous body according to any one of claims 1 to 3, wherein the ratio d / D is 0.1 to 0.2 .
  5.   The carbonaceous fine fibrous body according to any one of claims 1 to 4, wherein the fiber has a diameter D of 10 to 200 nm.
  6.   6. The carbonaceous fine fiber body according to claim 5, wherein the fiber has a diameter D of 15 to 100 nm.
  7.   The carbonaceous fine fibrous body according to any one of claims 1 to 6, wherein the carbonaceous fine fibrous body is produced using a carbon source gas as a raw material in the presence of a catalyst.
  8.   8. The carbonaceous fine fibrous body according to claim 7, wherein the carbonaceous fine fibrous body is produced using hydrocarbon and / or hydrogen and carbon oxide as the carbon source gas.
  9.   The carbonaceous fine fiber body according to claim 8, wherein the carbon oxide is carbon monoxide and / or carbon dioxide.
  10.   The carbonaceous fine fiber body according to claim 9, wherein the hydrocarbon and / or hydrogen is methane and / or hydrogen.
  11.   The carbonaceous fine fibrous body according to any one of claims 7 to 10, wherein the carbon source gas fed as a raw material is methane and carbon dioxide.
  12. In the transmission electron microscope (TEM) image, the crystal structure of graphite is a carbonaceous fine fibrous body having a fishbone (fishbone-like) arrangement structure in the fiber axis direction,
    The angle of the graphite surface is 5 to 80 ° with respect to the fiber axis,
    The ratio d / D between the innermost diameter of the hollow cavity (the diameter of the smallest diameter of the cavity observed by TEM) d and the diameter D of the fiber observed by TEM is 0.5 or less,
    A carbonaceous fine fiber produced by using a carbon source gas composed of methane and carbon dioxide as a raw material in the presence of a catalyst.
  13. The carbonaceous fine fiber body according to claim 12, wherein the fiber has a diameter D of 10 to 200 nm.
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