JP2014189432A - Manufacturing installation of fibrous carbon material and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing installation of a fibrous carbon material which can produce a desired fibrous carbon material stably and is superior in reliability.SOLUTION: A manufacturing installation of a fibrous carbon material comprises: a reaction part contacting sediment of catalyst support, which is particle substrate supporting catalyst, with reactant gas while heating, and producing the fibrous carbon material on the surface of the catalyst support; heating means heating the catalyst support in the reaction part; a gas supply passage supplying the reactant gas to the reaction part; and a gas discharge passage discharging the gas in the reaction part. In the reaction part, the reactant gas is supplied between the catalyst support in the sediment of the particle catalyst support.

Description

  The present invention relates to a manufacturing apparatus and a manufacturing method for a fibrous carbon material.

In recent years, research on fibrous carbon materials such as carbon nanofibers, carbon nanotubes, and carbon nanocoils has been underway. The fibrous carbon material is used as an electrode material for fuel cells, capacitors, and lithium batteries, for example.
The fibrous carbon material is produced by an atmospheric pressure chemical vapor deposition (CVD) method using an apparatus (fluidized bed) in which predetermined particles are flowed. For example, in Patent Documents 1 and 2, catalyst particles and a carbon raw material are introduced into an apparatus (fluidized bed) in which predetermined particles are flowed to produce a fibrous carbon material. A method of collecting from above has been proposed. Patent Document 3 proposes a method for producing a fibrous carbon material by introducing a carbon raw material into an apparatus (fluidized bed) in which catalyst-carrying particles are fluidized.

JP-A-1-260019 JP 2004-75457 A Japanese National Patent Publication No. 4-504445

However, in the methods described in Patent Documents 1 and 2, since the catalyst particles are blown up and collected together with the fibrous carbon material, it is difficult to control the time during which the catalyst particles stay in the fluidized bed. It has been difficult to stably obtain a fibrous carbon material having properties (particularly, fiber length).
Further, in the technique described in Patent Document 3, there are many physical contacts between the catalyst carriers, such as the catalyst carriers colliding with each other or the catalyst carrier colliding with the inner wall of the apparatus. For this reason, the growth of the fibrous carbon material on the surface of the catalyst carrier may be disturbed or hindered. As a result, it has been difficult to stably obtain a desired fibrous carbon material.

  Then, an object of this invention is to provide the manufacturing apparatus and manufacturing method of the fibrous carbon material excellent in the reliability which can obtain a desired fibrous carbon material stably.

The present invention is as follows.
(1) a reaction part for producing a fibrous carbon material on the surface of the catalyst carrier by heating a catalyst carrier deposit formed by supporting the catalyst on a particulate base material while contacting the reactant gas while heating;
Heating means for heating the catalyst carrier deposit in the reaction section;
A gas supply channel for supplying the reaction gas to the reaction section;
A gas discharge passage for discharging the gas in the reaction section;
With
An apparatus for producing a fibrous carbon material, wherein a reaction gas is supplied between catalyst supports in a deposit of a catalyst support in a reaction section.

(2) Furthermore,
A support member for supporting the deposit of the catalyst carrier;
A carry-in path for carrying the support member supporting the catalyst carrier deposit into the reaction section;
An unloading path for unloading the support member supporting the deposit of the catalyst carrier having the fibrous carbon material formed on the surface from the reaction section;
With
The support member can be sequentially transported to the reaction section, and the loading path, the reaction section, and the unloading path are arranged in this order in the horizontal direction.
The support member is
A recess for storing the deposit of the catalyst carrier;
A first partition that separates the carry-in path and the recess in the reaction section;
A second partition that separates the carry-out path and the recess in the reaction section;
A third partition that separates the gas supply channel and the recess in the reaction section;
A fourth partition that separates the gas discharge channel and the recess in the reaction section;
The third partition wall has a plurality of gas supply holes through which the gas supply flow path and the recess are communicated in the reaction section, the catalyst support is not passed, and the reaction gas is passed.
(4) The apparatus for producing a fibrous carbon material according to (1), wherein the fourth partition wall has a plurality of gas discharge holes through which the gas discharge channel and the recess are communicated in the reaction section, the catalyst support is not passed, and the gas is passed.

(3) The loading path and the unloading path are arranged on substantially the same straight line,
The gas supply channel and the gas discharge channel are arranged on substantially the same straight line,
(2) The apparatus for producing a fibrous carbon material according to (2), wherein the carry-in path and the carry-out path, the gas supply flow path, and the gas discharge flow path are arranged so as to intersect each other substantially perpendicularly.

(4) Furthermore,
In the vicinity of the entrance of the carry-in path, a first seal member for sealing between the inner wall of the carry-in path and the first partition, and preventing intrusion of outside air from the carry-in path to the reaction part;
In the vicinity of the outlet of the carry-out path, a second seal member for sealing between the inner wall of the carry-out path and the second partition wall and preventing intrusion of outside air from the carry-out path to the reaction section;
An apparatus for producing a fibrous carbon material according to (2) or (3).

(5) Furthermore,
A first inert gas introduction flow path provided on the downstream side of the first seal member of the carry-in path to replace the atmosphere in the carry-in path with an inert gas;
A second inert gas introduction flow path provided on the upstream side of the second seal member of the carry-out path for replacing the atmosphere in the carry-out path with an inert gas;
An apparatus for producing a fibrous carbon material according to any one of (2) to (4).

(6) The catalyst carrier is an apparatus for producing a fibrous carbon material according to any one of (1) to (5), wherein the particle size is 0.1 to 10 mm.
(7) In the catalyst carrier, the catalyst is made of any one of the fibrous carbon materials (1) to (6) supported on the surface of a particulate base material having a surface roughness Ra of 0.1 to 10 μm. manufacturing device.
(8) The apparatus for producing a fibrous carbon material according to any one of (1) to (7), wherein the catalyst includes at least one selected from the group consisting of Fe, In, Sn, and C.

(9) While heating the catalyst support deposit formed by supporting the catalyst on the particulate substrate, the reaction gas is supplied between the catalyst supports in the catalyst support deposit, A method for producing a fibrous carbon material, comprising producing a fibrous carbon material on a surface.

(10) The method for producing a fibrous carbon material according to (9), wherein the time for heating the catalyst support deposit is 5 to 90 minutes.
(11) The method for producing a fibrous carbon material according to (9) or (10), wherein the catalyst includes at least one selected from the group consisting of Fe, In, Sn, and C.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing apparatus and manufacturing method of the fibrous carbon material excellent in the reliability which can obtain a desired fibrous carbon material stably can be provided.

It is a schematic block diagram of the manufacturing apparatus of the fibrous carbon material which concerns on Embodiment 1 of this invention. It is AA sectional drawing of FIG. It is BB sectional drawing of FIG. It is a schematic block diagram which shows the state which set the boat to the reaction tube in the manufacturing apparatus of FIG. It is a schematic block diagram which shows the state which carries in and carries out the boat in the manufacturing apparatus of FIG. It is a schematic block diagram which shows the state after inserting and carrying out the boat in the manufacturing apparatus of FIG. It is a schematic block diagram which shows the state which removes the dirt in the reaction tube of the manufacturing apparatus of FIG. It is a schematic block diagram which shows another form of the manufacturing apparatus of FIG. It is a schematic block diagram of the manufacturing apparatus of the fibrous carbon material which concerns on Embodiment 2 of this invention. It is a schematic block diagram of the manufacturing apparatus of the fibrous carbon material which concerns on Embodiment 3 of this invention. It is CC sectional drawing of FIG. It is a schematic block diagram of the manufacturing apparatus of the fibrous carbon material which concerns on Embodiment 4 of this invention.

  The present invention relates to a production apparatus for producing a fibrous carbon material by an atmospheric pressure CVD method, and supplies a reaction gas into a deposit (fixed layer) of a heated particulate catalyst carrier. Examples of the fibrous carbon material include carbon nanofibers, carbon nanotubes, and carbon nanocoils.

  That is, the apparatus for producing a fibrous carbon material according to the present invention brings a catalyst carrier-supported deposit formed by supporting a catalyst on a particulate base material into contact with a reaction gas while heating, so that the surface of the catalyst carrier is fibrous. A reaction section for generating a carbon material, a heating means for heating the deposit of the catalyst carrier in the reaction section, a gas supply passage for supplying a reaction gas to the reaction section, and a gas discharge passage for discharging the gas in the reaction section And comprising. In the reaction section, a reaction gas is supplied between the catalyst supports in the deposit of the particulate catalyst support.

In the present invention, the reaction gas is supplied to the gaps between the particulate catalyst support formed in the deposit (fixed layer) without causing the catalyst support to flow almost efficiently, so that the reaction can be efficiently performed inside the deposit. Fibrous carbon materials can be produced.
In the production of fibrous carbon material using a fixed bed where the catalyst carrier hardly moves, compared to the production of fibrous carbon material using a conventional fluidized bed, the collision of the catalyst carriers and the catalyst carrier device There is very little physical contact of the catalyst carrier, such as colliding with the inner wall. Therefore, the physical contact of the catalyst carrier does not disturb or prevent the growth of the fibrous carbon material on the surface of the catalyst carrier. In addition, the variation in reaction time that occurs when using a device in which catalyst particles are blown upward together with the fibrous carbon material in a fluidized bed is recovered.
As a result, a desired fibrous carbon material can be stably produced, and the reliability for manufacturing the fibrous carbon material can be enhanced.

  In particular, in the case of carbon nanocoils, when the catalyst support flows and collides with the wall surface of the reaction part or the adjacent catalyst support, growth of the carbon nanocoils is suppressed in that portion, and the productivity tends to decrease. In the case of producing carbon nanocoils, the use of the apparatus of the present invention can significantly improve the reliability and productivity.

The reaction gas flowing through the reaction section needs to have a flow rate such that the catalyst carrier hardly flows, i.e., maintains the state where the catalyst carrier is deposited (fixed layer). The particle diameter and mass of the catalyst carrier also contribute to the ease of reaction gas flow in the fixed bed and the maintenance of the fixed bed. Further, as the fibrous carbon grows on the surface of the catalyst carrier, the reaction gas passing between the catalyst carriers becomes difficult to flow. In consideration of the above points, it is important to appropriately determine the particle diameter and mass of the catalyst carrier and the flow rate of the reaction gas.
As the fibrous carbon material grows, it becomes difficult for the reaction gas to flow through the deposit. By detecting the gas pressure on the upstream side (reaction gas introduction side), the degree of growth of the fibrous carbon material is monitored. Further, it is possible to prevent the space between the catalyst carriers from being blocked with the grown fibrous carbon material.

  A large amount of fibrous carbon material can be produced with the catalyst carrier deposited in a compact space, and the productivity of the fibrous carbon material can be increased. Among the fibrous carbon materials, the effect of improving the productivity is remarkably obtained particularly when producing carbon nanocoils that require a long reaction time of about 5 to 90 minutes.

Hereinafter, conditions for producing the carbon nanocoil will be described.
The material of the particulate base material is preferably alumina, silica, silicon, or zirconia.
The particulate substrate preferably has a surface roughness Ra of 0.1 to 10 μm. When the surface roughness Ra of the particulate base material is 0.1 μm or more, the catalyst can be stably supported on the surface of the particulate base material. When the surface roughness Ra of the particulate base material is 10 μm or less, the catalyst is easily supported uniformly on the surface of the particulate base material.

  The catalyst preferably contains at least one selected from the group consisting of Fe, In, Sn, and C, and more preferably contains Fe and C and at least one of In and Sn. The catalyst is, for example, alloy fine particles containing Fe, In, Sn, and C. The mixing ratio of the alloy fine particles is preferably the number of moles, Fe being 3, Sn being 0 to 2.0, In being 0 to 2.0, and C being 0.5 to 2.0. Here, the ratio of Sn to In is 0: 1 to 1: 0 in terms of moles. The mixing ratio of the alloy fine particles is more preferably Fe of 3, Sn of 0.8 to 1.2, In of 0.8 to 1.2, and C of 0.8 to 1.5. Here, the ratio between Sn and In is 1: 0 to 0.2: 0.8 in terms of moles.

The upper limit of the particle size of the catalyst carrier is preferably 10 mm, more preferably 7 mm, and particularly preferably 5 mm. The lower limit of the particle size of the catalyst carrier is preferably 0.1 mm, more preferably 0.5 mm, and particularly preferably 1 mm. The range of the particle size of the catalyst support may be arbitrarily combined with the above upper limit and lower limit.
When the particle size of the catalyst support is 10 mm or less, a sufficient reaction surface area for generating the fibrous carbon material can be secured. When the particle size of the catalyst carrier is 0.1 mm or more, a sufficient space for the reaction gas to flow is formed between the particulate catalyst carriers inside the deposit.

  As the reaction gas, a material gas diluted with an inert gas is used. For example, a hydrocarbon gas such as acetylene is used as the source gas. For example, nitrogen, argon, or helium is used as the inert gas.

The heating temperature by the heating means is, for example, 300 to 900 ° C.
The reaction time is, for example, 5 to 90 minutes, preferably 15 to 60 minutes.
When the particle size of the catalyst support is about 0.1 to 10 mm, the average flow rate of the reaction gas supplied to the reaction section is 1 to 5 cm / s (flow rate at normal temperature), and the reaction time is 30 minutes, the length is 10 A carbon nanocoil of ˜100 μm is obtained.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments.

Embodiment 1
As shown in FIGS. 1-3, the manufacturing apparatus of this Embodiment is
A reaction tube 1 (reaction part) for bringing a deposit of the catalyst carrier 6 into contact with a reaction gas while heating to produce a fibrous carbon material on the surface of the catalyst carrier 6;
A heater 2 (heating means) disposed around the side surface of the reaction tube 1;
A gas supply pipe 3 (gas supply flow path) connected to one end of the reaction pipe 1 and introducing a reaction gas (CVD gas) into the reaction pipe 1;
A gas discharge pipe 4 (gas discharge flow path) that is connected to the other end of the reaction pipe 1 and discharges the exhaust gas in the reaction section;
Is provided.

The manufacturing apparatus of the present embodiment further includes
A boat 5 (support member) for storing the deposit of the catalyst carrier;
A loading pipe 12 (loading path) connected to one side surface of the central portion of the reaction tube 1 and carrying the boat 5 storing the catalyst carrier deposits into the reaction tube 1;
A catalyst carrier 18 having a fibrous carbon material formed on the surface in the reaction tube 1 connected to the other side surface (the side surface opposite to the side surface to which the carry-in tube 12 is connected) of the central portion of the reaction tube 1. An unloading tube 13 (unloading path) for unloading the boat 5 storing the deposits of
Is provided.
In the reaction tube 1, the reaction gas is supplied between the catalyst carriers 6 in a state where the deposits of the catalyst carriers 6 are stored in the boat 5.

The gas supply pipe 3 (gas supply flow path), the reaction pipe 1 (reaction unit), and the gas discharge pipe 4 (gas discharge flow path) are arranged on substantially the same straight line.
The gas supply pipe 3 is also used as a pipe for introducing an inert gas into the reaction pipe 1.

  The carry-in tube 12 is disposed so as to extend in a direction substantially perpendicular to the longitudinal direction of the reaction tube 1 from one side surface of the central portion of the reaction tube 1. The carry-out pipe 13 is arranged so as to extend in a direction substantially perpendicular to the longitudinal direction of the reaction tube 1 from the other side face (the side face opposite to the side face to which the carry-in pipe 12 is connected) of the central portion of the reaction pipe 1. The carry-in pipe 12 and the carry-out pipe 13 are arranged on substantially the same straight line. In order to sequentially transport the boat 5 to the central portion of the reaction tube 1, the carry-in tube 12, the central portion of the reaction tube 1, and the carry-out tube 13 are arranged in this order in the horizontal direction. The carry-in pipe 12 and the carry-out pipe 13 are arranged in a direction substantially perpendicular to the gas supply pipe 3 and the gas discharge pipe 4.

The reaction tube 1, the carry-in tube 12, and the carry-out tube 13 are all rectangular tubes. The boat 5 is slidable inside the carry-in tube, the central portion of the reaction tube 1, and the inside of the carry-out tube 8, and between the boat 5 and the carry-in tube, the central portion of the reaction tube 1, and the inner wall of the carry-out tube 8. A moderate gap is provided.
For the reaction tube 1, the carry-in tube 12, the carry-out tube, and the boat 5, for example, a material having excellent heat resistance such as quartz glass and ceramics is used.

The boat 5 has a recess 7 for storing deposits of the catalyst carrier 6 in the center, a first partition 10 for isolating the inside of the carry-in pipe 12 and the recess 7 in the reaction tube 1, and carrying out in the reaction tube 1. A second partition 11 that separates the inside of the tube 13 and the recess 7, a third partition 8 that isolates the interior of the gas supply tube 3 and the recess 7 in the reaction tube 1, and a gas discharge tube 4 in the reaction tube 1. It has the 4th partition 9 which isolates an inside and the recessed part 7. As shown in FIG. The third partition wall 8 has a plurality of gas supply holes 8a that allow the reaction gas to pass through the inside of the gas supply pipe 3 and the recess 7 in the reaction pipe 1 without passing through the catalyst carrier 6. The fourth partition wall 9 has a plurality of gas discharge holes 9a that allow the inside of the gas discharge pipe 4 and the recess 7 to communicate with each other in the reaction tube 1 without passing through the catalyst carrier 6 and through which the exhaust gas passes.
The 3rd partition 8 and the 4th partition 9 may be comprised with the member which has many slits, or a porous body.

In the vicinity of the entrance of the carry-in pipe 12, a first seal member 14 is provided for sealing between the inner wall of the carry-in pipe 12 and the boat 5 and preventing outside air from entering the reaction pipe 1 from the carry-in pipe 7. ing. In the vicinity of the outlet of the carry-out pipe 13, a second seal member 15 is provided for sealing between the inner wall of the carry-out pipe 13 and the boat 5 and preventing intrusion of outside air from the carry-out pipe 13 into the reaction pipe 1. ing. The first seal member 14 is provided in a frame shape so as to surround the inner wall of the carry-in pipe 12. The second seal member 15 is provided in a frame shape so as to surround the inner wall of the carry-out pipe 13.
For the first seal member 14 and the second seal member 15, for example, nitrile rubber, fluorine rubber or silicone rubber having excellent heat resistance is used.

  A first inert gas introduction pipe 16 (first inert gas introduction flow path) for replacing the atmosphere in the carry-in pipe 12 with an inert gas is connected downstream of the first seal member 14 of the carry-in pipe 12. Has been. A second inert gas introduction pipe 17 (second inert gas introduction flow path) for replacing the atmosphere in the carry-out pipe 13 with an inert gas is connected upstream of the second seal member 15 of the carry-out pipe 13. Has been. For example, nitrogen, argon, or helium is used as the inert gas.

  The inert gas introduced into the carry-in pipe 12 and the carry-out pipe 13 from the inert gas introduction pipes 16 and 17 is supplied to the reaction pipe 1 through a gap between the inner walls of the carry-in pipe 12 and the carry-out pipe 13 and the boat 5. It is used to prevent the reaction gas from entering the carry-in pipe 12 and the carry-out pipe 13 and to prevent air from entering from the outside. Most of them flow to the reaction tube 1, but the same gas as the inert gas used for the above raw material gas is used, and the flow rate is controlled to a certain minimum amount, thereby affecting the concentration of the raw material gas. You can avoid giving.

Hereinafter, the operation of the manufacturing apparatus of the present embodiment will be described.
As shown in FIG. 4, a boat 5 is set in a reaction tube 1 heated to a predetermined temperature, and a reaction gas is supplied into the reaction tube 1 in which the boat 5 is set. At this time, the reaction gas introduced from the reaction tube 1 is supplied into the deposit (between the particulate catalyst support 6) through the gas supply hole 8 a of the boat 5, and is fibrous on the surface of the catalyst support 6. A carbon material is formed. From the viewpoint of the dispersibility of the reaction gas, it is preferable to provide a large number of gas supply holes 8a.
In a state where the boat 5 is set in the reaction tube 1, the portion between the boat 5 inserted in the carry-in tube 12 and the inner wall of the carry-in tube 12 is sealed by the first seal member 14 into the carry-out tube 13. The inside of the carry-in pipe 12, the reaction pipe 1, and the carry-out pipe 13 up to the place where the space between the inserted boat 5 and the carry-out pipe 13 is sealed by the second seal member 15 is sealed.
In order to prevent the reaction gas in the reaction tube 1 from moving to the carry-in tube 12 and the carry-out tube 13 and contaminating the carry-in tube 12 and the carry-out tube 13 with the reaction gas, after the fibrous carbon material is produced, An inert gas is introduced from the gas supply pipe 3.

  As shown in FIG. 5, when the production of the fibrous carbon material is completed, the boat 5 is newly inserted from the entrance of the carry-in pipe 12. At this time, the boats 5 inserted into the carry-in pipe 12, the reaction section 1, and the carry-out pipe 13 are sequentially pushed forward. More specifically, the boat 5 that has been inserted into the carry-in tube 12 is set in the reaction tube 1. The boat 5 after producing the fibrous carbon material in the reaction tube 1 is pushed into the carry-out tube 13 and cooled in the carry-out tube 13. The boat 5 cooled in the carry-out pipe 13 is pushed out from the exit of the carry-out pipe 13.

  In the process of newly inserting the boat 5 from the inlet of the carry-in pipe 12 into the carry-in pipe 12 and discharging the boat 5 in the carry-out pipe 13 from the outlet of the carry-out pipe 13 to the outside as shown in FIG. 12 and the inside of the carry-out pipe 13 are lost. At this time, the introduction of the inert gas from the inert gas pipes 16 and 17 installed in the carry-in pipe 12 and the carry-out pipe 13 respectively suppresses the intrusion of air into the carry-in pipe 12 and the carry-out pipe 13. At the same time, by introducing an inert gas from the gas supply pipe 3 into the reaction tube 1, the intrusion of air into the reaction tube 1 is suppressed. Thereby, it is possible to prevent the fibrous carbon material formed on the surface of the catalyst carrier from being thermally decomposed in the presence of oxygen.

  The introduction of the inert gas from the inert gas introduction pipe 16 into the carry-in pipe 12 and the introduction of the inert gas from the inert gas introduction pipe 17 into the carry-out pipe 13 react in the carry-in pipe 12 and the carry-out pipe 13. A catalyst carrier 6 accommodated in the boat 5 in the carry-in pipe 12 and a catalyst carrier 18 having a fibrous carbon material formed on the surface, which is accommodated in the boat 5 in the carry-out pipe 13, enter the gas. Also, it has a role of preventing contamination with the reaction gas.

After the carry-in and carry-out processes are completed, as shown in FIG. 6, the next boat 5 is set in the reaction tube 1 in a heated state, and a fibrous carbon material is produced in the boat 5.
By repeatedly performing the steps of FIGS. 4 to 6, a fibrous carbon material can be continuously produced while the reaction tube 1 is heated.

In the production process of the fibrous carbon material, dirt such as carbide and tar adheres inside the reaction tube 1. As a method for removing this dirt, as shown in FIG. 7, a boat 5 ′ on which no catalyst carrier is placed is set in the reaction tube 1, and air is supplied from the gas supply tube 3 into the reaction tube 1 while heating the reaction tube 1. A method of burning and removing carbides and tars in the reaction tube 1 by flowing is mentioned.
With the reaction tube 1 heated, the boat 5 can be carried in and out, and the dirt in the reaction tube 1 can be removed, and it is not necessary to repeat heating and cooling of the reaction tube 1 alternately. Can be increased.

  Further, when the heating temperature of the reaction tube 1 is high, the boat 5 may not be sufficiently cooled, and the produced fibrous carbon material and the sealing members 14 and 15 may be thermally damaged. As a method of reducing this thermal damage, as shown in FIG. 8, instead of the carry-in pipe 12 and the carry-out pipe 22, a method using a carry-in pipe 22 and a carry-out pipe 23 in which the lengths of the pipes are longer than those can be given. It is done. If the seal member 14 is not thermally damaged, the carry-in tube 12 may be used as it is.

<< Embodiment 2 >>
As shown in FIG. 9, the manufacturing apparatus of the present embodiment
A columnar reaction vessel 31 (reaction unit) arranged so that its axial direction is substantially perpendicular to the horizontal plane;
A heater 32 (heating means) disposed around the side surface of the reaction vessel 31;
A gas supply pipe 33 (gas supply flow path) connected to the upper end surface of the reaction container 31 and introducing a reaction gas (CVD gas) into the reaction container 31;
A gas discharge pipe 34 (gas discharge flow path) connected to the lower end surface of the reaction vessel 31 for discharging the exhaust gas in the reaction vessel 31;
The reaction vessel 31 is arranged so that the surface direction is substantially perpendicular to the axial direction of the reaction vessel 31, and deposits of the catalyst carrier 6 are placed on the reaction vessel 31 and moved along the axial direction of the reaction vessel 31. Possible support plate 35;
Is provided.

The deposit on the catalyst carrier 6 is stably placed inside the reaction vessel 31 by the support plate 35 and the side portion of the reaction vessel 31. The support plate 35 has a plurality of gas supply holes 35a through which the reaction gas is passed from below without passing through the catalyst carrier 6. The support plate 35 and the side portion of the reaction vessel 31 have a role of supporting the deposit.
The gas supply pipe 33 is also used as a pipe for introducing an inert gas into the reaction unit 31.

The reaction vessel 31 has an upper opening (loading port) for carrying the deposit of the catalyst carrier 6 together with the support plate 35 into the reaction vessel 31 and an upper lid member (not shown) for closing the upper opening. Have
The reaction vessel 31 has, on its lower end surface, a lower opening (unloading port) and a lower opening for carrying the catalyst carrier deposit on which the fibrous carbon material is formed together with the support plate 35 from the reaction vessel 31 to the outside. A lower lid member (not shown) for closing.

For the reaction vessel 31 and the support plate 35, for example, a material having excellent heat resistance such as quartz glass and ceramics is used.
A support piece 36 for supporting the support plate 35 is provided in the reaction vessel 31. The support plate 35 can be fixed at a predetermined position in the reaction vessel 31 by placing the peripheral end portion of the disk-like support plate 35 on the support piece 36 protruding from the inner surface of the reaction vessel 31. . The support piece 35 is a recess provided in a side portion of the reaction vessel 31 when the catalyst carrier deposit formed with the fibrous carbon material is carried out together with the support plate 35 from the lower opening of the reaction vessel 31. It is provided so that it can be stored in (not shown).

Hereinafter, the operation of the manufacturing apparatus of the present embodiment will be described.
The upper cover member of the reaction vessel 31 is opened, and the catalyst carrier 6 is introduced from the upper opening. After closing the upper lid member, an inert gas is introduced into the reaction vessel 31 from the gas supply pipe 33, and the atmosphere in the reaction vessel 31 is replaced with the inert gas. For example, nitrogen, argon, or helium is used as the inert gas.
Thereafter, the reaction vessel 31 is heated to a predetermined temperature, and then the reaction gas is supplied from the gas supply pipe 33 to the reaction vessel 31. At this time, the reaction gas introduced from the lower part of the reaction vessel 31 is supplied into the deposit (between the particulate catalyst support 6) through the gas supply hole 35 a of the support plate 35, and the surface of the catalyst support 6. A fibrous carbon material is formed. From the viewpoint of the dispersibility of the reaction gas, it is preferable to provide a large number of holes 35a.
After producing the fibrous carbon material, an inert gas is introduced into the reaction vessel 31 through the gas supply pipe 33, the atmosphere in the reaction vessel 31 is replaced with the inert gas, and the reaction vessel 31 is cooled. After the reaction vessel 31 is cooled, a catalyst carrier having a fibrous carbon material formed on the surface together with the support plate 35 is carried out from the lower lid member of the reaction vessel 31.

  In the production process of the fibrous carbon material, dirt such as carbide and tar adheres inside the reaction vessel 31. As a method for removing the dirt, by flowing air from the gas supply pipe 33 into the reaction vessel 31 while heating the reaction vessel 31 without the catalyst carrier in the reaction vessel 31, carbides and tars in the reaction vessel 31 are obtained. The method of burning off is mentioned.

<< Embodiment 3 >>
As shown in FIGS. 10 and 11, the manufacturing apparatus of the present embodiment is
A columnar reaction vessel 41 (reaction unit) arranged so that the axial direction is substantially perpendicular to the horizontal plane;
A heater 42 (heating means) disposed around the side surface of the reaction vessel 41;
A gas supply pipe 43 (gas supply flow path) connected to the lower part of the side surface of the reaction vessel 41;
A gas discharge pipe 44 (gas discharge flow path) connected to the upper end surface of the reaction vessel 41;
A bottomed cylindrical support container 45 (support member) for storing a deposit of the particulate catalyst support,
An inlet (loading port) for introducing a support container 45 for storing a catalyst carrier deposit, and a catalyst carrier deposit on which a fibrous carbon material is formed, provided on the lower end surface of the reaction vessel 41. A lower opening 46 serving also as an outlet (carrying outlet) for taking out the supporting container 45 to be stored;
In the reaction vessel 41, an extension jack 48 for moving the support vessel 45 in the vertical direction along the axial direction of the reaction vessel 41;
A rotating device 51;
Is provided.

The gas supply pipe 43 is also used as a pipe for introducing an inert gas into the reaction vessel 41.
The support container 45 has a plurality of gas supply holes 45a at the bottom thereof that do not pass the catalyst carrier and allow the reaction gas to pass from below.

The rotating device 51 is
A first container 53 in which a support container 45 containing a catalyst carrier deposit or a support container 45 containing a catalyst carrier deposit having a fibrous carbon material formed on the surface thereof is collected;
A second compartment 54 for preheating the support container containing the catalyst carrier deposit;
A support vessel 45 containing a catalyst carrier deposit deposited in contact with the lower opening 46 of the reaction vessel 41 is carried into the reaction vessel 41, or a catalyst carrier having carbon nanocoils formed on the surface thereof. A third compartment 55 for carrying out a support container 45 containing body deposits from the reaction container 41;
A fourth section 56 for cooling the support container 45 carried out from the reaction container 41;
A turntable 52 having
A rotating shaft 52a for rotating the rotating table 52;
The support container 45 containing the catalyst carrier is carried into the first section 53 of the rotating device 51, or the support container 45 containing the catalyst carrier having the fibrous carbon material formed on the surface thereof is used as the first container of the rotating device 51. An inlet / outlet port 50 for recovery from the compartment 53; and a valve 57 for opening and closing the inlet / outlet port;
Is provided.

  The first to fourth sections 53 to 56 are each composed of four chambers for storing the support container 45, and are arranged on substantially the same circumference around the rotation shaft 52a. The rotary table 52 is rotated clockwise by the rotation shaft 52a, and the chamber can be moved every 90 degrees in the order of the first section 53, the second section 54, the third section 55, and the fourth section 56.

  For the reaction vessel 41 and the support vessel 45, a material having excellent heat resistance such as quartz glass and ceramics is used. Moreover, the material excellent in heat resistance like quartz glass and ceramics is used for the inner wall of four chambers which accommodate the support container 45 of the 1st-4th division in the rotation apparatus 51 at least.

Hereinafter, the operation of the manufacturing apparatus of the present embodiment will be described.
By opening the gate valve 57, the support container 45 storing the deposit of the catalyst carrier is carried into the chamber of the first section 53 of the turntable 52 through the entrance / exit 50. After being carried into the chamber of the first section 53, the gate valve 57 is closed, and the atmosphere in the rotating device 51 including the chamber in which the support container 45 is stored is replaced with an inert gas. For example, nitrogen, argon, or helium is used as the inert gas. The support container 45 conveyed from the first section 53 to the second section 54 is preheated. The support container 45 transported from the second section 54 to the third section 55 is carried into the reaction container 41 by the extension jack 48. At this time, the atmosphere in the reaction vessel 41 is replaced with an inert gas.

  After the support container 45 is carried into the reaction container 41, the reaction gas is supplied into the reaction container 41 from the gas supply pipe. At this time, the reaction gas introduced from the lower part of the reaction vessel 41 is supplied into the deposit (between the particulate catalyst carrier 6) through the gas supply hole 45 a of the support vessel 45, and the surface of the catalyst carrier 6. A fibrous carbon material is formed. From the viewpoint of the dispersibility of the reaction gas, it is preferable to provide a large number of holes 45a.

  After the fibrous carbon material is produced, an inert gas is introduced into the reaction vessel 41 from the gas supply pipe 43, and the atmosphere in the reaction vessel 41 is replaced with the inert gas. Thereafter, the support container 45 is returned to the chamber of the third section 55 of the rotating device 51 by the extension jack 48. The chamber in which the returned high-temperature support container 45 is accommodated is transported to the fourth section 56 and cooled therein while the fibrous carbon material is produced in the next support container 45. After the production process of the fibrous carbon material of the next support container 45 is completed, the chamber of the support container 45 cooled in the fourth section 56 is transferred to the first section 53, and the gate valve 57 is opened and recovered from the entrance / exit 50. Is done.

  In the manufacturing apparatus of the present embodiment, the reaction vessel 41 is heated by the heater 42, and the support vessel 45 storing the deposits of the catalyst carrier 6 can be continuously carried into the reaction vessel 41. , Improve productivity.

  In the production process of the fibrous carbon material, dirt such as carbide and tar adheres inside the reaction vessel 41. As a method of removing this dirt, as shown in FIG. 7, air is allowed to flow from the gas supply pipe 43 into the reaction vessel 41 while heating the reaction vessel 41 without carrying the support vessel 45 into the reaction vessel 41. A method of burning and removing carbides and tar in the reaction vessel 41 can be mentioned.

  With the reaction vessel 41 heated, the support vessel 45 can be carried in and out, and dirt in the reaction vessel 41 can be removed, and heating and cooling of the reaction vessel 41 do not need to be repeated alternately. Can be increased.

<< Embodiment 4 >>
As shown in FIG. 12, the manufacturing apparatus of the present embodiment is
A columnar reaction vessel 61 (reaction unit) arranged such that the axial direction is inclined with respect to a horizontal plane;
A heater 62 (heating means) disposed around the side surface of the reaction vessel 61;
A gas supply pipe 63 (gas supply flow path) connected to the upper part of the side surface of the reaction vessel 61;
A gas discharge pipe 64 (gas discharge flow path) connected to the upper end surface of the reaction vessel 61;
The reaction vessel 61 is arranged so that the surface direction is substantially perpendicular to the axial direction of the reaction vessel 61, and deposits of the catalyst carrier 6 are placed on the inside of the reaction vessel 61 along the axial direction of the reaction vessel 61. Movable support plate 65,
A rod 74 connected to the support plate 65 for moving the support plate 65 along the axial direction of the reaction vessel 61;
Is provided.

The catalyst carrier 6 can be stably placed in the reaction vessel 61 by the support plate 65 and the side portion of the reaction vessel 61. The support plate 65 and the side portion of the reaction vessel 61 have a role of supporting the deposit.
The support plate 65 has a plurality of gas supply holes 65a through which the reaction gas is passed from below without passing through the catalyst carrier 6.
The gas supply pipe 63 is also used as a pipe for introducing an inert gas into the reaction vessel 61.

The manufacturing apparatus of the present embodiment further includes
A carry-in port 69 provided in the upper part of the side surface of the reaction vessel 61 for introducing the deposit of the catalyst carrier 6;
A storage container 66 for storing the catalyst carrier;
A carry-in pipe 67 (carry-in path) connecting the container 66 and the carry-in port 69;
A valve 68 for opening and closing the carry-in pipe 67;
A carry-out port 73 provided at the lower part of the side surface of the reaction vessel 61 for taking out the deposit of the catalyst carrier on which the fibrous carbon material is formed;
A collection container 70 for cooling and collecting the fibrous carbon material;
An unloading pipe 72 (unloading path) connecting the container 70 and the unloading port 73;
A valve 71 for opening and closing the carry-out pipe 72;
Is provided.

  For the reaction container 61, the support container 65, the storage container 66, the recovery container 70, the carry-in pipe 67, and the carry-out pipe 72, materials having excellent heat resistance such as quartz glass and ceramics are used.

Hereinafter, the operation of the manufacturing apparatus of the present embodiment will be described.
The catalyst carrier 6 preheated in the storage container 66 in the inert gas atmosphere is put on the support plate 65 in the reaction container 61 in the inert gas atmosphere by opening the valve 68. After the catalyst carrier 6 is put into the reaction vessel 61, the valve 68 is closed.
As the support plate 65 moves to a predetermined position by the rod 74, the deposit on the catalyst carrier 6 moves to the central portion of the reaction vessel 61 (the portion surrounded by the heater). Thereafter, the reaction gas is supplied from the gas supply pipe 63 into the reaction vessel 61. At this time, the reaction gas introduced into the reaction vessel 61 is supplied into the deposit (between the particulate catalyst support 6) through the gas supply hole 65 a of the support plate 65, and is applied to the surface of the catalyst support 6. A fibrous carbon material is formed. From the viewpoint of the dispersibility of the reaction gas, it is preferable to provide a large number of holes 65a.

After producing the fibrous carbon material, an inert gas is introduced from the gas supply pipe, and the atmosphere in the reaction vessel 61 is replaced with the inert gas. As the support plate 65 moves to a predetermined position by the rod 74, the catalyst carrier 6 having a fibrous carbon material formed on the surface moves to the carry-out port 73. By opening the valve 71, the catalyst carrier 6 having a fibrous carbon material formed on the surface is carried out from the carry-out port 73 to the recovery container 70. In the collection container 70, the catalyst carrier 6 having a fibrous carbon material formed on the surface is cooled.
By repeating the above operation, a fibrous carbon material can be continuously produced while the reaction vessel 61 is heated.

  It is preferable that the axial direction of the reaction vessel 61 is inclined by 5 ° to 30 ° with respect to the horizontal direction. When the inclination angle is 5 ° or more, the catalyst carrier deposit in the reaction vessel 61 is easily moved from the carry-in port 69 side to the carry-out port 73 side. When the inclination angle is 30 ° or less, the catalyst carrier deposit in the storage container 66 can easily be moved into the reaction vessel 61 via the carry-in pipe 67, and the catalyst carrier deposit in the reaction vessel 61 can be moved. Can be easily moved to the collection container 70 via the carry-out port 73.

  In the production process of the fibrous carbon material, dirt such as carbide and tar adheres inside the reaction vessel 61. As a method for removing this dirt, the carbide in the reaction vessel 61 is flowed from the gas supply pipe 63 into the reaction vessel 61 while heating the reaction vessel 61 without carrying the catalyst carrier into the reaction vessel 61. And a method of burning and removing tar.

  The catalyst carrier 6 can be carried in and out and the dirt in the reaction vessel 61 can be removed while the reaction vessel 61 is heated, and it is not necessary to repeat heating and cooling of the reaction vessel 61 alternately. Can increase the sex.

DESCRIPTION OF SYMBOLS 1 Reaction tube 2, 32, 42, 62 Heater 3, 33, 43, 63 Gas supply tube 4, 34, 44, 64 Gas discharge tube 5 Boat 6 Catalyst support body 7 Recessed part 8 Third partition 9 Fourth partition 10 First Partition 11 Second partition 12, 22 Carry-in pipe 13, 23 Carry-out pipe 14 First seal member 15 Second seal member 16 First inert gas introduction pipe 17 Second inert gas introduction pipe 31, 41, 61 Reaction vessel 35, 65 support plate 45 support container 46 lower opening 48 telescopic jack 50 doorway 51 rotating device 52 rotary table 53 first section 54 second section 55 third section 56 fourth section 57 gate valve 66 storage container 67 carry-in pipe 68, 71 valve 69 Carry-in port 70 Recovery container 72 Carry-out pipe 73 Carry-out port

Claims (11)

A reaction part for generating a fibrous carbon material on the surface of the catalyst carrier by contacting a reaction gas while heating the catalyst carrier deposit formed by supporting the catalyst on the particulate substrate;
Heating means for heating the catalyst carrier deposit in the reaction section;
A gas supply channel for supplying the reaction gas to the reaction section;
A gas discharge passage for discharging the gas in the reaction section;
With
An apparatus for producing a fibrous carbon material, wherein a reaction gas is supplied between catalyst supports in a deposit of a catalyst support in a reaction section. further,
A support member for supporting the deposit of the catalyst carrier;
A carry-in path for carrying the support member supporting the catalyst carrier deposit into the reaction section;
An unloading path for unloading the support member supporting the deposit of the catalyst carrier having the fibrous carbon material formed on the surface from the reaction section;
With
The support member can be sequentially transported to the reaction section, and the loading path, the reaction section, and the unloading path are arranged in this order in the horizontal direction.
The support member is
A recess for storing the deposit of the catalyst carrier;
A first partition that separates the carry-in path and the recess in the reaction section;
A second partition that separates the carry-out path and the recess in the reaction section;
A third partition that separates the gas supply channel and the recess in the reaction section;
A fourth partition that separates the gas discharge channel and the recess in the reaction section;
The third partition wall has a plurality of gas supply holes through which the gas supply flow path and the recess are communicated in the reaction section, the catalyst support is not passed, and the reaction gas is passed.
The fourth partition wall has a plurality of gas discharge holes that allow the gas discharge passage and the recess to communicate with each other in the reaction section, not to pass through the catalyst carrier, and to pass through the gas.
The manufacturing apparatus of the fibrous carbon material of Claim 1. The loading path and the unloading path are arranged on substantially the same straight line,
The gas supply channel and the gas discharge channel are arranged on substantially the same straight line,
The carry-in path and the carry-out path, and the gas supply flow path and the gas discharge flow path are arranged so as to intersect each other substantially perpendicularly.
The manufacturing apparatus of the fibrous carbon material of Claim 2. further,
In the vicinity of the entrance of the carry-in path, a first seal member for sealing between the inner wall of the carry-in path and the first partition, and preventing intrusion of outside air from the carry-in path to the reaction part;
In the vicinity of the outlet of the carry-out path, a second seal member for sealing between the inner wall of the carry-out path and the second partition wall and preventing intrusion of outside air from the carry-out path to the reaction section;
Having
The manufacturing apparatus of the fibrous carbon material of Claim 2 or 3. further,
A first inert gas introduction flow path provided on the downstream side of the first seal member of the carry-in path to replace the atmosphere in the carry-in path with an inert gas;
A second inert gas introduction flow path provided on the upstream side of the second seal member of the carry-out path for replacing the atmosphere in the carry-out path with an inert gas;
Having
The manufacturing apparatus of the fibrous carbon material of any one of Claims 2-4.   The apparatus for producing a fibrous carbon material according to any one of claims 1 to 5, wherein the catalyst carrier has a particle size of 0.1 to 10 mm.   The apparatus for producing a fibrous carbon material according to any one of claims 1 to 6, wherein the catalyst is supported on the surface of a particulate substrate having a surface roughness Ra of 0.1 to 10 µm. .   The apparatus for producing a fibrous carbon material according to any one of claims 1 to 7, wherein the catalyst contains at least one selected from the group consisting of Fe, In, Sn, and C.   While heating the catalyst support deposit formed by supporting the catalyst on the particulate base material, the reaction gas is supplied between the catalyst supports in the catalyst support deposit, and fibers are formed on the surface of the catalyst support. A method for producing a fibrous carbon material, comprising producing a fibrous carbon material.   The method for producing a fibrous carbon material according to claim 9, wherein the time for heating the catalyst support deposit is 5 to 90 minutes.   The method for producing a fibrous carbon material according to claim 9 or 10, wherein the catalyst contains at least one selected from the group consisting of Fe, In, Sn, and C.

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