JP2007070166A - Method and apparatus for producing raw material gas for producing carbon nanomaterial - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and apparatus for producing raw material gas for producing a carbon nanomaterial by which when various carbon nanomaterials such as carbon nanotubes, carbon nanofibers and fullerenes are produced, raw material gas having gas components adapted to production of each carbon nanomaterial having objective properties can be produced directly and efficiently from biomass which is a carbon source. <P>SOLUTION: Raw material gas based on a gaseous carbon-containing compound and supplied to a synthesis furnace 3 which is an apparatus for producing a carbon nanomaterial is generated by gasification treatment of biomass by indirect heating with an indirect heating unit 1. The gasification treatment is thermal decomposition gasification treatment in which biomass is thermally decomposed. The gas components of raw material gas obtained from biomass and capable of varying properties of a produced carbon nanomaterial are regulated by varying conditions in gasification treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, when various types of carbon nanomaterials such as carbon nanotubes, carbon nanofibers, and fullerenes are produced, the raw material gas of the gas component according to the production of the carbon nanomaterial having the target property is obtained from biomass as a carbon source. The present invention relates to a raw material gas production method for producing carbon nanomaterial that can be directly and efficiently produced, and an apparatus therefor.

  Fullerenes, carbon nanofibers, and carbon nanotubes (hereinafter collectively referred to as carbon nanomaterials) exist in nature, but it is very difficult to separate and extract them with high purity from impurities. Among them, carbon nanotubes have excellent physical properties, and development for mass production industrially using these as target substances has been actively conducted. For example, Patent Documents 1 and 2 are known as methods for producing carbon nanotubes using a carbon-containing material as a starting material.

In Patent Document 1, an amorphous metallosilicate is used as a support and a metal is used as the support in order to obtain a fine graphite carbon nanotube of very high quality with a good yield with almost no deposition of amorphous carbon. A carbon-nanotube is produced by contacting a carbon-containing catalyst and a carbon-containing compound at 500 to 1200 ° C. Further, a crystalline non-porous metallosilicate is used as a support, and a metal is supported on the surface of the support crystal. The carbon nanotubes are produced by contacting the catalyst and the carbon-containing compound at 500 to 1200 ° C. Further, in Patent Document 2, in order to provide a method for producing carbon nanotubes that can produce carbon nanotubes that are thin and have a small number of layers in a large amount and easily with high yield and high selectivity, gaseous fullerene molecules and metal elements are provided. Or it is made to contact the alloy containing a metal element at the temperature of 400-1200 degreeC.
JP 2003-238130 A JP 2003-292314 A

  By the way, the raw material used for the production of the carbon nanomaterial is often in the form of a gas, and for this raw material gas, it is necessary to adjust in advance according to the type and quality of the carbon nanomaterial to be produced. In any of the above-mentioned patent documents, a carrier gas or the like is added to various gaseous carbon-containing compounds, and hydrogen or the like is added for catalytic activity to mix them. It was necessary to prepare the adjusted source gas in advance.

  The present invention was devised in view of the above-described conventional problems, and when producing various carbon nanomaterials such as carbon nanotubes, carbon nanofibers, fullerenes, etc. Another object of the present invention is to provide a raw material gas production method for producing carbon nanomaterials and an apparatus therefor that can directly and efficiently produce a raw material gas of a gas component from biomass as a carbon source.

  A raw material gas production method for producing a carbon nanomaterial according to the present invention is to produce a raw material gas mainly composed of a carbon-containing compound gas supplied to a carbon nanomaterial production apparatus by gasification treatment of biomass by indirect heating. It is characterized by.

  The gasification treatment is preferably a pyrolysis gasification treatment for thermally decomposing the biomass.

  It is preferable to adjust the gas component of the raw material gas, which is obtained from the biomass and changes the properties of the carbon nanomaterial to be manufactured, by changing the conditions of the gasification treatment.

  The gasification treatment condition is preferably a heating temperature or a water vapor amount.

  The gasification treatment is preferably performed with an externally heated rotary kiln.

  The biomass is preferably woody biomass.

  Before supplying the raw material gas generated by the gasification treatment to the production apparatus, it is preferable to perform a gas purification treatment for removing substances that inhibit the production of the carbon nanomaterial from the raw material gas.

  It is preferable that the gas purification process includes a reforming process in which the raw material gas is heated and reformed.

  In the gas reforming treatment, it is desirable that the oxygen concentration of the source gas is 100 ppm or less.

  The gas purification process preferably includes a dehumidification process for dehumidifying the source gas.

  In the dehumidification treatment, it is desirable that the water content of the source gas is 2000 ppm or less.

  Of the purified source gas, it is preferable to supply the surplus that is not consumed by the manufacturing apparatus to another process.

  The carbon nanomaterial includes at least one selected from carbon nanotubes, carbon nanofibers, and fullerenes.

  Moreover, the raw material gas production apparatus for producing carbon nanomaterials according to the present invention is configured to produce biomass gas by indirect heating in order to produce a raw material gas mainly composed of a carbon-containing compound gas supplied to the production apparatus for carbon nanomaterials. It is characterized by having an indirect heating device for performing the chemical conversion treatment.

  The production apparatus is preferably an apparatus for producing a carbon nanomaterial by a chemical vapor deposition method.

  The indirect heating device includes a processing condition changing unit that changes a gasification processing condition in order to adjust a gas component of the raw material gas that is obtained from the biomass and changes a property of a carbon nanomaterial to be manufactured. It is preferable.

  It is preferable that the processing condition changing means change the heating temperature and water vapor amount of the indirect heating apparatus as conditions for gasification processing.

  In the raw material gas production method and apparatus for producing carbon nanomaterials according to the present invention, when producing various carbon nanomaterials such as carbon nanotubes, carbon nanofibers, fullerenes, etc. The raw material gas of the gas component according to the production of can be produced directly and efficiently from biomass which is a carbon source.

  Hereinafter, a preferred embodiment of a raw material gas production method and apparatus for producing a carbon nanomaterial according to the present invention will be described in detail with reference to the accompanying drawings. The raw material gas production method and its apparatus for producing carbon nanomaterials according to the present embodiment are basically carbon supplied to a synthesis furnace 3 which is a production apparatus for carbon nanomaterials, as shown in FIGS. The raw material gas mainly containing the contained compound gas is generated by biomass gasification by indirect heating, and for this purpose, an indirect heating apparatus 1 for gasifying biomass by indirect heating is provided. In the description of this embodiment, carbon nanotubes, carbon nanofibers, and fullerenes are collectively referred to as carbon nanomaterials.

  As a carbon nanomaterial manufacturing apparatus, various apparatuses are known. For example, a synthesis furnace 3 for manufacturing a carbon nanomaterial by depositing a source gas by a chemical vapor deposition method (CVD method) can be given. Among the chemical vapor deposition methods, in particular, a catalytic chemical vapor deposition method (CCVD method) using a catalyst, a raw material gas mainly composed of a carbon-containing compound gas is introduced into the synthesis furnace 3 to support a metal. And the source gas are brought into contact with each other, carbon atoms are adsorbed by the metal and grow, whereby a carbon nanomaterial can be produced. Biomass refers to organic resources derived from living organisms excluding fossil fuels, and may be anything in that sense, but it is particularly preferable to use woody biomass that is stable in quality and inexpensive.

  Explaining the gasification treatment of biomass, combustible gas (reducing gas containing carbon C) is generated when a fire type is brought close to organic matter and placed in a high temperature state. When the combustible gas is in a combustible temperature range in an atmosphere containing oxygen, combustion (oxidation) is performed, and further, the combustion reaction is continued while repeating the conversion of the organic matter into combustible gas by the heat. Biomass gasification refers to bringing biomass into a gasification state before combustion reaction occurs.

As a method for gasifying biomass, gasification with air and gasification with oxygen are known. In this embodiment, gasification by indirect heating is performed. This gasification by indirect heating is a method in which biomass is steamed and gasified in a high-temperature region (for example, 600 to 900 ° C.) in an oxygen-free atmosphere, and a medium heating value (2500 to 4000 kcal / Nm ³ ) gas is obtained. be able to. A heat source necessary for gasification is not obtained by burning biomass itself, but another heat source is used. By controlling this heat source, the gasification temperature at which biomass is gasified can be controlled.

The gasification treatment is preferably a pyrolysis gasification treatment in which biomass is thermally decomposed. When biomass is put in a container and ignited and air and oxygen are supplied, the biomass undergoes a combustion reaction. When the amount of air is large, the biomass is completely burned, and the organic components in the biomass are carbon dioxide and water. On the other hand, in the pyrolysis gasification treatment, an incomplete combustion state is achieved by, for example, reducing the amount of air, whereby a combustible gas mainly composed of carbon monoxide can be obtained. The thermal decomposition reaction of biomass (C _n H _m O _p ) at this time is roughly as follows.

C _n H _m O _p + aO ₂ + bH ₂ O → cCO + dCO ₂ + eH ₂ + C _x H _y

O ₂ and H ₂ O added at this time are called gasifying agents and are also contained in the biomass itself. When the above reaction is divided into elementary reactions, it consists mainly of the following reactions.

(1) Combustion: C + O ₂ → CO ₂
H ₂ + 1 / 2O ₂ → H ₂ O (gas)
(2) Partial oxidation: C + 1 / 2O ₂ → CO
(3) Generated gas: C + CO ₂ → 2CO
(4) Water gasification: C + H ₂ O (gas) → CO + H ₂
(5) Hydrogenation: C + 2H ₂ → CH ₄
(6) Shift reaction: CO + H ₂ O (gas) → CO ₂ + H ₂
(7) Methanation: CO + 3H ₂ → CH ₄ + H ₂ O (gas)
(8) Steam reforming: CH ₄ + H ₂ O (gas) → CO + 3H ₂

(1) and (2) are exothermic reactions, but other reactions are endothermic or exothermic, and proceed at high temperatures.

  When biomass is pyrolyzed and gasified in this way, a raw material gas mainly composed of a carbon-containing compound gas can be generated. The water vapor generated by this treatment promotes various reactions such as water gasification, shift reaction, and steam reforming, and hydrogen is useful for the activity of the catalyst used when the carbon nanomaterial is produced by catalytic chemical vapor deposition.

  In the production of carbon nanomaterials, depending on the amount of carbon-containing compound gas contained in the raw material gas, specifically the amount of carbon monoxide or methane, or the ratio of these components, carbon nanotubes can be obtained, or carbon nanofibers can be produced. It is known that the properties, that is, the type and quality of the obtained carbon nanomaterials differ depending on whether it is obtained and whether it is a single layer or a multilayer. In the pyrolysis gasification process by indirect heating, the gas components in the raw material gas produced by the reactions (1) to (8) above, that is, carbon monoxide, methane, etc., are changed by changing the conditions of the gasification process. The amount or ratio changes. For example, it has been found that the gas component in the raw material gas can be controlled to be preferable for the production of the target carbon nanomaterial, depending on the heating temperature and the amount of water vapor, among the gasification treatment conditions. This point will be described below.

  It is a gasification process by indirect heating, which is a pyrolysis gasification process, and it is possible to arbitrarily control the conditions of the gasification process, and at least the conditions of the heating temperature and the amount of water vapor can be changed. As the indirect heating device 1, for example, the external heating type rotary kiln 5 shown in FIG. 2 can be used. This externally heated rotary kiln 5 mainly includes a hollow cylindrical reaction cylinder 6 arranged horizontally, a hollow cylindrical chamber 7 arranged laterally surrounding the reaction cylinder 6, and a gas And a controller 8 as processing condition changing means for changing the processing conditions. The reaction cylinder 6 is provided so as to be rotatable relative to the chamber 7 and is driven to rotate. The reaction cylinder 6 is disposed so as to be slightly inclined from the inlet 6a toward the outlet 6b. The reaction tube 6 is configured to be hermetically sealed from the outside so as to obtain an oxygen-free state. The chamber 7 is supplied with a heat medium therein, and the chamber 7 heats the reaction tube 6 with the heat medium.

  Then, the biomass is charged into the reaction cylinder 6 from the charging port 6a, and the biomass is moved in the inclined reaction cylinder 6 while being stirred by the rotation of the reaction cylinder 6, and supplied to the chamber 7. The raw material gas generated from biomass by this indirect heating and the remaining char are discharged from the discharge port 6b. The char is used as a fuel for raising the temperature of the heat medium supplied to the chamber 7.

  In the external heat type rotary kiln 5, since it becomes contact heat transfer, the heat transfer coefficient is high, and biomass can be efficiently gasified. By adjusting the temperature of the heat medium in the chamber 7, the gasification temperature can be controlled to a desired temperature. Moreover, since the biomass can be quickly heated to the gasification temperature, the amount of tar generated can also be suppressed. Moreover, since it is a horizontal rotary furnace format, there are few restrictions with respect to the shape of the biomass used as a raw material, and the raw material which is easy to get entangled with fibers, such as a bamboo and a bark, can also be processed. Further, since there is no high-temperature combustion part, clinker is not generated and stable operation can be performed.

  The controller 8 that is a processing condition changing means adjusts the amount of the heating medium supplied to the chamber 7 and the temperature thereof, thereby adjusting the temperature of the reaction tube 6, and hence the biomass. In addition, as indicated by an arrow M in FIG. 2, control may be performed to change the heat medium supply position to the chamber 7 in the length direction or the circumferential direction of the chamber 7. The heating temperature can be directly changed and adjusted according to the amount of the heat medium and its temperature, and further, the gasification temperature (temperature gradient) can be adjusted in the length direction of the reaction cylinder 6 by adjusting the heat medium supply position. Thus, even in the same equipment, the gasification treatment condition of heating temperature can be changed in various ways, and a raw material gas containing various component ratios or amounts of carbon-containing compound gas can be generated. .

  Further, the controller 8 feeds water vapor into the reaction tube 6 through a steam pipe 9 connected to the reaction tube 6 or extracts water vapor generated from biomass from the reaction tube 6, so that the water vapor in the reaction tube 6 is removed. Adjust the amount. By changing the amount of water vapor in this way, the pyrolysis gasification treatment in the reaction cylinder 6 can be controlled, and the component ratio and amount of the carbon-containing compound gas in the generated raw material gas are adjusted. be able to. Further, as a condition for changing the gasification treatment by the external heating type rotary kiln 5, by changing the rotation speed of the reaction cylinder 6 or changing the sealing time of the inlet 6a and the outlet 6b, It is also possible to adjust the residence time of the biomass, which can change the gas yield.

In the externally heated rotary kiln 5, a raw material gas containing carbon monoxide, carbon dioxide, methane, and hydrogen as a main component and containing other carbon-containing compound gas is generated. Specifically, ethane, ethylene, acetylene, propane, oxygen, water, hydrogen chloride, hydrogen sulfide, hydrogen cyanide, ammonia, amines, hydrogen phosphide and the like are included. Further, the raw material gas includes dust, tar, and the like. According to the experimental example, as shown in Table 1, the composition of the raw material gas changes according to the gasification temperature and the amount of water vapor (including raw material moisture).

  As can be understood from Table 1, in the pyrolysis gasification treatment, when the gasification temperature is increased (see 350 ° C. → 550 ° C.), the concentrations of hydrogen, carbon monoxide, and methane increase, and the concentration of carbon dioxide is Lower. Moreover, there exists a tendency which can ensure a high hydrogen concentration, so that there is much moisture content (water vapor content), and the component ratio of carbon monoxide, a carbon dioxide, and methane changes with moisture content. In general, in the production of carbon nanotubes, if conditions with a large amount of hydrocarbons and carbon monoxide can be created, the amount of carbon nanotubes produced will increase and become multi-layered. In addition, the higher the hydrogen concentration, the more the catalyst is activated and the amount of carbon nanotubes generated can be increased. In other words, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, and fullerenes can be produced separately by adjusting the components of the source gas.

  Thus, the raw material gas mainly composed of carbon-containing compound gas generated from biomass by gasification by pyrolysis gasification in the external heating type rotary kiln 5 as the indirect heating device 1 is an apparatus for producing carbon nanomaterials. Before being supplied to the synthesis furnace 3, the material is sent to the gas purification device 2 that removes substances that obstruct the production of the carbon nanomaterial and subjected to gas purification treatment. As described above, the raw material gas contains substances that inhibit the production of the carbon nanomaterial, such as oxygen, water, ammonia, hydrogen sulfide, tar, and dust, as described above.

  As shown in FIG. 3, the gas purification process includes a reforming process in which the source gas is heated and reformed, a gas cooling process in which the reformed source gas is cooled, and a process for cleaning the source gas. A water treatment, a dehumidifying process for dehumidifying the raw material gas, and a dust removing process for removing the dust from the raw material gas are performed. For this purpose, gas reforming including a reformer 10 equipped with a heating device, a water spraying device, etc. A device 11, a water passage device 12 for cleaning gas through water, a dehumidifying device 13 having a dehumidifying agent and an adsorbent, and a dust removing device 14 having a filter are provided.

  In the reforming process, pure oxygen is supplied and the raw material gas is partially burned to heat the raw material gas to a high temperature, thereby decomposing the tar. It also removes oxygen contained in trace amounts by burning it. With this reforming process, the raw material gas undergoes further water gasification reaction and shift reaction, and the component ratio of hydrogen, carbon monoxide, and carbon dioxide changes. In the gas cooling process, the gas is cooled and dehumidified. In the water flow treatment, relatively large dust is removed and the raw material gas is cooled to dehumidify. Moreover, the tar remaining in a minute amount is agglomerated and removed. Furthermore, removal of a water-soluble catalyst poison that is not preferable for the catalyst of the carbon nanomaterial production apparatus is also performed.

  In the dehumidifying process, moisture is removed by a dehumidifying agent. Furthermore, by using an adsorbent, a gaseous catalyst poisoning substance contained in a trace amount is adsorbed and removed. In the dust removal treatment, dust is removed by a physical filter. In this gas purification treatment, it is preferable that the water content is 2000 ppm or less and the oxygen concentration is 100 ppm or less from the viewpoint of preventing deterioration of the catalyst used in the carbon nanomaterial production apparatus.

  The raw material gas subjected to the gas purification process as described above is supplied to a carbon nanomaterial manufacturing apparatus such as the synthesis furnace 3. As described above, the indirect heating by the indirect heating apparatus 1 capable of controlling the gasification treatment allows various changes in the properties of the carbon nanomaterial produced by using the biological biomass as it is. Since the raw material gas adjusted to the gas component can be directly produced, when producing various carbon nanomaterials such as carbon nanotubes, carbon nanofibers, fullerenes, etc., gas corresponding to the production of carbon nanomaterials with the desired properties The component raw material gas can be efficiently produced, and by supplying it to the carbon nanomaterial production equipment, the carbon nanomaterial with the desired properties such as single- or multi-walled carbon nanotubes, carbon nanofibers, fullerenes, etc. Can be manufactured efficiently.

  The surplus of the raw material gas sent to the carbon nanomaterial manufacturing apparatus is supplied to another utilization process 4. Since the source gas is a combustible gas, it can be used for other processes such as power generation as a heat source, hydrogen production, dimethyl ether production, energy production, conversion to industrial raw materials, etc. .

  As described above, in the raw material gas production method and apparatus for producing carbon nanomaterials according to this embodiment, carbon nanomaterials can be produced using biomass as a starting material. Then, according to indirect heating and also pyrolysis gasification treatment, it is possible to change the gasification conditions, and by changing the gasification conditions, the gas composition in the raw material gas originating from biomass can be arbitrarily set The raw material gas matched to the target carbon nanomaterial can be directly and efficiently produced from biomass.

  Using an externally heated rotary kiln, the woody biomass was indirectly heated at a gasification furnace temperature of 700 ° C. to be pyrolyzed and gasified. The obtained raw material gas was heated to 1150 ° C. and reformed. Thereafter, water was passed through and dehumidified, and dust was removed with a filter. Thereafter, secondary dehumidification was further performed. By the above gas purification treatment, the oxygen concentration was 100 ppm or less, the water content was 2000 ppm or less, ammonia and hydrogen sulfide were 1 ppm or less, and tar and dust were set to the detection limit or less. The raw material gas after the gas purification treatment was supplied to the carbon nanotube production apparatus, and the carbon nanotubes were produced by the CCVD method at a raw material gas flow rate of 100 to 150 ml / min, a synthesis temperature of 650 ° C., and a reaction time of 5 minutes.

  When the gasifier temperature is set to 830 ° C. and the obtained raw material gas is heated to 1150 ° C. for reforming treatment, the main four components are hydrogen 52.6%, carbon monoxide 10.9%, methane 3 .3% and carbon dioxide 21.3% were obtained.

  The present invention controls gasification processing conditions on the premise that a raw material gas containing a carbon-containing compound gas that can be supplied to a carbon nanomaterial manufacturing apparatus can be generated by simply gasifying biomass. By the indirect heating that can be performed, the raw material gas that should be adjusted and prepared in advance can be obtained directly from the biomass.

It is a process flow figure showing one suitable embodiment of a source gas manufacturing method for carbon nanomaterial manufacture concerning the present invention. It is explanatory drawing which shows schematic structure of the external heating type rotary kiln which is an example of the indirect heating apparatus applicable to the raw material gas manufacturing method for carbon nanomaterial manufacture of FIG. FIG. 2 is a process flow diagram showing a gas purification treatment process applicable to the raw material gas production method for producing the carbon nanomaterial of FIG. 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Indirect heating apparatus 3 Synthesis furnace 4 Utilization process 5 External heating type rotary kiln 8 Controller

Claims (17)

  A raw material gas production method for producing carbon nanomaterials, characterized in that a raw material gas mainly composed of a carbon-containing compound gas supplied to a carbon nanomaterial production apparatus is generated by gasification treatment of biomass by indirect heating.   The method for producing a raw material gas for producing a carbon nanomaterial according to claim 1, wherein the gasification treatment is a pyrolysis gasification treatment in which the biomass is pyrolyzed.   The gas component of the raw material gas that is obtained from the biomass and changes the properties of the produced carbon nanomaterial is adjusted by changing the conditions of the gasification treatment. The raw material gas manufacturing method for carbon nanomaterial manufacture of description.   The method for producing a raw material gas for producing carbon nanomaterials according to claim 3, wherein the gasification treatment conditions are a heating temperature and an amount of water vapor.   The method for producing a raw material gas for producing a carbon nanomaterial according to any one of claims 1 to 4, wherein the gasification treatment is performed by an externally heated rotary kiln.   The said biomass is woody biomass, The raw material gas manufacturing method for carbon nanomaterial manufacture in any one of Claims 1-5 characterized by the above-mentioned.   The gas purification treatment is performed to remove a substance that inhibits the production of the carbon nanomaterial from the raw material gas before supplying the raw material gas generated by the gasification treatment to the production apparatus. Item 7. A raw material gas production method for producing a carbon nanomaterial according to any one of Items 1 to 6.   The said gas purification process includes the modification | reformation process which heats and reforms the said source gas, The source gas manufacturing method for carbon nanomaterial manufacture of Claim 7 characterized by the above-mentioned.   9. The method for producing a raw material gas for producing carbon nanomaterials according to claim 8, wherein in the gas reforming treatment, the oxygen concentration of the raw material gas is set to 100 ppm or less.   The said gas purification process contains the dehumidification process which dehumidifies from the said source gas, The raw material gas manufacturing method for carbon nanomaterial manufacture in any one of Claims 7-9 characterized by the above-mentioned.   The method for producing a raw material gas for producing a carbon nanomaterial according to claim 10, wherein the moisture in the raw material gas is set to 2000 ppm or less in the dehumidifying treatment.   The method for producing a raw material gas for producing carbon nanomaterials according to any one of claims 1 to 11, wherein, in the purified raw material gas, a surplus that is not consumed by the production apparatus is supplied to another process. .   The said carbon nanomaterial contains at least 1 chosen from a carbon nanotube, a carbon nanofiber, and a fullerene, The raw material gas manufacturing method for carbon nanomaterial manufacture in any one of Claims 1-12 characterized by the above-mentioned.   Carbon nanomaterial manufacturing comprising an indirect heating device for gasifying biomass by indirect heating to generate a raw material gas mainly composed of carbon-containing compound gas to be supplied to the carbon nanomaterial manufacturing device Raw material gas production equipment.   The raw material gas production apparatus for producing carbon nanomaterial according to claim 14, wherein the production apparatus is an apparatus for producing a carbon nanomaterial by a chemical vapor deposition method.   The indirect heating device includes a processing condition changing unit that changes a gasification processing condition in order to adjust a gas component of the raw material gas that is obtained from the biomass and changes a property of a carbon nanomaterial to be manufactured. The raw material gas production apparatus for carbon nanomaterial manufacture of Claim 14 or 15 characterized by the above-mentioned.   The raw material gas production apparatus for producing carbon nanomaterials according to claim 16, wherein the treatment condition changing means changes the heating temperature and water vapor amount of the indirect heating device as gasification treatment conditions. .

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