JP2005272277A - Method for manufacturing nano carbon material - Google Patents
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 115
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 238000010438 heat treatment Methods 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000567 combustion gas Substances 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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Abstract
Description
本発明は、ナノカーボン材料の製造方法に関する。 The present invention relates to a method for producing a nanocarbon material.
ナノカーボン材料は、「炭素で構成され、分子１個が１０-9〜１０-7（１〜１００ｎｍ）程度のサイズを持つ材料」とされている。
ナノカーボン材料は、次世代材料として注目されており、例えば電子部品、ガス吸蔵材料、医薬品、触媒、構造材料等への応用が期待されている。
The nanocarbon material is regarded as “a material composed of carbon and having one molecule having a size of about 10 −9 to 10 −7 (1 to 100 nm)”.
Nanocarbon materials are attracting attention as next-generation materials, and are expected to be applied to electronic parts, gas storage materials, pharmaceuticals, catalysts, structural materials, and the like.
ナノカーボン材料の製造法としては、アーク放電法、レーザ蒸発法、ＣＶＤ反応（chemical vapor deposition）法の３種に大別される。その中ＣＶＤ反応法は、大量製造に適した方法として主流になりつつある。
ＣＶＤ反応法は、通常アセチレン、ベンゼン等の原料を外部ヒータにより加熱分解し、これにより生じた炭素蒸気を触媒層上に析出成長させて、ナノカーボン材料を製造する（特許文献１）。
The methods for producing nanocarbon materials are roughly classified into three types: an arc discharge method, a laser evaporation method, and a CVD reaction (chemical vapor deposition) method. Among them, the CVD reaction method is becoming mainstream as a method suitable for mass production.
In the CVD reaction method, raw materials such as acetylene and benzene are usually thermally decomposed by an external heater, and carbon vapor generated thereby is deposited and grown on a catalyst layer to produce a nanocarbon material (Patent Document 1).
また、上記ＣＶＤ反応法においては、バーナ火炎中に触媒を投入し、火炎中で原料を熱分解させると共にナノカーボン材料を上記触媒の表面に析出成長させる燃焼式のＣＶＤ反応法もある（特許文献２）。 In addition, in the above CVD reaction method, there is also a combustion type CVD reaction method in which a catalyst is put into a burner flame, a raw material is thermally decomposed in the flame, and a nanocarbon material is deposited and grown on the surface of the catalyst (Patent Document). 2).
ところで、上記加熱反応器内に触媒を投入する方法としては、ロータリーフィーダーを用いて加熱反応器に固体状の触媒粒子を直接に投入する方法、或いは触媒粒子に液体を混合したスラリー状物を直接に加熱反応器内に送り込む方法等が挙げられる。 By the way, as a method of charging the catalyst into the heating reactor, a method of directly charging solid catalyst particles into the heating reactor using a rotary feeder, or a slurry-like material in which a liquid is mixed into the catalyst particles is directly used. And the like, and the like.
しかしながら、これらの触媒粒子送入方法は、触媒粒子を直接に加熱反応器内に送入する方法であるため、加熱反応器内における触媒粒子の流動性、分散性、触媒粒子の投入量等のコントロールが困難であり、大型の加熱反応器を準備しなければならないという問題がある。 However, since these catalyst particle feeding methods are methods in which the catalyst particles are directly fed into the heating reactor, the fluidity and dispersibility of the catalyst particles in the heating reactor, the input amount of the catalyst particles, etc. There is a problem that it is difficult to control and a large heating reactor has to be prepared.
本発明は、かかる問題点に鑑み、加熱反応器内への触媒粒子の送入が容易であると共に加熱反応器内における触媒粒子の流動性、分散性に優れ、小型の加熱反応器を用いることができるナノカーボン材料の製造方法を提供しようとするものである。 In view of such problems, the present invention uses a small heating reactor that facilitates the feeding of catalyst particles into the heating reactor and is excellent in fluidity and dispersibility of the catalyst particles in the heating reactor. It is an object of the present invention to provide a method for producing a nanocarbon material that can be used.
本発明は、炭素化合物を含有する原料ガスと触媒粒子とを酸素含有ガスと共に加熱反応器内に送入し、該加熱反応器内において上記炭素化合物を部分燃焼させて、ＣＶＤ反応によって触媒粒子の表面にナノカーボン材料を析出成長させる方法において、
上記触媒粒子は、該触媒粒子よりも密度が小さいと共に上記部分燃焼時の温度によって熱分解する性質を有する担体によって被覆された担持粉末の状態で、上記加熱反応器内に供給され、
上記担持粉末は、流動層タンク内において上記原料ガスの導入によって流動化されていると共に、その一部が上記原料ガスと共に上記加熱反応器内に送入され、
上記加熱反応器においては、上記原料ガスを上記酸素含有ガスによって部分燃焼させると共に該部分燃焼の火炎中に上記担持粉末を投入して、該担持粉末中の上記担体を熱分解させて触媒粒子の表面を露出させ、
ＣＶＤ反応により上記触媒粒子の表面にナノカーボン材料を析出成長させることを特徴とするナノカーボン材料の製造方法にある（請求項１）。
In the present invention, a raw material gas containing carbon compound and catalyst particles are fed into a heating reactor together with an oxygen-containing gas, and the carbon compound is partially burned in the heating reactor, and the catalyst particles are formed by CVD reaction. In a method of depositing and growing a nanocarbon material on the surface,
The catalyst particles are supplied into the heating reactor in a state of a supported powder having a density lower than that of the catalyst particles and coated with a carrier having a property of being thermally decomposed by the temperature at the time of partial combustion,
The supported powder is fluidized by introducing the raw material gas in a fluidized bed tank, and a part thereof is fed into the heating reactor together with the raw material gas,
In the heating reactor, the raw material gas is partially combusted by the oxygen-containing gas, and the supported powder is introduced into a flame of the partial combustion, and the carrier in the supported powder is thermally decomposed to form catalyst particles. Exposing the surface,
The method of producing a nanocarbon material is characterized in that the nanocarbon material is deposited and grown on the surface of the catalyst particles by a CVD reaction.
本発明において、最も注目すべきことは、加熱反応器へ送入する触媒粒子が、上記担体によって被覆された担持粉末の状態であること、該担持粉末は加熱反応器よりも上流側に設けた流動層タンク内において上記原料ガスによって流動化され、その一部の担持粉末が順次加熱反応器へ送入され、加熱反応器内においては上記担持粉末の表面部の担体が熱分解により離散し、露出した触媒粒子の表面にナノカーボン材料が析出成長するようにしたことである。 In the present invention, the most notable point is that the catalyst particles fed into the heating reactor are in the state of a supported powder coated with the carrier, and the supported powder is provided on the upstream side of the heated reactor. In the fluidized bed tank, fluidized by the raw material gas, a part of the supported powder is sequentially fed into the heating reactor, and in the heating reactor, the support on the surface portion of the supported powder is dispersed by pyrolysis, That is, the nanocarbon material is deposited and grown on the exposed surfaces of the catalyst particles.
本発明においては、触媒粒子を上記のごとく担体によって被覆して担持粉末としている。そして、上記担体は触媒粒子よりも密度が小さい。そのため、担持粉末は触媒粒子自体よりも密度が小さくなり、上記流動層タンク内において上記原料ガスの導入により流動化し易い。
それ故、原料ガスの導入速度等を調整することにより、所望量の担持粉末を加熱反応器に容易に送入することができ、そのコントロールが容易となる。
In the present invention, the catalyst particles are coated with a carrier as described above to form a supported powder. The carrier has a density lower than that of the catalyst particles. Therefore, the density of the supported powder is smaller than that of the catalyst particles themselves, and it is easy to fluidize by introducing the raw material gas in the fluidized bed tank.
Therefore, by adjusting the introduction speed of the raw material gas and the like, a desired amount of the supported powder can be easily fed into the heating reactor, and the control becomes easy.
また、流動層タンクにある担持粉末を加熱反応器に送入するので、加熱反応器内における触媒粒子の流動性、分散性にも優れている。
そのため、加熱反応器を小型化することができる。
Further, since the supported powder in the fluidized bed tank is fed into the heating reactor, the fluidity and dispersibility of the catalyst particles in the heating reactor are also excellent.
Therefore, the heating reactor can be reduced in size.
もしも、担持粉末の状態でなく、触媒粒子のみを流動層タンク内で流動化させようとすると、触媒粒子はニッケル、鉄等の金属粒子であるために比重が大きく、多量の原料ガスを流動層タンク内に送入して流動化しなければならず、原料ガスの使用量が大きくなり、原料ガスが無駄になると共にコスト高となる。
また、触媒粒子は、流動層タンク内において担持粉末の状態で流動化しているので、触媒粒子自体は何らの損傷もない状態で加熱反応器内に送られ、触媒粒子本来の触媒活性を発揮できる。
If only the catalyst particles are fluidized in the fluidized bed tank instead of the supported powder, the catalyst particles are metal particles such as nickel and iron, so the specific gravity is large and a large amount of raw material gas is fed into the fluidized bed. It must be sent into the tank and fluidized, and the amount of the raw material gas used becomes large, so that the raw material gas is wasted and the cost is increased.
In addition, since the catalyst particles are fluidized in the state of a supported powder in the fluidized bed tank, the catalyst particles themselves are sent into the heating reactor without any damage and can exhibit the original catalytic activity of the catalyst particles. .
また、触媒粒子を被覆している担体は、加熱反応器内の部分燃焼時の温度によって熱分解し離散するので、加熱反応器内に送入された担持粉末は早急に触媒粒子のみとなる。そのため、部分燃焼によって発生した炭素は直ちに触媒粒子の表面に析出成長することができ、ナノカーボン構造に優れたナノカーボン材料を得ることができる。 In addition, since the carrier covering the catalyst particles is thermally decomposed and dispersed according to the temperature at the time of partial combustion in the heating reactor, the supported powder sent into the heating reactor quickly becomes only the catalyst particles. Therefore, carbon generated by partial combustion can immediately precipitate and grow on the surface of the catalyst particles, and a nanocarbon material having an excellent nanocarbon structure can be obtained.
また、火炎温度は高温度（約１２００〜２２００℃）であるため、反応性の低いメタンを炭素化合物として用いた場合でも炭素蒸気が形成され易く、ナノカーボン材料が析出成長し易いという利点がある。
そのため、本発明においては、特に炭素化合物として、メタンを用いる場合にその効果が発揮される。
Further, since the flame temperature is high (about 1200 to 2200 ° C.), even when methane having low reactivity is used as the carbon compound, carbon vapor is easily formed, and there is an advantage that the nanocarbon material is easily precipitated and grown. .
Therefore, in the present invention, the effect is exhibited particularly when methane is used as the carbon compound.
上記のごとく、本発明によれば加熱反応器内への触媒粒子の送入が容易であると共に加熱反応器内における触媒粒子の流動性、分散性に優れ、小型の加熱反応器を用いることができるナノカーボン材料の製造方法を提供することができる。 As described above, according to the present invention, the catalyst particles can be easily fed into the heating reactor and the fluidity and dispersibility of the catalyst particles in the heating reactor are excellent, and a small heating reactor can be used. The manufacturing method of the nano carbon material which can be provided can be provided.
次に、本発明において、炭素化合物を含有する原料ガスとしては、後述するメタン等の炭素化合物を含有しているガスであり、このガス中には炭素化合物の含有割合を調整するために、アルゴン、ヘリウム、水素、窒素などの調整用ガスを混入させることもできる。
上記酸素含有ガスは、部分燃焼の酸素源として用いるものであり、酸素ガスの他空気を用いることもできる。
Next, in the present invention, the raw material gas containing a carbon compound is a gas containing a carbon compound such as methane described later, and in order to adjust the content ratio of the carbon compound in this gas, argon is used. In addition, an adjustment gas such as helium, hydrogen, or nitrogen can be mixed.
The oxygen-containing gas is used as an oxygen source for partial combustion, and air other than oxygen gas can be used.
上記原料ガスに対する酸素含有ガスの割合は、上記炭素化合物を部分燃焼させてナノカーボン材料を触媒粒子表面に析出成長させるに適度な割合であり、通常は炭素化合物を完全燃焼させるために必要な酸素量の０〜７５％の酸素含有量とすることが好ましい。
上記加熱反応器は、通常、反応筒とその外部に配設した電熱ヒータとからなり、上記反応筒内において、上記部分燃焼、触媒粒子へのナノカーボン材料の析出成長が行なわれる。
The ratio of the oxygen-containing gas to the raw material gas is an appropriate ratio for causing partial combustion of the carbon compound to cause the nanocarbon material to precipitate and grow on the catalyst particle surface, and usually oxygen necessary for complete combustion of the carbon compound. The oxygen content is preferably 0 to 75% of the amount.
The heating reactor is usually composed of a reaction cylinder and an electric heater arranged outside the reaction cylinder, and the partial combustion and precipitation growth of the nanocarbon material on the catalyst particles are performed in the reaction cylinder.
上記部分燃焼は、原料ガス中の炭素化合物を部分燃焼させてメタン等の炭素化合物を炭素とするための手段である。
そして、上記部分燃焼による火炎の中において、ＣＶＤ反応により、上記炭素の蒸気が触媒粒子の表面にナノカーボン材料として析出成長する。
本発明において得られる上記ナノカーボン材料は、カーボンナノホーン（ＣＮＨ）、フラーレン、カーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（ＣＮＦ）などの構造を有するが、特に本発明では、ＣＮＦ状の構造のものが多く得られる。
また、上記ＣＮＦ状構造には、らせん形状を持つカーボンナノコイル（ＣＮＣ）、ねじれ形状を持つカーボンナノツイスト（ＣＮＴｗ）などのヘリカルカーボンナノファイバー（ＨＣＮＦ）も含まれる。
The partial combustion is a means for partially burning a carbon compound in a raw material gas to convert a carbon compound such as methane into carbon.
And in the flame by the said partial combustion, the vapor | steam of the said carbon deposits and grows as a nanocarbon material on the surface of a catalyst particle by CVD reaction.
The nanocarbon material obtained in the present invention has a structure such as carbon nanohorn (CNH), fullerene, carbon nanotube (CNT), carbon nanofiber (CNF), etc. In particular, the present invention has a CNF-like structure. You can get a lot.
The CNF-like structure also includes helical carbon nanofibers (HCNF) such as carbon nanocoils (CNC) having a spiral shape and carbon nanotwists (CNTw) having a twisted shape.
上記触媒粒子を被覆する担体は、触媒粒子を略中心部に埋め込む状態であっても、触媒粒子の一部が若干露出している状態であってもよい（図４参照）。
上記担体は、触媒粒子の密度よりも小さいものを用いる。
そして、担持粉末とした状態の密度は、通常は０．５〜５ｇ／ｃｍ3とすることが好ましい。
０．５ｇ／ｃｍ3未満では担持粉末の流動化が激しく、一方５ｇ／ｃｍ3を超えると流動化が不充分となり、加熱反応器への供給調整が困難となるおそれがある。
なお、担持粉末は、流動層を形成する場合にアルキメデス数（後述）が１０3〜１０6となるよう調整しておくことが好ましい。アルキメデス数が１０3未満では担持粉末の流動化が激しく、一方１０6を超えると流動化が不充分となる。
The carrier covering the catalyst particles may be in a state where the catalyst particles are embedded in a substantially central portion or in a state where some of the catalyst particles are slightly exposed (see FIG. 4).
The carrier used is smaller than the density of the catalyst particles.
The density of the supported powder is usually preferably 0.5 to 5 g / cm 3 .
If it is less than 0.5 g / cm 3 , the fluidization of the supported powder is vigorous, whereas if it exceeds 5 g / cm 3 , fluidization becomes insufficient and adjustment of the supply to the heating reactor may be difficult.
The supported powder is preferably adjusted so that the Archimedes number (described later) is 10 3 to 10 6 when forming the fluidized bed. When the Archimedes number is less than 10 3 , fluidization of the supported powder is severe, whereas when it exceeds 10 6 , fluidization becomes insufficient.
また、上記担持粉末は、部分燃焼時の温度によって熱分解する性質を有するものを用いるが、通常は有機物を用いる。
加熱反応器内への担持粉末の送入は、通常、原料ガス１ｍ3当り１０7〜１０8個の担持粉末とすることが好ましい。
１０7個／ｍ3未満では触媒粒子量が少なく、１０8個／ｍ3を越えても触媒粒子量が多すぎて担持粉末の損失を生ずるおそれがある。
Moreover, although the said support | carrier powder uses the property which thermally decomposes with the temperature at the time of partial combustion, normally organic substance is used.
Usually, it is preferable that 10 7 to 10 8 supported powders per 1 m 3 of the raw material gas are fed into the heating reactor.
If it is less than 10 7 particles / m 3 , the amount of catalyst particles is small, and even if it exceeds 10 8 particles / m 3 , the amount of catalyst particles is too large, and there is a possibility of causing loss of the supported powder.
加熱反応器の出口においては、ナノカーボン材料が析出成長した触媒粒子である成長粒子、及び燃焼排ガスが排出され、両者はサイクロン等により固気分離される。
また、ナノカーボン材料は触媒粒子表面に析出成長した状態で採取され、必要に応じて、熱硝酸中での煮沸処理などの手段によりナノカーボン材料のみに分離される。
At the outlet of the heating reactor, the growth particles, which are catalyst particles on which the nanocarbon material is deposited and grown, and the combustion exhaust gas are discharged, and both are solid-gas separated by a cyclone or the like.
In addition, the nanocarbon material is collected in a state of being deposited and grown on the surface of the catalyst particles, and is separated into only the nanocarbon material by means such as boiling in hot nitric acid, if necessary.
次に、上記担体は、ポリビニルアルコール、ポリエチレン、樟脳、デンプンのいずれか一種以上であることが好ましい（請求項２）。
この場合には、上記熱分解が早急に行なわれ、また触媒粒子の触媒活性点を損傷するおそれがない。
Next, the carrier is preferably one or more of polyvinyl alcohol, polyethylene, camphor, and starch (Claim 2).
In this case, the thermal decomposition is performed immediately, and there is no possibility of damaging the catalyst active points of the catalyst particles.
次に、上記触媒粒子はニッケル、鉄、フェロセン、酢酸鉄、鉄・スズ系材料、鉄・スズ・インジウム系、ニッケル・スズ系材料のいずれか一種以上であることが好ましい（請求項３）。
この場合には、特に効率的にナノカーボン材料を析出成長させることができる。
なお、上記ニッケル、鉄、スズ、インジウムは、酸化物も含まれる。
Next, the catalyst particles are preferably one or more of nickel, iron, ferrocene, iron acetate, iron / tin based material, iron / tin / indium based, and nickel / tin based material (Claim 3).
In this case, the nanocarbon material can be deposited and grown particularly efficiently.
The nickel, iron, tin, and indium include oxides.
次に、上記炭素化合物は、アルカン、アルケン、アルキン及び芳香族系のガス状炭化水素及び一酸化炭素のいずれか一種以上であることが好ましい（請求項４）。
この場合には、効率的に、触媒粒子表面にナノカーボン材料を析出成長させることができる。上記アルカン系としては、メタン、エタン、プロパン、ブタンなどが、アルケン系としてはエチレン、プロピレンなどが、アルキンとしてはアセチレン、ブチンなどが、芳香族系としてはベンゼン、トルエン、ナフタレンなどがある。
また、この中、メタンは本発明の製造法を実施する場合、通常のＣＶＤ法でメタンを原料とした場合よりもナノカーボンの生成効率が高く、その実施効果が最も高い。
Next, the carbon compound is preferably at least one of alkanes, alkenes, alkynes, aromatic gaseous hydrocarbons, and carbon monoxide (Claim 4).
In this case, the nanocarbon material can be efficiently deposited and grown on the surfaces of the catalyst particles. Examples of the alkane series include methane, ethane, propane, and butane, examples of the alkene series include ethylene and propylene, examples of the alkyne include acetylene and butyne, and examples of the aromatic series include benzene, toluene, and naphthalene.
Of these, methane, when carrying out the production method of the present invention, has higher production efficiency of nanocarbon than the case where methane is used as a raw material in the usual CVD method, and its implementation effect is the highest.
次に、上記ナノカーボン材料は、上記触媒粒子の表面に析出成長した状態で上記加熱反応器より排出し、サイクロンにより燃焼ガスと分離し、採取することが好ましい（請求項５）。
この場合には、生産効率良く、ナノカーボン材料を採取することができる。
Next, it is preferable that the nanocarbon material is discharged from the heating reactor in a state of being deposited and grown on the surface of the catalyst particles, separated from the combustion gas by a cyclone, and collected (claim 5).
In this case, the nanocarbon material can be collected with high production efficiency.
（実施例１）
本発明の実施例にかかる、ナノカーボン材料の製造方法について、図１〜図５を用いて説明する。
本例は、図１に示すごとく、炭素化合物を含有する原料ガス２と触媒粒子とを酸素含有ガスと共に加熱反応器５内に送入し、該加熱反応器５内において上記炭素化合物を部分燃焼させて、ＣＶＤ反応によって触媒粒子１０の表面にナノカーボン材料を析出成長させる方法において、上記触媒粒子１０は、該触媒粒子１０よりも密度が小さいと共に上記部分燃焼時の温度によって熱分解する性質を有する担体１１によって被覆された担持粉末１の状態（図２、図４）で、上記加熱反応器５内に供給される。
(Example 1)
The manufacturing method of the nanocarbon material concerning the Example of this invention is demonstrated using FIGS.
In this example, as shown in FIG. 1, a raw material gas 2 containing carbon compound and catalyst particles are fed into a heating reactor 5 together with an oxygen-containing gas, and the carbon compound is partially burned in the heating reactor 5. In the method of depositing and growing a nanocarbon material on the surface of the catalyst particle 10 by a CVD reaction, the catalyst particle 10 has a property of being smaller in density than the catalyst particle 10 and thermally decomposing depending on the temperature at the time of partial combustion. The powder is supplied into the heating reactor 5 in the state of the supported powder 1 covered with the carrier 11 (FIGS. 2 and 4).
上記担持粉末１は、流動層タンク３内において上記原料ガス２の導入によって流動化されていると共に、その一部が上記原料ガス２と共に上記加熱反応器５内に送入される（図１、図２）。なお、バイブレータ等により流動層タンク３に振動を与えると、効率的に担持粉末を搬送できる。
上記加熱反応器５においては、図３に示すごとく、上記原料ガス２を上記酸素含有ガスとしての酸素ガスによって部分燃焼させると共に該部分燃焼の火炎１９中に上記担持粉末１を投入して、該担持粉末中の上記担体を熱分解させて触媒粒子１０の表面を露出させる。
そして、ＣＶＤ反応により上記触媒粒子１０の表面にナノカーボン材料２０を析出成長させた、成長粒子２１を得る（図３、図５）。
The supported powder 1 is fluidized by introducing the raw material gas 2 in the fluidized bed tank 3 and a part thereof is sent into the heating reactor 5 together with the raw material gas 2 (FIG. 1, Figure 2). Note that when the fluidized bed tank 3 is vibrated by a vibrator or the like, the supported powder can be efficiently conveyed.
In the heating reactor 5, as shown in FIG. 3, the raw material gas 2 is partially combusted by oxygen gas as the oxygen-containing gas, and the supported powder 1 is introduced into the flame 19 of the partial combustion. The carrier in the supported powder is pyrolyzed to expose the surfaces of the catalyst particles 10.
And the growth particle 21 which made the nanocarbon material 20 precipitate and grow on the surface of the said catalyst particle 10 by CVD reaction is obtained (FIG. 3, FIG. 5).
以下、これらにつき詳しく説明する。
上記流動層タンク３は、図１及び図２に示すごとく、その内部に通気性の多孔板３１を有する。多孔板３１の上には担持粉末１を投入する。そして、多孔板３１の下方に炭素化合物を含有する原料ガス２を導入することによって、担持粉末１を流動化させ流動層３２を形成する。
また、流動層タンク３にはバイパス３６を設ける。バイパス３６には流動層タンク３内への原料ガス２の送入量を調整するための調整弁３６１を介設する。なお、符号３３は、担持粉末補給口である。
These will be described in detail below.
As shown in FIGS. 1 and 2, the fluidized bed tank 3 has a gas-permeable porous plate 31 therein. The carrier powder 1 is put on the porous plate 31. Then, by introducing the raw material gas 2 containing a carbon compound below the porous plate 31, the supported powder 1 is fluidized to form a fluidized bed 32.
The fluidized bed tank 3 is provided with a bypass 36. The bypass 36 is provided with an adjustment valve 361 for adjusting the amount of the raw material gas 2 fed into the fluidized bed tank 3. Reference numeral 33 denotes a supported powder supply port.
次に、加熱反応器５は、図１、図３に示すごとく、反応筒５１とその外部に設けた電気ヒータ５５とを有する。反応筒５１の上部には上記流動層タンク３に連結した送入パイプ３７、及び酸素ガス導入用の酸素パイプ４を接続する。
また、反応筒５１の下部には、ナノカーボン材料２０を触媒粒子１０の表面に析出成長させた成長粒子２１及び排ガスをサイクロン６に排出するための排ガスパイプ５７を接続する。サイクロン６の下部には上記成長粒子２１を捕集する捕集タンク６１を設け、一方、サイクロン６の上部には排ガスを放出するブロワー６２を、放出パイプ５８を介して接続する。
Next, as shown in FIGS. 1 and 3, the heating reactor 5 includes a reaction cylinder 51 and an electric heater 55 provided outside thereof. An inlet pipe 37 connected to the fluidized bed tank 3 and an oxygen pipe 4 for introducing oxygen gas are connected to the upper part of the reaction cylinder 51.
Further, a growth particle 21 obtained by depositing and growing the nanocarbon material 20 on the surface of the catalyst particle 10 and an exhaust gas pipe 57 for discharging the exhaust gas to the cyclone 6 are connected to the lower part of the reaction cylinder 51. A collection tank 61 for collecting the growing particles 21 is provided at the lower part of the cyclone 6, while a blower 62 for discharging exhaust gas is connected to the upper part of the cyclone 6 via a discharge pipe 58.
上記加熱反応器５内においては、図３に示すごとく、流動層タンク３から送られて来た担持粉末１と原料ガス２とが、反応筒５１内に送入されると共に酸素パイプ４から酸素が供給され、原料ガス２中の炭素化合物が上記酸素によって部分燃焼される。この時の温度は約１２００〜２２００℃である。また、加熱反応器５のヒータ５５は約５００〜９００℃に加熱されている。 In the heating reactor 5, as shown in FIG. 3, the supported powder 1 and the raw material gas 2 sent from the fluidized bed tank 3 are sent into the reaction tube 51 and oxygen from the oxygen pipe 4. Is supplied, and the carbon compound in the raw material gas 2 is partially burned by the oxygen. The temperature at this time is about 1200 to 2200 ° C. The heater 55 of the heating reactor 5 is heated to about 500 to 900 ° C.
そして、図３に示すごとく、部分燃焼の火炎１９中においては、火炎中に送入された担持粉末１（図３のＡ）の表面の担体１１が、火炎の熱によって熱分解し、更には火炎によって燃焼する（図３のＢ）。
これにより、担持粉末１の内部の触媒粒子１０が露出する（図３のＣ）。
次いで、上記炭素化合物の部分燃焼により発生した炭素蒸気が上記触媒粒子１０の表面に析出成長してナノカーボン材料２０を形成し、成長粒子２１となる。この状態の概念図を図５に示す。
As shown in FIG. 3, in the partially burned flame 19, the carrier 11 on the surface of the supported powder 1 (A in FIG. 3) fed into the flame is thermally decomposed by the heat of the flame, It burns with a flame (B in FIG. 3).
As a result, the catalyst particles 10 inside the supported powder 1 are exposed (C in FIG. 3).
Next, carbon vapor generated by partial combustion of the carbon compound precipitates and grows on the surface of the catalyst particles 10 to form the nanocarbon material 20, thereby forming grown particles 21. A conceptual diagram of this state is shown in FIG.
図５は、触媒粒子１０の表面にナノカーボン材料２０が析出成長した成長粒子２１を示している。成長粒子２１は、上記のごとく、排気ガスと共にサイクロン６に送られ、捕集タンク６１に捕集される。
なお、上記担持粉末１は、図４、図５に示すごとく、触媒粒子１０の全表面を覆っていても（図４Ａ）、また触媒粒子１０の一部が露出した状態で覆っていてもよい（図４Ｂ）。
FIG. 5 shows growing particles 21 in which the nanocarbon material 20 is deposited and grown on the surfaces of the catalyst particles 10. As described above, the growth particles 21 are sent to the cyclone 6 together with the exhaust gas, and are collected in the collection tank 61.
As shown in FIGS. 4 and 5, the supported powder 1 may cover the entire surface of the catalyst particles 10 (FIG. 4A) or may cover the catalyst particles 10 with a part of the catalyst particles 10 exposed. (FIG. 4B).
また、上記流動層タンク３から加熱反応器５へ送入する原料ガス及び担持粉末１の量は、炭素化合物の種類、触媒粒子１０、触媒粒子１０の表面の担体の種類等によって変動するが、一般的には原料ガス１ｍ3当り、担持粉末１０7〜１０8個とすることが好ましい。 Further, the amount of the raw material gas and the supported powder 1 fed from the fluidized bed tank 3 to the heating reactor 5 varies depending on the type of the carbon compound, the catalyst particles 10, the type of the carrier on the surface of the catalyst particles 10, etc. Generally, it is preferable to use 10 7 to 10 8 supported powders per 1 m 3 of the raw material gas.
次に、本例の作用効果につき説明する。
本例においては、触媒粒子１０を上記のごとく担体１１によって被覆して担持粉末１としている。そして、上記担体１１は触媒粒子１０よりも密度が小さい。そのため、担持粉末１は触媒粒子自体よりも密度が小さくなり、上記流動層タンク３内において上記原料ガス２の導入により流動化し易い。
それ故、原料ガス２の導入速度等を調整することにより、担持粉末１を加熱反応器５に送入することができ、そのコントロールが容易となる。
Next, the function and effect of this example will be described.
In this example, the catalyst particles 10 are coated with the carrier 11 as described above to form the supported powder 1. The carrier 11 has a density lower than that of the catalyst particles 10. For this reason, the density of the supported powder 1 is smaller than that of the catalyst particles themselves, and is easily fluidized by introducing the raw material gas 2 in the fluidized bed tank 3.
Therefore, by adjusting the introduction speed of the raw material gas 2 and the like, the supported powder 1 can be fed into the heating reactor 5 and the control becomes easy.
また、流動層タンク３にある担持粉末１を加熱反応器５に送入するので、加熱反応器内における触媒粒子の流動性、分散性にも優れている。そのため、加熱反応器５を小型化することができる。
また、触媒粒子１０は、流動層タンク３内において担持粉末１の状態で流動化しているので、触媒粒子１０自体は何らの損傷もない状態で加熱反応器５内に送られ、触媒粒子本来の触媒活性を発揮できる。
Further, since the supported powder 1 in the fluidized bed tank 3 is fed into the heating reactor 5, the fluidity and dispersibility of the catalyst particles in the heating reactor are also excellent. Therefore, the heating reactor 5 can be reduced in size.
Further, since the catalyst particles 10 are fluidized in the state of the supported powder 1 in the fluidized bed tank 3, the catalyst particles 10 themselves are sent into the heating reactor 5 without any damage, It can exhibit catalytic activity.
また、触媒粒子１０を被覆している担体１１は、加熱反応器５内の部分燃焼時の温度によって熱分解し離散するので、加熱反応器内に送入された担持粉末は早急に触媒粒子１０のみとなる。そのため、部分燃焼によって発生した炭素は直ちに触媒粒子１０の表面に析出成長することができ、ナノカーボン構造に優れたナノカーボン材料を得ることができる。 In addition, since the carrier 11 covering the catalyst particles 10 is thermally decomposed and dispersed according to the temperature at the time of partial combustion in the heating reactor 5, the supported powder fed into the heating reactor is rapidly struck. It becomes only. Therefore, carbon generated by partial combustion can immediately precipitate and grow on the surface of the catalyst particle 10, and a nanocarbon material having an excellent nanocarbon structure can be obtained.
また、本例においては、触媒粒子１０が火炎の中を通過する僅かな時間（例えば０．０１〜０．２秒）に、ナノカーボン材料の前駆体が生成するため、ナノカーボンの構造が維持され易い。また、火炎温度は高温度（約１２００〜２２００℃）であるため、反応性の低いメタンを炭素化合物として用いた場合でも炭素蒸気が形成され易く、ナノカーボン材料が析出成長し易いという利点がある。 In this example, since the precursor of the nanocarbon material is generated in a short time (for example, 0.01 to 0.2 seconds) when the catalyst particles 10 pass through the flame, the structure of the nanocarbon is maintained. It is easy to be done. In addition, since the flame temperature is high (about 1200 to 2200 ° C.), even when methane having low reactivity is used as the carbon compound, carbon vapor is easily formed, and there is an advantage that the nanocarbon material is easily precipitated and grown. .
（実施例２）
次に、本発明の具体例につき、上記図１〜図５を用いて説明する。
本例において、上記炭素化合物としてはメタンガスを、触媒粒子１０としては平均粒径５〜６μｍのニッケル粒子を用いた。
触媒粒子としてのニッケル粒子の表面には、担体１１としてのＰＶＡ（ポリビニルアルコール）を、ボールミル混合によりコーティングし、平均粒径約５０μｍとした。
これにより、全体密度が１．５ｇ／ｃｍ3の担持粉末１を形成した。
(Example 2)
Next, specific examples of the present invention will be described with reference to FIGS.
In this example, methane gas was used as the carbon compound, and nickel particles having an average particle diameter of 5 to 6 μm were used as the catalyst particles 10.
The surface of the nickel particles as the catalyst particles was coated with PVA (polyvinyl alcohol) as the carrier 11 by ball mill mixing to have an average particle size of about 50 μm.
Thereby, the carrier powder 1 having an overall density of 1.5 g / cm 3 was formed.
また、酸素含有ガスとしては酸素ガスを用いた。
ナノカーボン材料の製造に当っては、まず加熱反応器５の電気ヒータ５５を約８００℃に加熱しておいた。また、流動層タンク３の多孔板３１の上には上記担持粉末１を入れ、この中に炭素化合物としてのメタンガスを含有する原料ガス２を送入し、担持粉末１を流動化させた。
そして、この流動化時において、原料ガス２の流動層タンク３内における流速を約０．０１ｍ／秒とした。これにより、担持粉末１の一部が流動化層３２よりも浮遊して、気泡流動層を形成し、原料ガス２と共に加熱反応器５に送入された。
Moreover, oxygen gas was used as the oxygen-containing gas.
In producing the nanocarbon material, first, the electric heater 55 of the heating reactor 5 was heated to about 800 ° C. The supported powder 1 was placed on the porous plate 31 of the fluidized bed tank 3, and the raw material gas 2 containing methane gas as a carbon compound was fed into the fluidized bed tank 3 to fluidize the supported powder 1.
At the time of fluidization, the flow rate of the raw material gas 2 in the fluidized bed tank 3 was set to about 0.01 m / second. As a result, a part of the supported powder 1 floated from the fluidized bed 32 to form a bubble fluidized bed, and was sent to the heating reactor 5 together with the raw material gas 2.
このとき担持粉末１は、原料ガス２の１ｍ3に当り、約３ｇ含まれていた。
そして、上記担持粉末１と原料ガス２とが加熱反応器５の反応筒５１内に送入され、酸素によって原料ガス２中の炭素化合物としてのメタンガスが部分燃焼された。
この部分燃焼時において、反応筒５１内の圧力は約７６０Ｔｏｒｒ、火炎温度は約２０００℃であった。上記原料ガス２に対する酸素ガスのモル比は１倍であった。
At this time, the supported powder 1 was about 3 g per 1 m 3 of the raw material gas 2.
Then, the supported powder 1 and the raw material gas 2 were fed into the reaction tube 51 of the heating reactor 5, and methane gas as a carbon compound in the raw material gas 2 was partially burned by oxygen.
During this partial combustion, the pressure in the reaction tube 51 was about 760 Torr, and the flame temperature was about 2000 ° C. The molar ratio of the oxygen gas to the raw material gas 2 was 1 time.
これにより、上記のごとく、担持粉末１の担体としてのＰＶＡは熱分解、燃焼して触媒粒子としてのニッケル粒子から離脱する。そして、露出したニッケル粒子の表面に、上記部分燃焼によって発生した炭素蒸気が析出成長してナノカーボン材料を形成した。
上記の火炎中において担持粉末１の状態から触媒粒子の露出、触媒粒子へのナノカーボン材料の析出成長までの時間は約１秒である。
As a result, as described above, PVA as the carrier of the supported powder 1 is thermally decomposed and burned and separated from the nickel particles as the catalyst particles. Then, carbon vapor generated by the partial combustion was deposited and grown on the exposed surfaces of the nickel particles to form a nanocarbon material.
In the flame, the time from the state of the supported powder 1 to the exposure of the catalyst particles and the deposition and growth of the nanocarbon material on the catalyst particles is about 1 second.
上記ナノカーボン材料は、上記成長粒子２１として捕集タンク６１により捕集された。
上記成長粒子における触媒粒子表面のナノカーボン材料をピンセットにより採取し、走査型顕微鏡（日立製作所（株）製、Ｓ−４５００）によりナノカーボン材料の状態を観察し、写真撮影した（図６）。
図６において、左側及び下側に示す写真は倍率３，０００倍の、右上は倍率１０，０００倍の上記顕微鏡写真である。
図６より知られるごとく、得られたナノカーボン材料はカーボンナノファイバー状の形状を示し、直径５０ｎｍ前後の優れたナノカーボン材料であった。
The nanocarbon material was collected by the collection tank 61 as the growing particles 21.
The nanocarbon material on the surface of the catalyst particles in the grown particles was collected with tweezers, and the state of the nanocarbon material was observed with a scanning microscope (S-4500, manufactured by Hitachi, Ltd.) and photographed (FIG. 6).
In FIG. 6, the photographs shown on the left side and the lower side are the above-mentioned micrographs at a magnification of 3,000 times, and the upper right is at a magnification of 10,000 times.
As can be seen from FIG. 6, the obtained nanocarbon material showed a carbon nanofiber-like shape and was an excellent nanocarbon material having a diameter of about 50 nm.
なお、上記流動層タンク内において、担持粉末の気泡流動層を形成する方法としては、一般に流動層形成設計に用いられる、フローレジームマップを利用する。このフローレジームマップは、レイノルズ数（Ｒｅp＝ｄpρgｕo／ηg）を横軸に、アルキメデス数［Ａｒ＝ｄp 3ρg（ρp−ρg）ｇ／ηg 2］を縦軸に用いたグラフで示されるものである。 In addition, as a method of forming the bubble fluidized bed of the supported powder in the fluidized bed tank, a flow regime map generally used for fluidized bed formation design is used. This flow regime map is based on the Reynolds number (Re p = d p ρ g u o / η g ) and the Archimedes number [Ar = d p 3 ρ g (ρ p −ρ g ) g / η g 2 ]. Is indicated by a graph using the vertical axis.
このグラフにおける気泡流動層形成領域において、担持粉末を加熱反応器へ送入する流動層を形成する。
上式における各記号は次のものを示す。
ｄp：粒子直径（ｍ）、ρs：粒子の密度（ｋｇ／ｍ3）、ρg：流動ガスの密度（ｋｇ／ｍ3）、ｇ：重力加速度（ｍ／ｓ2）、ηg：ガス粘度（Ｐａ・ｓ）、ｕo：流動層の空塔速度（ｍ／ｓ）
In the bubble fluidized bed formation region in this graph, a fluidized bed is formed in which the supported powder is fed into the heating reactor.
Each symbol in the above formula indicates the following.
d p : Particle diameter (m), ρ s : Particle density (kg / m 3 ), ρ g : Fluid gas density (kg / m 3 ), g: Gravitational acceleration (m / s 2 ), η g : Gas viscosity (Pa · s), u o : Superficial velocity of fluidized bed (m / s)
１ 担持粉末
１０ 触媒粒子
１１ 担体
１９ 火炎
２ 原料ガス
２１ 成長粒子
３ 流動層タンク
４ 酸素ガスパイプ
５ 加熱反応器
５１ 反応筒
DESCRIPTION OF SYMBOLS 1 Supported powder 10 Catalyst particle 11 Carrier 19 Flame 2 Raw material gas 21 Growing particle 3 Fluidized bed tank 4 Oxygen gas pipe 5 Heating reactor 51 Reaction cylinder
Claims (5)
上記触媒粒子は、該触媒粒子よりも密度が小さいと共に上記部分燃焼時の温度によって熱分解する性質を有する担体によって被覆された担持粉末の状態で、上記加熱反応器内に供給され、
上記担持粉末は、流動層タンク内において上記原料ガスの導入によって流動化されていると共に、その一部が上記原料ガスと共に上記加熱反応器内に送入され、
上記加熱反応器においては、上記原料ガスを上記酸素含有ガスによって部分燃焼させると共に該部分燃焼の火炎中に上記担持粉末を投入して、該担持粉末中の上記担体を熱分解させて触媒粒子の表面を露出させ、
ＣＶＤ反応により上記触媒粒子の表面にナノカーボン材料を析出成長させることを特徴とするナノカーボン材料の製造方法。 The raw material gas containing the carbon compound and the catalyst particles are fed into the heating reactor together with the oxygen-containing gas, and the carbon compound is partially burned in the heating reactor, and nanocarbon is formed on the surface of the catalyst particles by the CVD reaction. In a method of depositing and growing a material,
The catalyst particles are supplied into the heating reactor in a state of a supported powder having a density lower than that of the catalyst particles and coated with a carrier having a property of being thermally decomposed by the temperature at the time of partial combustion.
The supported powder is fluidized by introducing the raw material gas in a fluidized bed tank, and a part thereof is fed into the heating reactor together with the raw material gas,
In the heating reactor, the raw material gas is partially combusted by the oxygen-containing gas, and the supported powder is introduced into a flame of the partial combustion, and the carrier in the supported powder is thermally decomposed to form catalyst particles. Exposing the surface,
A method for producing a nanocarbon material, comprising depositing and growing a nanocarbon material on the surface of the catalyst particles by a CVD reaction.
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