JP6810408B2 - Catalyst carrier and its preparation method - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims description 226
- 238000002360 preparation method Methods 0.000 title claims description 15
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- 239000002245 particle Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 38
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- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000000969 carrier Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
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- 239000002041 carbon nanotube Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
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- 229910052786 argon Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- -1 and iron carbonyl Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
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- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 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 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RBUCAPSNRDZVKR-UHFFFAOYSA-N [Fe+]C1C=CC=C1 Chemical compound [Fe+]C1C=CC=C1 RBUCAPSNRDZVKR-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- FUFKFNZOGMJPAL-UHFFFAOYSA-N nickel(2+);hydrate Chemical compound O.[Ni+2] FUFKFNZOGMJPAL-UHFFFAOYSA-N 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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Description
本発明は、触媒担持体及びその調製方法に関するものであり、特には、繊維状炭素材料の合成に使用可能な触媒担持体及びその調製方法に関するものである。 The present invention relates to a catalyst carrier and a method for preparing the same, and more particularly to a catalyst carrier that can be used for synthesizing a fibrous carbon material and a method for preparing the catalyst carrier.
近年、導電性、熱伝導性および機械的特性に優れる材料として、繊維状炭素材料、特にはカーボンナノチューブ（以下、「ＣＮＴ」と称することがある。）等の繊維状炭素ナノ構造体が注目されている。ＣＮＴは、炭素原子により構成される筒状グラフェンシートからなり、その直径はナノメートルオーダーである。 In recent years, fibrous carbon materials, particularly fibrous carbon nanostructures such as carbon nanotubes (hereinafter, may be referred to as “CNT”), have attracted attention as materials having excellent conductivity, thermal conductivity, and mechanical properties. ing. CNTs consist of tubular graphene sheets composed of carbon atoms, the diameter of which is on the order of nanometers.
ここで、ＣＮＴ等の繊維状炭素ナノ構造体は、概して、製造コストが高いため他の材料よりも高価であった。このため、上述したような優れた特性を有するにもかかわらず、その用途は限られていた。さらに、近年、比較的高効率でＣＮＴ等を製造することができる製造方法として、触媒を用いたＣＶＤ（Chemical Vapor Deposition）法（以下、「触媒ＣＶＤ法」と称することがある）が用いられてきた。しかし、触媒ＣＶＤ法でも、製造コストを十分に低減することができなかった。 Here, fibrous carbon nanostructures such as CNTs are generally more expensive than other materials due to their high manufacturing costs. Therefore, although it has the above-mentioned excellent characteristics, its use is limited. Further, in recent years, a CVD (Chemical Vapor Deposition) method using a catalyst (hereinafter, may be referred to as a "catalytic CVD method") has been used as a production method capable of producing CNTs and the like with relatively high efficiency. It was. However, even with the catalytic CVD method, the manufacturing cost could not be sufficiently reduced.
そこで、基板の代わりに多孔質粒子、セラミックビーズなどを支持体として用いて、かかる支持体の上に触媒担体層が形成され、触媒担体層により触媒が担持された構成を有する触媒担持体により流動層を形成して、ＣＮＴを合成するＣＮＴ製造方法が開発されてきた（例えば、特許文献１参照）。具体的には、特許文献１では、支持体としてアルミナビーズを用い、アルミナビーズ上にＡｌ２Ｏ３により触媒担体層を形成し、かかる触媒担体層上にＦｅ触媒を担持させることにより形成した触媒担持体により流動層を形成してＣＮＴを合成する製造方法が開示されている。
Therefore, using porous particles, ceramic beads, or the like as a support instead of the substrate, a catalyst carrier layer is formed on the support, and the catalyst carrier has a structure in which the catalyst is supported by the catalyst carrier layer. A CNT manufacturing method for forming a layer and synthesizing a CNT has been developed (see, for example, Patent Document 1). Specifically, in
ここで、特許文献１に記載された製造方法には、触媒担持体により発揮されうる触媒能を一層高めるという点で改善の余地があった。
Here, the production method described in
そこで、本願発明は、触媒能の高い触媒担持体及びその調製方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a catalyst carrier having high catalytic ability and a method for preparing the same.
本発明者らは、上記課題を解決することを目的として鋭意検討を行った。その結果、本発明者らは、特定の成分を含有するセラミック粒子を支持体として、かかる支持体の表面上に、硫黄原子及び特定成分を含有する触媒部を形成してなる触媒担持体が、触媒能に優れることを新たに見出し、本願発明を完成させた。 The present inventors have conducted diligent studies for the purpose of solving the above problems. As a result, the present inventors have formed a catalyst carrier in which ceramic particles containing a specific component are used as a support and a catalyst portion containing a sulfur atom and the specific component is formed on the surface of the support. The present invention has been completed by newly discovering that it has excellent catalytic ability.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の触媒担持体は、支持体表面に触媒部を有する触媒担持体であって、前記支持体は、Ａｌ、Ｓｉ、及びＺｒの内の何れか１種以上の元素を含むセラミックス粒子であり、前記触媒部は、Ｆｅ、Ｃｏ、及びＮｉの内の何れか一種以上の元素と、Ｓ元素とを含むことを特徴とする。このような、特定の成分を含有するセラミック粒子を支持体として、かかる支持体の表面上に、硫黄原子及び特定成分を含有する触媒部を形成してなる触媒担持体によれば、繊維状炭素ナノ構造体を良好に合成することができる。 That is, the present invention aims to advantageously solve the above problems, and the catalyst carrier of the present invention is a catalyst carrier having a catalyst portion on the surface of the support, and the support is a catalyst carrier. Ceramic particles containing any one or more elements of Al, Si, and Zr, and the catalyst portion contains any one or more elements of Fe, Co, and Ni, and an S element. It is characterized by that. According to the catalyst carrier formed by forming a catalyst portion containing a sulfur atom and a specific component on the surface of the support using such ceramic particles containing a specific component as a support, fibrous carbon. Nanostructures can be synthesized well.
また、本発明の触媒担持体において、前記触媒部は、Ｓ元素の含有量が、Ｆｅ、Ｃｏ、及びＮｉ元素の合計質量を１００質量％として、１質量％以上であることが好ましい。触媒部におけるＳ元素の含有量が上記下限値以上であれば、一層良好に繊維状炭素ナノ構造体を合成することができる。 Further, in the catalyst carrier of the present invention, the content of the S element in the catalyst portion is preferably 1% by mass or more, with the total mass of Fe, Co, and Ni elements being 100% by mass. When the content of the S element in the catalyst portion is at least the above lower limit value, the fibrous carbon nanostructure can be synthesized more satisfactorily.
また、本発明の触媒担持体は、前記支持体の体積平均粒子径が、０．０５ｍｍ以上２．０ｍｍ以下であることが好ましい。支持体の体積平均粒子径Ｄ５０がかかる範囲内であれば、得られる触媒担持体の触媒能を一層高めることができ、結果的に、一層良好に繊維状炭素ナノ構造体を合成することができる。 Further, in the catalyst carrier of the present invention, the volume average particle diameter of the support is preferably 0.05 mm or more and 2.0 mm or less. When the volume average particle diameter D50 of the support is within such a range, the catalytic ability of the obtained catalyst carrier can be further enhanced, and as a result, the fibrous carbon nanostructure can be synthesized more satisfactorily. ..
また、本発明の触媒担持体は、前記支持体の見かけ密度が２．０ｇ／ｃｍ３以上であることが好ましい。支持体の見かけ密度が上記下限値以上であれば、繊維状炭素ナノ構造体の合成に用いた場合に、得られる繊維状炭素ナノ構造体を長尺化するとともに、直線性を高めることができる。 Further, in the catalyst carrier of the present invention, the apparent density of the support is preferably 2.0 g / cm 3 or more. When the apparent density of the support is equal to or higher than the above lower limit, the obtained fibrous carbon nanostructures can be lengthened and linearized when used for the synthesis of fibrous carbon nanostructures. ..
また、本発明の触媒担持体は、前記支持体表面に、Ａｌ、Ｓｉ、及びＭｇの内の何れか１種以上の元素を含む担体部を更に備えることが好ましい。触媒担持体がＡｌ、Ｓｉ、及びＭｇの内の何れか１種以上の元素を含む担体部を更に備えていれば、得られる触媒担持体の触媒能を一層向上させることができる。 Further, the catalyst carrier of the present invention preferably further includes a carrier portion containing any one or more elements of Al, Si, and Mg on the surface of the support. If the catalyst carrier further includes a carrier portion containing any one or more elements of Al, Si, and Mg, the catalytic ability of the obtained catalyst carrier can be further improved.
また、本発明の触媒担持体は、少なくとも前記触媒部を含む層を２層以上備えても良い。かかる触媒担持体は、例えば、使用済みの触媒担持体を支持体として再利用することにより形成しうる。 Further, the catalyst carrier of the present invention may include at least two or more layers including the catalyst portion. Such a catalyst carrier can be formed, for example, by reusing a used catalyst carrier as a support.
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の触媒担持体の調製方法は、調製器内に対象粒子を充填する工程（１）と、前記調製器内に、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含有する触媒原料気体を供給して、加熱環境下で、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含む触媒部を前記対象粒子表面上に形成する工程（２）とを含むことが好ましい。上記工程（１）及び工程（２）を経ることで、触媒能の高い触媒担持体を良好に製造することができる。 Further, the present invention aims to advantageously solve the above problems, and the method for preparing the catalyst carrier of the present invention includes a step (1) of filling the preparation device with the target particles and the above-mentioned preparation. A catalyst raw material gas containing one or more elements of Fe, Co, and Ni and S element is supplied into the vessel, and one or more of Fe, Co, and Ni are supplied in a heating environment. It is preferable to include the step (2) of forming the catalyst portion containing the element S and the element S on the surface of the target particle. By going through the above steps (1) and (2), a catalyst carrier having high catalytic ability can be satisfactorily produced.
また、本発明の触媒担持体の調製方法は、前記触媒原料気体が、Ｆｅ含有分子及び硫黄含有分子を含むことが好ましい。触媒原料気体が、Ｆｅ含有分子及び硫黄含有分子を含んでいれば、得られる触媒の触媒能を顕著に高めることができる。 Further, in the method for preparing a catalyst carrier of the present invention, it is preferable that the catalyst raw material gas contains Fe-containing molecules and sulfur-containing molecules. If the catalyst raw material gas contains Fe-containing molecules and sulfur-containing molecules, the catalytic ability of the obtained catalyst can be significantly enhanced.
また、本発明の触媒担持体の調製方法は、前記調製器内に、Ａｌ、Ｓｉ、及びＭｇの内の何れか１種以上の元素を含む担体原料気体を供給することを更に含むことが好ましい。担体原料気体がＡｌ、Ｓｉ、及びＭｇの内の何れか１種以上の元素を含んでいれば、得られる触媒担持体の触媒能を一層高めることができる。 Further, the method for preparing the catalyst carrier of the present invention further preferably further comprises supplying a carrier raw material gas containing any one or more elements of Al, Si, and Mg into the preparatory device. .. If the carrier raw material gas contains any one or more elements of Al, Si, and Mg, the catalytic ability of the obtained catalyst carrier can be further enhanced.
また、本発明の触媒担持体の調製方法は、前記担体原料気体がＡｌ含有分子を含むことが好ましい。担体原料気体がＡｌ含有分子を含んでいれば、支持体との親和性が向上し、触媒担持体としての性能を一層向上させることができることがある。 Further, in the method for preparing a catalyst carrier of the present invention, it is preferable that the carrier raw material gas contains Al-containing molecules. If the carrier raw material gas contains Al-containing molecules, the affinity with the support can be improved, and the performance as a catalyst carrier may be further improved.
また、本発明の触媒担持体の調製方法は、前記工程（２）を経た前記触媒担持体を、酸素元素含有ガスを含む雰囲気下でアニーリングする工程（３）を含むことが好ましい。かかる工程（３）を実施することで、調製された触媒担持体を用いて合成した繊維状炭素ナノ構造体を、小径化すると共に長尺化し得ることがある。 Further, the method for preparing the catalyst carrier of the present invention preferably includes a step (3) of annealing the catalyst carrier that has undergone the step (2) in an atmosphere containing an oxygen element-containing gas. By carrying out the step (3), the fibrous carbon nanostructure synthesized by using the prepared catalyst carrier may be reduced in diameter and lengthened.
本発明によれば、触媒能の高い触媒担持体及びその調製方法を提供することができる。 According to the present invention, it is possible to provide a catalyst carrier having high catalytic ability and a method for preparing the same.
以下、本発明の実施形態について詳細に説明する。
ここで、本発明の触媒担持体は、固定層、流動層、移動層を形成して繊維状ナノ構造体を含む繊維状炭素材料を製造するために好適に用いることができる。また、本発明の触媒担持体により合成可能な繊維状炭素ナノ構造体は、特に限定されることなく、カーボンナノチューブ、及びカーボンナノファイバー等でありうる。
Hereinafter, embodiments of the present invention will be described in detail.
Here, the catalyst carrier of the present invention can be suitably used for forming a fixed layer, a fluidized bed, and a moving layer to produce a fibrous carbon material containing fibrous nanostructures. Further, the fibrous carbon nanostructures that can be synthesized by the catalyst carrier of the present invention are not particularly limited, and may be carbon nanotubes, carbon nanofibers, and the like.
本発明の触媒担持体は、支持体表面に触媒部を有する触媒担持体であって、支持体は、Ａｌ、Ｓｉ、及びＺｒの内の何れか１種以上の元素を含むセラミックス粒子であり、触媒部は、Ｆｅ、Ｃｏ、及びＮｉの内の何れか一種以上の元素と、Ｓ元素とを含むことを特徴とする。かかる触媒担持体は、触媒能に優れる。 The catalyst carrier of the present invention is a catalyst carrier having a catalyst portion on the surface of the support, and the support is ceramic particles containing any one or more elements of Al, Si, and Zr. The catalyst unit is characterized by containing any one or more of Fe, Co, and Ni, and an S element. Such a catalyst carrier has excellent catalytic ability.
触媒担持体は、かかる触媒担持体を用いて固定層、流動層、又は移動層を形成し、炭素源を含む原料ガスを供給して所定の合成条件とした際に、担持した触媒上に繊維状炭素ナノ構造体を成長させうる物質である。 The catalyst carrier forms a fixed layer, a fluidized layer, or a moving layer using such a catalyst carrier, and when a raw material gas containing a carbon source is supplied to obtain predetermined synthetic conditions, fibers are placed on the supported catalyst. It is a substance capable of growing a state-like carbon nanostructure.
＜支持体＞
支持体は、触媒部及び担体部をその外側に形成しうる粒子である。ここで、「外側に形成する」とは、支持体の外表面に直接形成することだけでなく、支持体の外表面上に、例えば、任意で下地層を形成して、かかる下地層上に触媒部及び担体部を生成する構成も含む。なお、下地層とは、触媒部と支持体との間の密着性を向上させたり、触媒部及び担体部の形成反応を促進したりするための層である。下地層は、各種の金属の酸化物、窒化物、炭化物やそれらの複合材料により形成されうる触媒部を含まない層である。すなわち、後述する担体部と同様の組成の層であり、担体部よりなる担体層が、支持体表面上に直接形成された場合には、「下地層」と称されうる。なお、下地層の形成方法は、特に限定されることなく、例えば、所謂、「湿式」又は「乾式」の層形成方法を用いることができる。
ここで、本発明において、「粒子」とは、アスペクト比が５未満である粒子をいう。例えば、粒子の顕微鏡像上で、任意に選択した複数個の粒子について（長径／長径に直交する幅）の値を算出し、その平均値を対象とする粒子のアスペクト比とすることができる。
<Support>
The support is a particle capable of forming a catalyst portion and a carrier portion on the outside thereof. Here, "forming on the outside" means not only forming directly on the outer surface of the support, but also forming a base layer on the outer surface of the support, for example, optionally, on the base layer. It also includes a configuration for forming a catalyst portion and a carrier portion. The base layer is a layer for improving the adhesion between the catalyst portion and the support and for promoting the formation reaction of the catalyst portion and the carrier portion. The underlayer is a layer that does not contain a catalyst portion that can be formed of oxides, nitrides, carbides of various metals and composite materials thereof. That is, it is a layer having the same composition as the carrier portion described later, and when the carrier layer composed of the carrier portion is directly formed on the surface of the support, it can be called a “base layer”. The method for forming the base layer is not particularly limited, and for example, a so-called "wet" or "dry" layer forming method can be used.
Here, in the present invention, the "particle" means a particle having an aspect ratio of less than 5. For example, on a microscope image of particles, a value (width orthogonal to major axis / major axis) of a plurality of arbitrarily selected particles can be calculated, and the average value can be used as the aspect ratio of the target particles.
［支持体組成］
支持体は、Ａｌ、Ｓｉ、及びＺｒの内の何れか１種以上の元素を含むセラミックス粒子である。支持体であるセラミックス粒子は、Ａｌ、Ｓｉ、及びＺｒの内の何れか１種以上の元素を含む金属酸化物粒子であることが好ましい。好ましくは、支持体であるセラミックス粒子は、粒子状のアルミナであるアルミナビーズ、粒子状のシリカであるシリカビーズ、粒子状のジルコニアであるジルコニアビーズ、又は粒子状のムライトであるムライトビーズでありうる。中でも、支持体は、Ａｌを含むことが好ましく、アルミナ（Ａｌ２Ｏ３）ビーズが特に好ましい。
[Support composition]
The support is a ceramic particle containing at least one element of Al, Si, and Zr. The ceramic particles as the support are preferably metal oxide particles containing at least one element of Al, Si, and Zr. Preferably, the ceramic particles that are the support can be alumina beads that are particulate alumina, silica beads that are particulate silica, zirconia beads that are particulate zirconia, or mullite beads that are particulate mullite. .. Among them, the support preferably contains Al, and alumina (Al 2 O 3 ) beads are particularly preferable.
［体積平均粒子径Ｄ５０］
支持体の体積平均粒子径Ｄ５０は、０．０５ｍｍ以上が好ましく、０．１ｍｍ以上がより好ましく、２．０ｍｍ以下が好ましく、１．０ｍｍ以下がより好ましく、０．５ｍｍ以下がより好ましい。支持体の体積平均粒子径Ｄ５０がかかる範囲内であれば、得られる触媒担持体の触媒能を一層高めることができ、結果的に、一層良好に繊維状炭素ナノ構造体を合成することができる。また、本発明において、「支持体の体積平均粒子径」は、例えば、ＪＩＳ Ｚ８８２５等に準拠して測定することができ、レーザー回折法で測定された粒度分布（体積基準）において、小径側から計算した累積体積が５０％となる粒子径（Ｄ５０）を表す。
[Volume average particle size D50]
The volume average particle diameter D50 of the support is preferably 0.05 mm or more, more preferably 0.1 mm or more, preferably 2.0 mm or less, more preferably 1.0 mm or less, and even more preferably 0.5 mm or less. When the volume average particle diameter D50 of the support is within such a range, the catalytic ability of the obtained catalyst carrier can be further enhanced, and as a result, the fibrous carbon nanostructure can be synthesized more satisfactorily. .. Further, in the present invention, the "volume average particle size of the support" can be measured according to, for example, JIS Z8825 or the like, and in the particle size distribution (volume basis) measured by the laser diffraction method, from the small diameter side. It represents the particle size (D50) at which the calculated cumulative volume is 50%.
［密度］
また、支持体の見かけ密度は２．０ｇ／ｃｍ3以上が好ましく、２．５ｇ／ｃｍ3以上がより好ましく、８．０ｇ／ｃｍ3以下が好ましく、６．０ｇ／ｃｍ3以下がより好ましい。なお、支持体の「見かけ密度」とは、支持体が内部に空隙（閉気孔）をもつ粒子である場合には、その空隙を含めた単位容積当たりの質量を意味する。「支持体の見かけ密度」は、ピクノメーター法に従って測定することができる。支持体の見かけ密度が上記下限値以上であれば、繊維状炭素ナノ構造体の合成に用いた場合に、得られる繊維状炭素ナノ構造体を長尺化するとともに、直線性を高めることができる。
[density]
Further, the apparent density of the support is preferably 2.0 g / cm 3 or more, 2.5 g / cm 3 or more, and preferably 8.0 g / cm 3 or less, 6.0 g / cm 3 or less is more preferable. The "apparent density" of the support means the mass per unit volume including the voids when the support is particles having voids (closed pores) inside. The "apparent density of the support" can be measured according to the pycnometer method. When the apparent density of the support is equal to or higher than the above lower limit, the obtained fibrous carbon nanostructures can be lengthened and linearized when used for the synthesis of fibrous carbon nanostructures. ..
［触媒部］
触媒部は、繊維状炭素ナノ構造体の合成に寄与する触媒を含んでなる部分であり、触媒としての触媒金属微粒子を含む。触媒部はＦｅ、Ｃｏ、及びＮｉの内の何れか一種以上の元素と、Ｓ元素とを含む。さらに、触媒部は、Ｆｅ、Ｃｏ、及びＮｉ元素の合計質量を１００質量％として、Ｓ元素の含有量が、１質量％以上であることが好ましく、９質量％以上であることがより好ましい。触媒部におけるＳ元素の含有量が上記下限値以上であれば、得られる触媒担持体を用いて繊維状炭素ナノ構造体を合成した場合に、一層良好に繊維状炭素ナノ構造体を合成することができる。
「触媒部におけるＳ元素の含有量」は、Ｘ線蛍光分光法（ＸＲＦ）により測定することができる。
[Catalyst part]
The catalyst portion is a portion including a catalyst that contributes to the synthesis of fibrous carbon nanostructures, and contains catalyst metal fine particles as a catalyst. The catalyst portion contains any one or more elements of Fe, Co, and Ni, and an S element. Further, in the catalyst section, the total mass of Fe, Co, and Ni elements is 100% by mass, and the content of S element is preferably 1% by mass or more, and more preferably 9% by mass or more. When the content of the S element in the catalyst portion is equal to or higher than the above lower limit value, the fibrous carbon nanostructures can be synthesized more satisfactorily when the fibrous carbon nanostructures are synthesized using the obtained catalyst carrier. Can be done.
The "content of S element in the catalyst section" can be measured by X-ray fluorescence spectroscopy (XRF).
触媒部の形成に使用し得る触媒原料としては、例えば、単体硫黄、チオフェン、二硫化炭素等の硫黄含有分子を含む触媒材料、トリス(２，４−ペンタンジオナト)鉄(III)、ビス(シクロペンタジエニル)鉄（II）（以下、「フェロセン」とも称する）、塩化鉄（ＩＩＩ）、及び鉄カルボニル等のＦｅ含有分子を含む触媒材料、トリス(２，４−ペンタンジオナト)コバルト(III)、ビス(シクロペンタジエニル)コバルト(II)、及び塩化コバルト(II)等のＣｏ含有分子を含む触媒材料、及び、ビス(２，４−ペンタンジオナト)ニッケル(II)水和物、及びビス(シクロペタジエニル)ニッケル(II)、塩化ニッケル(II)等のＮｉ含有分子を含む触媒材料が挙げられる。なかでも、触媒原料気体が、Ｆｅ含有分子及び硫黄含有分子を含むことが好ましい。得られる触媒担持体の触媒能を顕著に高めうるからである。特に、硫黄含有分子としては、単体硫黄を用いることが好ましい。また、硫黄元素以外の供給源としての触媒材料としては、Ｆｅを約３０質量％含むフェロセンを用いることが好ましい。触媒部の形成効率が良好となるからである。 Examples of the catalyst raw material that can be used for forming the catalyst portion include catalyst materials containing sulfur-containing molecules such as simple sulfur, thiophene, and carbon disulfide, tris (2,4-pentandionato) iron (III), and bis ( Catalytic material containing Fe-containing molecules such as cyclopentadienyl iron (II) (hereinafter also referred to as "ferrocene"), iron (III) chloride, and iron carbonyl, tris (2,4-pentandionato) cobalt ( Catalytic materials containing Co-containing molecules such as III), bis (cyclopentadienyl) cobalt (II), and cobalt (II) chloride, and bis (2,4-pentandionato) nickel (II) hydrate. , And catalyst materials containing Ni-containing molecules such as bis (cyclopetadienyl) nickel (II) and nickel (II) chloride. Among them, it is preferable that the catalyst raw material gas contains Fe-containing molecules and sulfur-containing molecules. This is because the catalytic ability of the obtained catalyst carrier can be significantly enhanced. In particular, it is preferable to use elemental sulfur as the sulfur-containing molecule. Further, as a catalyst material as a supply source other than the sulfur element, it is preferable to use ferrocene containing about 30% by mass of Fe. This is because the formation efficiency of the catalyst portion is improved.
触媒部は支持体上に層状をなす触媒層として形成されていても良いし、後述する担体部と触媒部とが一つの層中に混在する混合層として支持体上に存在していても良い。 The catalyst portion may be formed as a layered catalyst layer on the support, or may exist on the support as a mixed layer in which the carrier portion and the catalyst portion described later are mixed in one layer. ..
触媒部は、支持体上に上記特定の成分を良好に付着させることができる限りにおいて特に限定されることなく、あらゆる方法により形成することができる。特に、触媒部は、後述する本発明の触媒担持体の調製方法を経て、良好に形成することができる。そして、触媒部の触媒金属換算厚みが、０．１ｎｍ以上１０ｎｍ以下であることが好ましく、０．３ｎｍ以上５．０ｎｍ以下であることがより好ましい。触媒部の触媒金属換算厚みは、本明細書の実施例に記載の方法により算出することができる。触媒金属換算厚みは、例えば、触媒材料ガスの組成、濃度、及び流量、さらには触媒部形成工程の時間を変更することにより変更することができる。なお、触媒部の厚みは、実施例に記載の方法により測定することができる。 The catalyst portion can be formed by any method without particular limitation as long as the specific component can be satisfactorily adhered to the support. In particular, the catalyst portion can be satisfactorily formed through the method for preparing a catalyst carrier of the present invention, which will be described later. The catalyst metal equivalent thickness of the catalyst portion is preferably 0.1 nm or more and 10 nm or less, and more preferably 0.3 nm or more and 5.0 nm or less. The catalyst metal equivalent thickness of the catalyst portion can be calculated by the method described in the examples of the present specification. The catalyst metal equivalent thickness can be changed, for example, by changing the composition, concentration, and flow rate of the catalyst material gas, as well as the time of the catalyst portion forming step. The thickness of the catalyst portion can be measured by the method described in Examples.
なお、上記段落にて説明した触媒部の触媒金属換算厚みの好適範囲は、特に、層状に形成した触媒部（即ち、触媒層）、及び、担体部と触媒部とが共存する混合層の双方について当てはまる。 In addition, the preferable range of the catalyst metal equivalent thickness of the catalyst part described in the above paragraph is particularly both the catalyst part (that is, the catalyst layer) formed in layers and the mixed layer in which the carrier part and the catalyst part coexist. Is true for.
そして、本発明の触媒担持体は、少なくとも触媒部を含む層を２層以上備えても良い。触媒担持体が「少なくとも触媒部を含む層を２層以上備える」とは、層状に形成された触媒層や、触媒部を含む混合層を２層以上備えることをいう。そして、「少なくとも触媒部を含む層を２層以上備える触媒担持体」は、例えば、繊維状炭素ナノ構造体の合成に用いた使用済触媒担持体を処理して、使用済触媒担持体上に、更なる触媒層や混合層を形成することで得ることができる。換言すると、本発明の触媒担持体は、使用済触媒担持体を再利用して形成した触媒担持体であっても良いし、未使用の支持体（いわゆる、無垢のセラミックス粒子）を用いて形成した触媒担持体であっても良い。
なお、本発明において、触媒部を含む層の層数は、電子顕微鏡により断面観察することや、Ar+イオンでスパッタリングしながらＸ線光電子分光法（ＸＰＳ）で組成分析をすることで確認することができる。
The catalyst carrier of the present invention may include at least two or more layers including a catalyst portion. The phrase "the catalyst carrier has at least two or more layers including a catalyst portion" means that the catalyst carrier includes two or more layers of a catalyst layer formed in a layered manner and a mixed layer including a catalyst portion. Then, the "catalyst carrier having at least two layers including a catalyst portion" is prepared, for example, by treating the used catalyst carrier used for synthesizing the fibrous carbon nanostructures on the used catalyst carrier. , It can be obtained by forming a further catalyst layer or a mixed layer. In other words, the catalyst carrier of the present invention may be a catalyst carrier formed by reusing a used catalyst carrier, or may be formed by using an unused support (so-called solid ceramic particles). It may be a catalyst carrier.
In the present invention, the number of layers including the catalyst portion can be confirmed by observing the cross section with an electron microscope or by performing composition analysis by X-ray photoelectron spectroscopy (XPS) while sputtering with Ar + ions. it can.
［担体部］
担体部は、触媒とともに用いて触媒を担持したりする等の助触媒的に機能する部分である。担体部を構成する材料としては、例えば、Ｓｉ、Ａｌ、及びＭｇの中から選択される１種以上の元素を含む材料により形成されうる。この場合、得られる触媒担持体の触媒能を一層高めることができる。例えば、担体部は、ＳｉＯ２、Ａｌ2Ｏ3やＭｇＯ等の酸化物、Ｓｉ3Ｎ4やＡｌＮ等の窒化物、及びＳｉＣ等の炭化物及びこれらの複合体を含む群より選択される少なくとも一種の化合物を含んで形成されていることが好ましい。さらに、担体部はＡｌを含むことが好ましく、例えば、Ａｌ2Ｏ3のようなアルミニウム酸化物により形成されることが好ましい。担体部がＡｌを含有すれば支持体との親和性が向上し、触媒担持体としての性能を一層向上させることができることがある。
[Carrier part]
The carrier portion is a portion that functions as a co-catalyst, such as being used together with a catalyst to support a catalyst. The material constituting the carrier portion can be formed of, for example, a material containing one or more elements selected from Si, Al, and Mg. In this case, the catalytic ability of the obtained catalyst carrier can be further enhanced. For example, the carrier portion is at least one selected from the group containing oxides such as SiO 2 , Al 2 O 3 and Mg O, nitrides such as Si 3 N 4 and Al N, carbides such as SiC, and composites thereof. It is preferable that the compound is formed. Further, the carrier portion preferably contains Al, and is preferably formed of, for example, an aluminum oxide such as Al 2 O 3 . If the carrier portion contains Al, the affinity with the support is improved, and the performance as a catalyst carrier may be further improved.
担体部は、支持体上に上記特定の成分を良好に付着させることができる限りにおいて特に限定されることなく、あらゆる方法により形成することができる。特に、担体部は、後述する本発明の触媒担持体の調製方法により、良好に形成することができる。 The carrier portion can be formed by any method without particular limitation as long as the above-mentioned specific component can be satisfactorily adhered to the support. In particular, the carrier portion can be satisfactorily formed by the method for preparing a catalyst carrier of the present invention, which will be described later.
［混合層］
混合層は、触媒部と担体部とが共存してなる層である。混合層では、触媒の担持が強固となる場合がある。混合層は、上記触媒部及び担体部にて列挙した各種成分と同様の成分を含みうる。混合層における触媒部と担体部の比率は、特に限定されることなく、例えば、５０体積％ずつでありうる。
[Mixed layer]
The mixed layer is a layer in which a catalyst portion and a carrier portion coexist. In the mixed layer, the support of the catalyst may be strong. The mixed layer may contain components similar to the various components listed in the catalyst section and the carrier section. The ratio of the catalyst portion and the carrier portion in the mixed layer is not particularly limited, and may be, for example, 50% by volume each.
（触媒担持体の調製方法）
本発明の触媒担持体の調製方法は、調製器内に対象粒子を充填する工程（１）と、調製器内に、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含有する触媒原料気体を供給して、加熱環境下で、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含む触媒部を対象粒子表面上に形成する工程（２）とを含む。かかる調製方法によれば、Ｆｅ、Ｃｏ、及びＮｉの内の何れか一種以上の元素と、Ｓ元素とを含む触媒部を有する触媒担持体を効率的かつ良好に製造することができる。さらに、本発明の触媒担持体の調製方法は工程（２）を経た触媒担持体を、酸素元素含有ガスを含む雰囲気下でアニーリングする工程（３）を含むことが好ましい。かかる工程（３）を実施することで、調製された触媒担持体を用いて合成した繊維状炭素ナノ構造体を、小径化すると共に長尺化し得る。
(Method for preparing catalyst carrier)
In the method for preparing the catalyst carrier of the present invention, the step (1) of filling the preparation device with the target particles and one or more elements of Fe, Co, and Ni and the S element are added to the preparation device. The step (2) of supplying the contained catalyst raw material gas and forming a catalyst portion containing one or more elements of Fe, Co, and Ni and S element on the surface of the target particles in a heating environment. including. According to such a preparation method, a catalyst carrier having a catalyst portion containing any one or more elements of Fe, Co, and Ni and an element S can be efficiently and satisfactorily produced. Further, the method for preparing the catalyst carrier of the present invention preferably includes a step (3) of annealing the catalyst carrier that has undergone the step (2) in an atmosphere containing an oxygen element-containing gas. By carrying out the step (3), the fibrous carbon nanostructures synthesized using the prepared catalyst carrier can be reduced in diameter and lengthened.
＜工程（１）＞
工程（１）は、調製器内に対象粒子を充填する充填工程である。調製器としては、特に限定されることなく、内部にて対象粒子の流動層を形成可能な流動層装置、内部にて対象粒子の固定層を形成可能な固定層装置等を用いることができる。そして、対象粒子としては、上述したような支持体や、使用済触媒担持体を使用しうる。これらに加えて、対象粒子として、使用済み触媒担持体や無垢のセラミックス粒子に対して、スパッタ法や湿式担持法等の既知の触媒担持体調製法を用いて担体層等の、触媒部を含まない層（即ち、いわゆる「下地層」）を付加して得た粒子を用いることもできる。
<Process (1)>
The step (1) is a filling step of filling the preparation device with the target particles. The preparator is not particularly limited, and a fluidized bed device capable of forming a fluidized bed of target particles inside, a fixed bed device capable of forming a fixed layer of target particles inside, and the like can be used. Then, as the target particles, a support as described above or a used catalyst carrier can be used. In addition to these, as the target particles, the used catalyst carrier and the solid ceramic particles do not contain a catalyst part such as a carrier layer by using a known catalyst carrier preparation method such as a sputtering method or a wet carrier method. Particles obtained by adding a layer (that is, a so-called "underlayer") can also be used.
＜工程（２）＞
工程（２）は、対象粒子表面上に所定の触媒部を形成する工程である。かかる工程では、上述したような触媒原料を含む気体を供給する。「触媒原料を含む気体」は、上述したような触媒原料のガスである触媒原料気体と、水素ガスやアルゴンガス等の不活性ガスとを含む気体でありうる。そして、かかる工程（２）は、例えば、４００℃以上１２００℃未満の加熱環境下で行う必要がある。
<Process (2)>
The step (2) is a step of forming a predetermined catalyst portion on the surface of the target particle. In such a step, a gas containing the catalyst raw material as described above is supplied. The "gas containing the catalyst raw material" may be a gas containing the catalyst raw material gas which is the gas of the catalyst raw material as described above and an inert gas such as hydrogen gas or argon gas. Then, the step (2) needs to be performed in a heating environment of, for example, 400 ° C. or higher and lower than 1200 ° C.
さらに、工程（２）において、或いは、工程（１）と（２）の間に、調製器内に、Ａｌ、Ｓｉ、及びＭｇの内の何れか１種以上の元素を含む担体原料気体を供給することが好ましい。工程（２）において担体原料気体を調製器内に供給すれば、混合層を形成することができる。また、工程（１）と（２）の間に担体原料気体を調製器内に供給すれば、担体層を形成してから、触媒層を形成することができる。担体原料気体の含みうる担体原料としては、上述した担体部を形成し得る化合物を形成可能であるあらゆる原料を用いることができる。中でも、担体原料気体として、Ａｌ含有アルコキシドを用いることが好ましく、アルミニウムイソプロポキシド（化学式：Ａｌ（Ｏ-ｉ-Ｐｒ）3［ｉ-Ｐｒはイソプロピル基−ＣＨ（ＣＨ３）２］）ガスを用いることが特に好ましい。担体原料のガスである担体原料気体と共に、任意で、水素ガスやアルゴンガス等の不活性ガス、及び酸素元素含有ガスを調製器内に供給しうる。酸素元素含有ガスとしては、空気、酸素、水蒸気、及び／又は、二酸化炭素等が挙げられる。 Further, in step (2) or between steps (1) and (2), a carrier raw material gas containing any one or more of Al, Si, and Mg is supplied into the preparation device. It is preferable to do so. If the carrier raw material gas is supplied into the preparation device in the step (2), a mixed layer can be formed. Further, if the carrier raw material gas is supplied into the preparation device between the steps (1) and (2), the carrier layer can be formed and then the catalyst layer can be formed. As the carrier raw material that can be contained in the carrier raw material gas, any raw material that can form the compound that can form the carrier portion described above can be used. Among them, it is preferable to use an Al-containing alkoxide as the carrier raw material gas, and an aluminum isopropoxide (chemical formula: Al (O-i-Pr) 3 [i-Pr is an isopropyl group-CH (CH 3 ) 2 ]) gas. It is particularly preferable to use it. An inert gas such as hydrogen gas or argon gas, and an oxygen element-containing gas can be optionally supplied into the preparation device together with the carrier raw material gas which is the carrier raw material gas. Examples of the oxygen element-containing gas include air, oxygen, water vapor, and / or carbon dioxide.
＜工程（３）＞
そして、工程（２）を経て得られた表面に所定の触媒部を有する触媒担持体は、アニーリング処理（工程（３））等を経て、所望の繊維状炭素ナノ構造体合成方法に用いられうる。ここで、アニーリング処理は、触媒担持体における触媒部又は触媒層の定着性を高めるために、触媒担持体を加熱する処理である。本発明の触媒担持体の調製方法においては、アニーリング処理を、酸素元素含有ガスを含む雰囲気下で実施してもよい。酸素元素含有ガスを含む雰囲気下でアニーリング処理を行うことで、得られる触媒担持体の触媒能を一層高めて、得られる繊維状炭素ナノ構造体を一層小径化且つ長尺化できる場合がある。なお、酸素元素含有ガスとしては、特に限定されることなく、例えば、空気、酸素、水蒸気、及び／又は、二酸化炭素等を挙げることができる。また、アニーリング処理の際の温度は、４００℃以上１２００℃以下であることが好ましい。
<Process (3)>
Then, the catalyst carrier having a predetermined catalyst portion on the surface obtained through the step (2) can be used in a desired fibrous carbon nanostructure synthesis method through an annealing treatment (step (3)) and the like. .. Here, the annealing treatment is a treatment of heating the catalyst carrier in order to improve the fixability of the catalyst portion or the catalyst layer in the catalyst carrier. In the method for preparing the catalyst carrier of the present invention, the annealing treatment may be carried out in an atmosphere containing an oxygen element-containing gas. By performing the annealing treatment in an atmosphere containing an oxygen element-containing gas, the catalytic ability of the obtained catalyst carrier may be further enhanced, and the obtained fibrous carbon nanostructure may be further reduced in diameter and lengthened. The oxygen element-containing gas is not particularly limited, and examples thereof include air, oxygen, water vapor, and / or carbon dioxide. The temperature during the annealing treatment is preferably 400 ° C. or higher and 1200 ° C. or lower.
なお、本発明の触媒担持体は、繊維状炭素ナノ構造体の合成に用いられた場合に、表面上にて繊維状炭素ナノ構造体を成長させる。このため、合成直後の触媒担持体は、表面に繊維状炭素ナノ構造体を有する。繊維状炭素ナノ構造体の合成プロセスの最終段階において、触媒担持体から繊維状炭素ナノ構造体が剥離されて回収されるが、回収された繊維状炭素ナノ構造体中に、表面に繊維状炭素ナノ構造体を有する触媒担持体が混在することがある。
なお、繊維状炭素ナノ構造体の合成方法としては、特に限定されることなく、本発明の触媒担持体をＣＶＤ（Chemical Vapor Deposition）法に従う合成方法における固定層触媒として、或いは、流動層合成法における流動層の形成媒体として用いる合成方法が挙げられる。
The catalyst carrier of the present invention grows fibrous carbon nanostructures on the surface when used for the synthesis of fibrous carbon nanostructures. Therefore, the catalyst carrier immediately after synthesis has a fibrous carbon nanostructure on the surface. In the final stage of the synthesis process of the fibrous carbon nanostructures, the fibrous carbon nanostructures are peeled off from the catalyst carrier and recovered, but the fibrous carbon on the surface in the recovered fibrous carbon nanostructures. Catalyst carriers with nanostructures may coexist.
The method for synthesizing the fibrous carbon nanostructure is not particularly limited, and the catalyst carrier of the present invention can be used as a fixed layer catalyst in a synthesis method according to a CVD (Chemical Vapor Deposition) method, or a fluidized bed synthesis method. A synthetic method used as a medium for forming a fluidized bed in
以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（実施例１）
＜触媒担持体の調製＞
支持体として、体積平均粒子径（Ｄ５０）０．３ｍｍのＡｌ２Ｏ３ビーズ（見かけ密度：３．９〜４．０ｇ／ｃｍ３）を用いた。Ａｌ２Ｏ３ビーズ７０ｇを、ドラムスパッタ装置の反応器内に載置し、アルゴンガス雰囲気下で、平均膜厚が１５ｎｍとなるようにアルミニウム層を成膜した。成膜後、反応器を大気開放して、アルミニウム層を自然酸化させて、下地層（担体層）である酸化アルミニウム層を形成した。
得られた下地層（担体層）を有する支持体を対象粒子として、調製器内に導入した（工程１）。調製器としては、流動層装置を用いた。流動層を形成する対象粒子に対して、触媒原料ガスとして、硫黄含有分子ガスである単体硫黄（和光純薬工業社製、「194-04651」）の蒸気と、Ｆｅ含有分子ガスであるフェロセン（和光純薬工業社製、「062-05985」）の蒸気とを、５０００ｓｃｃｍの窒素ガスに同伴して３００秒間供給して触媒担持体を得た（工程２）。また、調製器内の温度は８００℃とした。得られた触媒担持体について、走査型電子顕微鏡（日立ハイテクノロジーズ社製Ｓ−４８００）付属のエネルギー分散Ｘ線分光装置（アメテック社製、ＥＤＡＸ Ｇｅｎｅｓｉｓ）を用いて、特性Ｘ線強度を測定し、得られた特性Ｘ線強度測定値を予め得たＡｌ標準膜／Ｆｅ標準膜を用いて得た検量線と比較して、触媒部の換算厚みを測定したところ、触媒部のＦｅ換算厚みは３ｎｍであった。
そして、工程２を経た触媒担持体を、温度７５０℃で５分間、水素１０体積％、二酸化炭素１体積％、アルゴン８９体積％の気流を５００ｓｃｃｍで流通させる雰囲気下でアニーリング処理した（工程３）。
(Example 1)
<Preparation of catalyst carrier>
As a support, Al 2 O 3 beads (apparent density: 3.9 to 4.0 g / cm 3 ) having a volume average particle diameter (D50) of 0.3 mm were used. 70 g of Al 2 O 3 beads were placed in a reactor of a drum sputtering apparatus, and an aluminum layer was formed under an argon gas atmosphere so that the average film thickness was 15 nm. After the film formation, the reactor was opened to the atmosphere and the aluminum layer was naturally oxidized to form an aluminum oxide layer as a base layer (carrier layer).
The support having the obtained base layer (carrier layer) was introduced into the preparator as the target particles (step 1). A fluidized bed device was used as the preparer. For the target particles forming the fluidized bed, the vapor of elemental sulfur (manufactured by Wako Pure Chemical Industries, Ltd., "194-04651"), which is a sulfur-containing molecular gas, and ferrocene, which is an Fe-containing molecular gas, are used as catalyst raw materials. A catalyst carrier was obtained by supplying steam of "062-05985") manufactured by Wako Pure Chemical Industries, Ltd. with 5000 sccm of nitrogen gas for 300 seconds (step 2). The temperature inside the preparation device was 800 ° C. The characteristic X-ray intensity of the obtained catalyst carrier was measured using an energy dispersive X-ray spectroscope (EDAX Genesis, manufactured by Ametec) attached to a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies). When the converted thickness of the catalyst part was measured by comparing the obtained characteristic X-ray intensity measurement value with the calibration curve obtained by using the Al standard film / Fe standard film obtained in advance, the Fe equivalent thickness of the catalyst part was 3 nm. Met.
Then, the catalyst carrier that had undergone step 2 was subjected to an annealing treatment at a temperature of 750 ° C. for 5 minutes in an atmosphere in which an air flow of 10% by volume of hydrogen, 1% by volume of carbon dioxide, and 89% by volume of argon was circulated at 500 sccm (step 3). ..
＜ＣＮＴの合成＞
アニーリング処理（工程３）を経た触媒担持体に対して、水素１０体積％、二酸化炭素１体積％、アセチレン０．３体積％を含み、アルゴンガスでバランスしたガスを５００ｓｃｃｍで供給し、７５０℃で１０分間にわたりＣＮＴ合成を行った。合成後の触媒担持体をＳＥＭ観察した結果を図１に示す。視野内の略全ての触媒担持体の全面にて、図１に示したような長さ１００μｍ超のＣＮＴが成長していることを確認した。さらに、得られたＣＮＴについて、ラマンスペクトルを取得したところＲＢＭピークが確認された。よって、得られたＣＮＴ中に、単層ＣＮＴが含まれていたことが分かった。図１に得られた単層ＣＮＴのＳＥＭ画像を示す。
また、得られた触媒担持体について、ＸＲＦ分析によりＳ元素の含有量（Ｆｅ元素の含有量を１００質量％とする）を測定したところ、３６０質量％であった。Ｓ元素は触媒成分のＦｅに対して結合するだけでなく、触媒担体成分のＡｌに対しても結合していたと考えられる。
<Synthesis of CNT>
A gas containing 10% by volume of hydrogen, 1% by volume of carbon dioxide, and 0.3% by volume of acetylene and balanced with argon gas was supplied at 500 sccm to the catalyst carrier that had undergone the annealing treatment (step 3) at 750 ° C. CNT synthesis was performed for 10 minutes. The result of SEM observation of the catalyst carrier after the synthesis is shown in FIG. It was confirmed that CNTs having a length of more than 100 μm as shown in FIG. 1 were growing on the entire surface of almost all catalyst carriers in the field of view. Furthermore, when the Raman spectrum of the obtained CNT was acquired, an RBM peak was confirmed. Therefore, it was found that the obtained CNTs contained single-walled CNTs. FIG. 1 shows an SEM image of the obtained single-walled CNT.
Further, when the content of S element (the content of Fe element was 100% by mass) was measured by XRF analysis on the obtained catalyst carrier, it was 360% by mass. It is considered that the S element was not only bonded to Fe, which is a catalyst component, but also to Al, which is a catalyst carrier component.
（実施例２）
工程２におけるガス供給時間を１００秒間に変更したこと以外は実施例１と同様にして、触媒部のＦｅの平均膜厚を１ｎｍに制御した触媒担持体を得た。得られた触媒担持体を用いて、実施例１と同様にしてアニーリング処理（工程３）をし、ＣＮＴを合成した。合成後の触媒担持体をＳＥＭ観察した結果を図２（ａ）（ｂ）に示す。図２（ａ）より明らかなように、視野内の略全ての触媒担持体の全面にてＣＮＴが成長しており、図２（ｂ）より明らかなように、長さ１００μｍ超のＣＮＴが成長していたことが分かる。また、得られたＣＮＴのＴＥＭ画像を図３に示すが、単層ＣＮＴの生成が認められた。かかるＴＥＭ画像内の、４７本のＣＮＴについて層数をカウントしたところ、平均層数は３．４層であった。さらに、得られたＣＮＴについて、ラマンスペクトルを取得したところＲＢＭピークが確認された。よって、得られたＣＮＴ中に、単層ＣＮＴが含まれていたことが分かった。
(Example 2)
A catalyst carrier in which the average film thickness of Fe in the catalyst portion was controlled to 1 nm was obtained in the same manner as in Example 1 except that the gas supply time in step 2 was changed to 100 seconds. Using the obtained catalyst carrier, an annealing treatment (step 3) was carried out in the same manner as in Example 1 to synthesize CNTs. The results of SEM observation of the catalyst carrier after synthesis are shown in FIGS. 2 (a) and 2 (b). As is clear from FIG. 2 (a), CNTs are grown on the entire surface of almost all catalyst carriers in the field of view, and as is clear from FIG. 2 (b), CNTs having a length of more than 100 μm are grown. You can see that it was done. Moreover, the TEM image of the obtained CNT is shown in FIG. 3, and the formation of single-walled CNT was confirmed. When the number of layers was counted for 47 CNTs in the TEM image, the average number of layers was 3.4. Furthermore, when the Raman spectrum of the obtained CNT was acquired, an RBM peak was confirmed. Therefore, it was found that the obtained CNTs contained single-walled CNTs.
（実施例３）
工程２におけるガス供給時間を１５０秒間に変更したこと以外は実施例１と同様にして、触媒部のＦｅの平均膜厚を１．５ｎｍに制御した触媒担持体を得た。得られた触媒担持体を用いて、工程（３）でのアニーリング処理に際して、二酸化炭素を供給せず、不足分をアルゴンでバランスした以外は、実施例１と同様にしてＣＮＴを合成した。合成後の触媒担持体をＳＥＭ観察した結果を図４（ａ）（ｂ）に示す。図４（ａ）より明らかなように、視野内の略全ての触媒担持体の全面にてＣＮＴが成長しており、図４（ｂ）より明らかなように、長さ１００μｍ超のＣＮＴが成長していたことが分かる。さらに、得られたＣＮＴについて、ラマンスペクトルを取得したところＲＢＭピークが確認された。よって、得られたＣＮＴ中に、単層ＣＮＴが含まれていたことが分かった。
(Example 3)
A catalyst carrier in which the average film thickness of Fe in the catalyst portion was controlled to 1.5 nm was obtained in the same manner as in Example 1 except that the gas supply time in step 2 was changed to 150 seconds. Using the obtained catalyst carrier, CNTs were synthesized in the same manner as in Example 1 except that carbon dioxide was not supplied and the shortage was balanced with argon during the annealing treatment in step (3). The results of SEM observation of the catalyst carrier after synthesis are shown in FIGS. 4 (a) and 4 (b). As is clear from FIG. 4 (a), CNTs are grown on the entire surface of almost all catalyst carriers in the field of view, and as is clear from FIG. 4 (b), CNTs having a length of more than 100 μm are grown. You can see that it was done. Furthermore, when the Raman spectrum of the obtained CNT was acquired, an RBM peak was confirmed. Therefore, it was found that the obtained CNTs contained single-walled CNTs.
（実施例４）
支持体として、実施例１と同じアルミナビーズを用いた。該アルミナビーズを２４ｍＭアルミニウムイソプロポキシドのエタノール溶液に対して浸漬して乾燥し、下地層（担体層）である酸化アルミニウム層を形成した。そして、工程２におけるガス供給時間を１５０秒間に変更したこと以外は実施例１と同様にして、触媒部のＦｅの平均膜厚を１．５ｎｍに制御した触媒担持体を得た。得られた触媒担持体を用いて、工程（３）でのアニーリング処理に際して、二酸化炭素を供給せず、不足分をアルゴンでバランスした以外は、実施例１と同様にしてＣＮＴを合成した。合成後の触媒担持体をＳＥＭ観察した結果を図５（ａ）（ｂ）に示す。図５（ａ）より明らかなように、視野内の略全ての触媒担持体の全面にてＣＮＴが成長しており、図５（ｂ）より明らかなように、長さ１００μｍ超のＣＮＴが成長していたことが分かる。
(Example 4)
As the support, the same alumina beads as in Example 1 were used. The alumina beads were immersed in an ethanol solution of 24 mM aluminum isopropoxide and dried to form an aluminum oxide layer as a base layer (carrier layer). Then, a catalyst carrier was obtained in which the average film thickness of Fe in the catalyst portion was controlled to 1.5 nm in the same manner as in Example 1 except that the gas supply time in step 2 was changed to 150 seconds. Using the obtained catalyst carrier, CNTs were synthesized in the same manner as in Example 1 except that carbon dioxide was not supplied and the shortage was balanced with argon during the annealing treatment in step (3). The results of SEM observation of the catalyst carrier after synthesis are shown in FIGS. 5 (a) and 5 (b). As is clear from FIG. 5 (a), CNTs are grown on the entire surface of almost all catalyst carriers in the field of view, and as is clear from FIG. 5 (b), CNTs having a length of more than 100 μm are grown. You can see that it was done.
このように、所定のセラミックス粒子上にＳ元素及びＦｅ元素を含む触媒部を形成してなる触媒担持体によれば、比較的長尺（長さ１００μｍ以上）の繊維状炭素ナノ構造体を高頻度で合成可能であったことが分かる。 As described above, according to the catalyst carrier formed by forming the catalyst portion containing the S element and the Fe element on the predetermined ceramic particles, the fibrous carbon nanostructure having a relatively long length (length of 100 μm or more) is high. It can be seen that it was possible to synthesize with frequency.
本発明によれば、触媒能の高い触媒担持体及びその調製方法を提供することができる。 According to the present invention, it is possible to provide a catalyst carrier having high catalytic ability and a method for preparing the same.
Claims (11)
前記支持体は、Ａｌ、Ｓｉ、及びＺｒの内の何れか１種以上の元素を含むセラミックス粒子であり、
前記触媒部は、Ｆｅ、Ｃｏ、及びＮｉの内の何れか一種以上の元素と、Ｓ元素とを含む、
繊維状炭素ナノ構造体（コイル状炭素繊維を除く。）合成用の触媒担持体。 A catalyst carrier having a catalyst portion on the surface of the support.
The support is a ceramic particle containing at least one element of Al, Si, and Zr.
The catalyst portion contains one or more elements of Fe, Co, and Ni, and an S element.
Fibrous carbon nanostructures (excluding coiled carbon fibers) Catalyst carriers for synthesis .
前記調製器内に、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含有する触媒原料気体を供給して、加熱環境下で、Ｆｅ、Ｃｏ、及びＮｉの内の１種以上の元素とＳ元素とを含む触媒部を前記対象粒子表面上に形成する工程（２）と、
を含む、繊維状炭素ナノ構造体（コイル状炭素繊維を除く。）合成用の触媒担持体の調製方法。 Step (1) of filling the target particles in the preparatory unit and
A catalyst raw material gas containing one or more elements of Fe, Co, and Ni and an element S is supplied into the preparation device, and one of Fe, Co, and Ni is supplied under a heating environment. The step (2) of forming a catalyst portion containing a seed or more element and an S element on the surface of the target particle, and
A method for preparing a catalyst carrier for synthesizing fibrous carbon nanostructures (excluding coiled carbon fibers) .
The method for preparing a catalyst carrier according to any one of claims 7 to 10, further comprising a step (3) of annealing the catalyst carrier that has undergone the step (2) in an atmosphere containing an oxygen element-containing gas.
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