JP2012031015A - Method for producing carbon nanotube - Google Patents
Method for producing carbon nanotube Download PDFInfo
- Publication number
- JP2012031015A JP2012031015A JP2010172296A JP2010172296A JP2012031015A JP 2012031015 A JP2012031015 A JP 2012031015A JP 2010172296 A JP2010172296 A JP 2010172296A JP 2010172296 A JP2010172296 A JP 2010172296A JP 2012031015 A JP2012031015 A JP 2012031015A
- Authority
- JP
- Japan
- Prior art keywords
- dispersant
- metal particles
- carbon nanotube
- carrier
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 80
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 71
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- 239000002245 particle Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000007789 gas Substances 0.000 claims description 15
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- -1 transition metal compound salt Chemical class 0.000 claims description 7
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- 239000002994 raw material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 24
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- 230000001276 controlling effect Effects 0.000 abstract 2
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- 238000000034 method Methods 0.000 description 35
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- 239000001095 magnesium carbonate Substances 0.000 description 1
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- 150000002681 magnesium compounds Chemical class 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
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- 239000012256 powdered iron Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 1
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Images
Abstract
Description
本発明はカーボンナノチューブの製造方法に関する。 The present invention relates to a method for producing carbon nanotubes.
触媒化学気相成長法（ＣＣＶＤ法）によるカーボンナノチューブの合成法では、担体上に触媒金属を担持させた触媒体を用いる。触媒体の形状は粉末状、ゲル状、板状と様々である。用いる触媒量に対して得られるカーボンナノチューブの収量の点では、比表面積の大きい粉末状、エアロゾル状の担体を用いるのが良く、取り扱い易さの点では板状、粉末状の担体を用いることが好まれる。収量、扱い易さの両方のバランスを考えた場合、粉末状の担体使用が好まれる。また、担体の材質は有機物も無機物も使われているが、扱い易さと汎用性の点から無機物が用いられることが多い。 In the carbon nanotube synthesis method by the catalytic chemical vapor deposition method (CCVD method), a catalyst body in which a catalyst metal is supported on a support is used. The shape of the catalyst body is various such as powder, gel, and plate. In terms of the yield of carbon nanotubes obtained with respect to the amount of catalyst used, it is better to use a powdery or aerosol-like carrier having a large specific surface area, and in terms of ease of handling, a plate-like or powdery carrier should be used. Liked. In consideration of the balance between yield and ease of handling, the use of a powdery carrier is preferred. Moreover, although the organic substance and the inorganic substance are used as the material of the carrier, the inorganic substance is often used from the viewpoint of easy handling and versatility.
カーボンナノチューブ合成用の担持触媒を調製するために用いられる無機担体は、酸化物、水酸化物、その他炭酸塩などの金属塩、またはこれらの混合物が挙げられる（特許文献１）。しかしながら、特許文献１、２、３のように無機担体と触媒金属を溶媒中で単純に混ぜて乾燥する方法では触媒金属の分散性が低く、触媒製造時に活性金属が凝集粗粒子化する。このためカーボンナノチューブの生成する部位が減少し、アモルファスカーボンなどの不純物が多くなり高純度で高品質なカーボンナノチューブを収率よく得ることは難しい。また、得られるカーボンナノチューブも直径の太い多層カーボンナノチューブであることが多い。
Examples of the inorganic carrier used for preparing the supported catalyst for carbon nanotube synthesis include oxides, hydroxides, other metal salts such as carbonates, and mixtures thereof (Patent Document 1). However, as disclosed in
このような触媒製造時の活性金属の凝集粗粒子化を抑える手法として、特許文献４のように担体と親和性の高いアルカリ金属、アルカリ土類金属を凝集防止材として添加する方法や特許文献５のように粒径制御した活性金属を担体へ担持した後に、焼成により担体と活性金属との拡散層を形成し、該拡散層により活性金属の一部を覆うといった方法がある。 As a technique for suppressing the formation of coarse particles of active metal during the production of such a catalyst, a method of adding an alkali metal or alkaline earth metal having a high affinity with the carrier as a method for preventing aggregation as in Patent Document 4 or Patent Document 5 As described above, there is a method in which an active metal having a controlled particle size is supported on a carrier, a diffusion layer of the carrier and the active metal is formed by firing, and a part of the active metal is covered with the diffusion layer.
しかしながら、特許文献５の場合、拡散層によって活性金属の一部が覆われてしまうため添加した活性金属量に対して、実際にカーボンナノチューブの製造触媒として働いている活性金属量は少なく、非効率的なカーボンナノチューブの製造方法と考えられる。 However, in the case of Patent Document 5, since a part of the active metal is covered by the diffusion layer, the amount of the active metal actually acting as a catalyst for producing carbon nanotubes is less than the amount of the added active metal, which is inefficient. This is considered to be a typical method for producing carbon nanotubes.
本発明は、高純度で高品質なカーボンナノチューブ組成物を収率よく製造することができるカーボンナノチューブ組成物の製造方法を提供することを課題とする。 An object of the present invention is to provide a method for producing a carbon nanotube composition capable of producing a high-purity and high-quality carbon nanotube composition with high yield.
本発明者らは上記課題を解決するために鋭意検討を行った結果、分散剤被覆金属粒子を担体に担持し、その後分散剤を除去することにより担体上で金属同士が凝集粗粒子化することなく、担持前の金属粒子の粒径が良く反映された金属粒子触媒が得られる。該触媒をカーボンナノチューブ製造用触媒として用いることで、カーボンナノチューブ合成中においても活性金属が凝集粗粒子化することなく、活性金属成分がカーボンナノチューブの成長に効率よく働くこと、および本手法によりあらかじめ金属粒子の粒径を制御することにより高純度、高品質、かつ直径の細く、長いカーボンナノチューブを収率良く製造し得ることを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the metal particles are aggregated into coarse particles on the carrier by supporting the dispersant-coated metal particles on the carrier and then removing the dispersant. Thus, a metal particle catalyst in which the particle size of the metal particles before loading is well reflected can be obtained. By using the catalyst as a catalyst for producing carbon nanotubes, the active metal component efficiently works for the growth of carbon nanotubes without agglomerating coarse particles during carbon nanotube synthesis. The inventors have found that by controlling the particle size of the particles, high-purity, high-quality, thin-diameter, long carbon nanotubes can be produced with good yield, and the present invention has been achieved.
すなわち本発明は、下記の構成を有する。 That is, the present invention has the following configuration.
（１）分散剤被覆金属粒子を得る工程、（２）得られた分散剤被覆金属粒子を担体に担持する工程、（３）分散剤を除去する工程、により製造されるカーボンナノチューブ製造用触媒と原料ガスを接触させることを特徴とするカーボンナノチューブの製造方法。 A catalyst for producing carbon nanotubes produced by (1) a step of obtaining dispersant-coated metal particles, (2) a step of supporting the obtained dispersant-coated metal particles on a carrier, and (3) a step of removing the dispersant. A method for producing a carbon nanotube, comprising contacting a raw material gas.
本発明によれば、担体上に分散剤被覆金属粒子を担持し、その後分散剤を除去することにより担体上で金属同士を凝集粗粒子化せずに触媒を製造することが可能となる。かかる触媒を使用することにより、効率よくカーボンナノチューブを成長させ、高純度かつ高品質なカーボンナノチューブを収率よく得ることが可能となる。また、担体上の金属粒子は担持する分散剤被覆金属粒子の粒径をよく反映させることができるので、予め用いる金属粒子の粒径を制御しておくことにより、担体上の金属粒子の粒径も制御でき、さらに分散剤種及び量をコントロールすることによって担持する金属の粒径を調節することでカーボンナノチューブの直径を制御することも可能となる。 According to the present invention, it is possible to produce a catalyst without agglomerating coarse particles of metals on a carrier by supporting the dispersant-coated metal particles on the carrier and then removing the dispersant. By using such a catalyst, it is possible to efficiently grow carbon nanotubes and to obtain high-purity and high-quality carbon nanotubes with a high yield. In addition, since the metal particles on the carrier can well reflect the particle size of the dispersant-coated metal particles to be supported, the particle size of the metal particles on the carrier can be controlled by controlling the particle size of the metal particles used in advance. Further, the diameter of the carbon nanotube can be controlled by adjusting the particle size of the supported metal by controlling the kind and amount of the dispersant.
本発明で用いるカーボンナノチューブ製造用触媒は、分散剤被覆金属粒子を担体に担持し、その後分散剤を除去してなるものである。
本発明に用いる分散剤被覆金属粒子の合成法としては、溶液中で行う湿式法、熱分解法、共沈法等が挙げられる。この中で湿式法による金属粒子の調製は、最も簡便で良く用いられる。
The catalyst for producing carbon nanotubes used in the present invention is obtained by supporting a dispersant-coated metal particle on a carrier and then removing the dispersant.
Examples of the method for synthesizing the dispersant-coated metal particles used in the present invention include a wet method performed in a solution, a thermal decomposition method, a coprecipitation method, and the like. Among these, the preparation of metal particles by a wet method is the simplest and often used.
湿式法は、分散剤存在下における金属イオンの還元による０価金属原子からの凝集制御による手法である。金属イオンの還元に用いる還元剤としては、水素、アルコール、アルデヒド、ヘミアセタール、ヘミケタール構造を有しているもの、さらにポリオール、水素化ホウ素塩、ヒドラジン、クエン酸、γ線、ＵＶ、超音波などが挙げられる。好ましくはポリオールを用いる。ポリオールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、トリメチレングリコール、ヘキサデカンジオール、さらにグルコース、スクロース、グルコン酸、カルボキシメチルセルロースアンモニウムなどの糖類が例示される。また、下記にも述べるがこれらの還元剤は金属イオンの還元だけでなく、生成金属粒子の分散剤の機能を有していても良い。さらに、溶媒の役割を担っても良い。 The wet method is a method based on controlling aggregation from zero-valent metal atoms by reduction of metal ions in the presence of a dispersant. Reducing agents used for reducing metal ions include hydrogen, alcohols, aldehydes, hemiacetals, hemiketal structures, polyols, borohydrides, hydrazine, citric acid, gamma rays, UV, ultrasound, etc. Is mentioned. A polyol is preferably used. Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, trimethylene glycol, hexadecanediol, and sugars such as glucose, sucrose, gluconic acid, and carboxymethylcellulose ammonium. In addition, as will be described below, these reducing agents may have a function of a dispersing agent for generated metal particles as well as reduction of metal ions. Further, it may serve as a solvent.
前記金属としては、特に限定されないが、好ましくは３〜１２族の金属、特に好ましくは、５〜１１族の金属が用いられる。中でも、Ｖ、Ｍｏ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｐｄ、Ｐｔ、Ｒｈ、Ｗ、Ｃｕ等が好ましい。さらに好ましくは、８〜１０族のＦｅ、ＣｏおよびＮｉであり、最も好ましいのはＦｅである。また、これらの金属の平均粒径は１０ｎｍ以下が望ましい。特に、２層カーボンナノチューブを得たい場合、好ましくは１〜１０ｎｍ、さらに好ましくは１〜５ｎｍである。 Although it does not specifically limit as said metal, Preferably a 3-12 group metal, Most preferably, a 5-11 group metal is used. Among these, V, Mo, Mn, Fe, Co, Ni, Pd, Pt, Rh, W, Cu and the like are preferable. More preferred are group 8 to group 10 Fe, Co and Ni, and most preferred is Fe. The average particle size of these metals is preferably 10 nm or less. In particular, when it is desired to obtain a double-walled carbon nanotube, the thickness is preferably 1 to 10 nm, more preferably 1 to 5 nm.
金属の前駆体としては、例えば、ギ酸塩、酢酸塩、トリフルオロ酢酸塩、クエン酸アンモニウム塩、硝酸塩、硫酸塩、ハロゲン化物塩などの有機塩または無機塩、エチレンジアミン４酢酸錯体やアセチルアセトナート錯体のような錯塩などが挙げられる。
前記分散剤としては、金属粒子の被覆が可能であれば特に制限はないが、好ましい分散剤として高分子分散剤が挙げられる。
Examples of the metal precursor include organic salts or inorganic salts such as formate, acetate, trifluoroacetate, ammonium citrate, nitrate, sulfate, halide salt, ethylenediaminetetraacetate complex and acetylacetonate complex. And complex salts such as
The dispersant is not particularly limited as long as the metal particles can be coated, and a preferable dispersant is a polymer dispersant.
分散剤とは分子内に疎水性と親水性部位の相反する性質を有しており、液体中に分散しにくい無機、有機顔料などの固体粒子を均一に分散させて、固体粒子の沈降や凝集を防止する薬剤のことを指す。高分子の分散剤は、一分子が多数の点で金属粒子表面に吸着しているため脱着が起こりにくく、又分散剤が金属粒子を覆うような形態で存在するため金属粒子同士の凝集粗粒子化も起こりにくいという点で好ましい。さらに好ましくは、分子構造中に酸素原子を有する高分子分散剤である。また、高分子は生成する金属粒子の粒径、形状の制御においても重要な役割を果たす。 Dispersants have the opposite nature of hydrophobic and hydrophilic parts in the molecule, and solid particles such as inorganic and organic pigments that are difficult to disperse in the liquid are uniformly dispersed, so that the solid particles settle or aggregate. It refers to drugs that prevent Polymeric dispersants are adsorbed on the surface of metal particles at a number of points, making it difficult for desorption, and the dispersant is present in a form that covers the metal particles. It is preferable in that it does not easily occur. More preferred is a polymer dispersant having an oxygen atom in the molecular structure. Polymers also play an important role in controlling the particle size and shape of the metal particles produced.
分子構造中に酸素原子を含む高分子分散剤は、無機担体との相互作用が強い。そのため担体への分散剤被覆金属粒子の担持工程においてはもちろん、分散剤除去工程においても金属粒子の担体への吸着が金属粒子同士の凝集粗粒子化よりもはやく起こるため、担体上で金属粒子を安定に保持できる。 The polymer dispersant containing an oxygen atom in the molecular structure has a strong interaction with the inorganic carrier. For this reason, in the step of supporting the dispersant-coated metal particles on the carrier, as well as in the step of removing the dispersant, the adsorption of the metal particles to the carrier no longer occurs than the aggregation and coarsening of the metal particles. It can be held stably.
分子構造中に酸素を含む分散剤としては、ポリエチレングリコール、ポリビニルエーテル、ポリビニルピロリドン、ポリビニルアルコール、さらにグルコース、スクロース、カルボキシメチルセルロースなどの糖類、グルコン酸などが例示される。この中で特に好ましくは、カルボキシル基を有するものである。例えば、上記のポリマーの末端や側鎖に酸化反応やグリニャール試薬をはじめとした求核剤とドライアイスとの反応等を利用しカルボキシ基を導入して、カルボキシル基を有する高分子分散剤とすることもできる。また、これらの分散剤は金属粒子の保護だけでなく、還元剤の機能を有していても良い。 Examples of the dispersant containing oxygen in the molecular structure include polyethylene glycol, polyvinyl ether, polyvinyl pyrrolidone, polyvinyl alcohol, saccharides such as glucose, sucrose, and carboxymethyl cellulose, and gluconic acid. Among these, particularly preferred are those having a carboxyl group. For example, a polymer dispersant having a carboxyl group is introduced by introducing a carboxy group into the terminal or side chain of the above polymer by utilizing a reaction of a nucleophilic agent such as an oxidation reaction or a Grignard reagent with dry ice. You can also. These dispersants may have a function of a reducing agent as well as protection of metal particles.
得られる分散剤被覆金属粒子の粒径は、金属前駆体と高分子分散剤のモル比によって決まる。金属前駆体に対して高分子分散剤のモル比が大きいと、分散剤被覆金属粒子の粒径は小さくなる傾向にある。 The particle size of the resulting dispersant-coated metal particles is determined by the molar ratio of the metal precursor to the polymer dispersant. When the molar ratio of the polymer dispersant to the metal precursor is large, the particle diameter of the dispersant-coated metal particles tends to be small.
溶解性などの取り扱いの観点から、用いる高分子の数平均分子量は１００万以下が好ましく、さらに好ましくは５０万以下である。数平均分子量が小さい分散剤を用いた場合でも、粒径の小さい金属粒子の調製は可能である。しかしながら、調製後の安定性の点で数平均分子量の大きい分散剤を用いることが好ましい。ここで数平均分子量はゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定し、ポリスチレン換算により求めた分子量である。 From the viewpoint of handling such as solubility, the number average molecular weight of the polymer used is preferably 1,000,000 or less, more preferably 500,000 or less. Even when a dispersant having a small number average molecular weight is used, metal particles having a small particle size can be prepared. However, it is preferable to use a dispersant having a large number average molecular weight in terms of stability after preparation. Here, the number average molecular weight is a molecular weight determined by gel permeation chromatography (GPC) and determined in terms of polystyrene.
上記の還元剤、金属前駆体、分散剤を組み合わせ、これらを大気下またはオートクレーブなどの密閉系中で加熱還流を行う。この際の加熱温度は、該金属前駆体を構成する金属イオンの還元温度以上であればよい。例えば、還元剤としてトリエチレングリコール、金属前駆体として塩化鉄（ＩＩＩ）、分散剤として両末端にカルボキシル基を有するポリエチレングリコールを用いた場合には、酸化鉄粒子を得ることができる。反応条件は大気下の場合、加熱温度は好ましくは１００℃〜３００℃であり、さらに好ましくは２５０℃〜３００℃である。 The above reducing agent, metal precursor, and dispersant are combined, and these are heated to reflux in the air or in a closed system such as an autoclave. The heating temperature at this time should just be more than the reduction temperature of the metal ion which comprises this metal precursor. For example, iron oxide particles can be obtained when triethylene glycol is used as the reducing agent, iron (III) chloride is used as the metal precursor, and polyethylene glycol having carboxyl groups at both ends is used as the dispersing agent. When the reaction conditions are atmospheric, the heating temperature is preferably 100 ° C to 300 ° C, more preferably 250 ° C to 300 ° C.
温度が低すぎると還元終了までに時間がかかる、また温度が高すぎると還元速度は速いがその制御が困難となる。加熱時間は、１〜４８時間が好ましく、さらに好ましくは２４〜４８時間である。 If the temperature is too low, it takes time to complete the reduction. If the temperature is too high, the reduction rate is fast, but its control becomes difficult. The heating time is preferably 1 to 48 hours, more preferably 24 to 48 hours.
得られたポリエチレングリコール被覆酸化鉄粒子は、アセトン、アルコールなどの極性溶媒を用い洗浄してもよい。さらに遠心分離などにより沈降させることで該粒子を単離することができる。単離後、溶媒を除去することでパウダー状の酸化鉄粒子を得ることもできる。単離された酸化鉄粒子は、水や有機溶媒中に再分散させることが可能である。
還元剤、金属前駆体、分散剤を用いる場合においても上記に準じて実施することが可能である。
The obtained polyethylene glycol-coated iron oxide particles may be washed using a polar solvent such as acetone or alcohol. Further, the particles can be isolated by sedimentation by centrifugation or the like. Powdered iron oxide particles can also be obtained by removing the solvent after isolation. The isolated iron oxide particles can be redispersed in water or an organic solvent.
Even when a reducing agent, a metal precursor, or a dispersing agent is used, it can be carried out according to the above.
還元剤は金属前駆体に対しモル比で等量以上添加することが好ましい。さらに好ましくは、金属前駆体に対して過剰量添加である。また、生成する分散剤被覆金属粒子の粒径は、添加する金属前駆体と分散剤のモル比によって決まるため、そのバランスが重要である。小さい粒子が得たい場合、分散剤は金属前駆体に対してモル比で等量以上の添加が好ましい。さらに好ましくは金属前駆体に対して過剰量添加である。このような観点から適宜最適化を行えばよい。 The reducing agent is preferably added in an equivalent amount or more in molar ratio to the metal precursor. More preferably, an excessive amount is added to the metal precursor. Further, since the particle diameter of the produced dispersant-coated metal particles is determined by the molar ratio of the metal precursor to be added and the dispersant, the balance is important. When it is desired to obtain small particles, the dispersant is preferably added in an equivalent amount or more in molar ratio with respect to the metal precursor. More preferably, an excessive amount is added to the metal precursor. Optimization may be appropriately performed from such a viewpoint.
上記で合成した分散剤被覆金属粒子の金属部分の形状および平均粒径は透過型電子顕微鏡（ＴＥＭ）（例えば、日本電子社製ＪＥＭ−２１００）により評価することができる。例えば、倍率２５０，０００倍の観察写真より５０個の金属粒子の粒径を相加平均したものを平均粒径とする。なお、ＴＥＭ像が真円形でない場合、長径を測定するものとする。また、1視野中に５０個の金属粒子がない場合は、視野数を増やしても良い。 The shape and average particle diameter of the metal part of the dispersant-coated metal particles synthesized above can be evaluated by a transmission electron microscope (TEM) (for example, JEM-2100 manufactured by JEOL Ltd.). For example, the average particle diameter is obtained by arithmetically averaging the particle diameters of 50 metal particles from an observation photograph at a magnification of 250,000 times. When the TEM image is not a perfect circle, the major axis is measured. If there are no 50 metal particles in one field of view, the number of fields of view may be increased.
該分散剤被覆金属粒子は、Ｘ線回折測定（例えば、理学社製ＲＩＮＴ２１００ＵｌｔｉｍａＰＬ）により同定することができる。Ｘ線回折測定は粉末Ｘ線回折装置に粉末試料を設置した後に、２θ＝１．５°から９０°まで操作し分析を行う。Ｘ線源はＣｕＫα線である。ステップ幅は０．０１０°、計測時間は１．０秒である。例えば、酸化鉄粒子の場合、（１１１）、（２２０）、（３１１）、（４００）、（４２２）、（５１１）、（４４０）面の回折が得られる。また、結晶子径はＳｃｈｅｒｒｅｒの式を用い評価することもできる。 The dispersant-coated metal particles can be identified by X-ray diffraction measurement (for example, RINT2100UltimaPL manufactured by Rigaku Corporation). In the X-ray diffraction measurement, a powder sample is set in a powder X-ray diffractometer, and then analysis is performed by operating from 2θ = 1.5 ° to 90 °. The X-ray source is CuKα ray. The step width is 0.010 ° and the measurement time is 1.0 second. For example, in the case of iron oxide particles, diffraction of (111), (220), (311), (400), (422), (511), and (440) planes is obtained. The crystallite diameter can also be evaluated using Scherrer's equation.
上記で合成した分散剤被覆金属粒子における分散剤と金属粒子の割合は、示差熱分析装置（例えば、島津製作所製 ＴＧＡ-６０）により求めることができる。試料約１ｍｇを装置に設置し、室温から９００℃の範囲、大気中又は窒素雰囲気下、１０℃／ｍｉｎで昇温した時の重量変化により評価することができる。上記で評価される分散剤被覆金属粒子における分散剤と金属粒子の割合は、分散剤被覆金属粒子合成時の仕込みのモル比を反映することが好ましい。 The ratio of the dispersant to the metal particles in the dispersant-coated metal particles synthesized above can be determined by a differential thermal analyzer (for example, TGA-60 manufactured by Shimadzu Corporation). About 1 mg of the sample is placed in the apparatus, and the evaluation can be made based on the change in weight when the temperature is raised from room temperature to 900 ° C. in the air or in a nitrogen atmosphere at 10 ° C./min. It is preferable that the ratio of the dispersant to the metal particles in the dispersant-coated metal particles evaluated above reflects the molar ratio of preparation during the synthesis of the dispersant-coated metal particles.
担体に上記粒径を制御した分散剤被覆金属粒子を担持する方法は、特に限定されない。例えば、分散剤被覆金属粒子を分散させた水溶液中またはメタノールやエタノールなどの非水溶液中に、担体を含浸し、攪拌や超音波などにより充分に分散混合した後、乾燥させる。さらに大気、窒素、水素、不活性ガスおよびそれらの混合ガスから選ばれたガス中または真空中で加熱することができ、４００〜１０００℃の範囲で加熱することが好ましく、４００〜７００℃の範囲がさらに好ましい。加熱時間は１〜５時間の範囲で行うことが好ましい。 There is no particular limitation on the method of supporting the dispersant-coated metal particles with the above particle size controlled on the carrier. For example, the carrier is impregnated in an aqueous solution in which the dispersant-coated metal particles are dispersed or in a non-aqueous solution such as methanol or ethanol, sufficiently dispersed and mixed by stirring or ultrasonic waves, and then dried. Furthermore, it can be heated in a gas selected from the atmosphere, nitrogen, hydrogen, an inert gas and a mixed gas thereof or in a vacuum, and is preferably heated in the range of 400 to 1000 ° C, and in the range of 400 to 700 ° C. Is more preferable. The heating time is preferably 1 to 5 hours.
該加熱中に担体への触媒金属の担持と同時に、分散剤を除去することができる。上記加熱範囲内で分散剤が除去できない場合は、さらに加熱処理を行うことで残存した分散剤を除去することができる。 During the heating, the dispersing agent can be removed simultaneously with the loading of the catalyst metal on the support. When the dispersant cannot be removed within the above heating range, the remaining dispersant can be removed by further heat treatment.
前記担体としては、酸化物（例えば、シリカ、アルミナ、シリカ-アルミナ混合物、酸化マグネシウム、酸化カルシウム、酸化チタン、酸化セリウム、ゼオライト）、水酸化物（例えば、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、水酸化セシウム、水酸化チタン、水酸化ランタン）、その他炭酸塩（例えば、炭酸カルシウム、炭酸マグネシウム、炭酸アルミニウム、炭酸セシウム、炭酸チタン、炭酸ランタン）などの金属塩、またはこれらの混合物が挙げられる。この中でも特に酸化物または水酸化物が好ましい。さらに好ましくは、マグネシウム化合物から成るものがよい。これらは、市販品を使用しても良いし、合成したものを使用しても良い。 Examples of the carrier include oxides (eg, silica, alumina, silica-alumina mixture, magnesium oxide, calcium oxide, titanium oxide, cerium oxide, zeolite), hydroxides (eg, calcium hydroxide, magnesium hydroxide, hydroxide) Metal salts such as aluminum, cesium hydroxide, titanium hydroxide, lanthanum hydroxide) and other carbonates (for example, calcium carbonate, magnesium carbonate, aluminum carbonate, cesium carbonate, titanium carbonate, lanthanum carbonate), or a mixture thereof. It is done. Among these, an oxide or a hydroxide is particularly preferable. More preferably, it is made of a magnesium compound. These may be commercially available products or synthesized ones.
分散剤被覆金属粒子と担体の使用量は、分散剤被覆金属粒子中の金属成分量が担体の重量に対して０．１〜１０ｗｔ％となるよう混合しておくことが好ましい。担体に担持する分散剤被覆金属粒子中の金属成分量が上記範囲よりも大きい場合には、分散剤で金属粒子を被覆しても担体上で金属粒子同士の凝集粗粒子化が起こりやすくなり、得られるカーボンナノチューブも太くなる傾向にある。 The amount of the dispersant-coated metal particles and the carrier used is preferably mixed so that the amount of the metal component in the dispersant-coated metal particles is 0.1 to 10 wt% with respect to the weight of the carrier. When the amount of the metal component in the dispersant-coated metal particles supported on the carrier is larger than the above range, even if the metal particles are coated with the dispersant, aggregation and coarsening of the metal particles are likely to occur on the carrier. The resulting carbon nanotubes also tend to be thick.
本発明において、担体に担持した遷移金属粒子の分散性は、金属分散度測定装置（例えば日本ベル社製金属分散度測定装置（ＢＥＬ−ＭＥＴＡＬ−１））を用いて、該触媒体中の遷移金属粒子による単位体積あたりの水素吸着量を指標とすることができる。水素吸着はパルス法で行う金属分散度測定である。測定条件を以下記す。測定用石英管中にカーボンナノチューブ製造用触媒体を約０．３ｇ導入し、測定系に接続する。次にＮ2雰囲気下３０分間で９００℃まで加熱し、その後４００℃まで放冷する。４００℃の状態で１時間安定化させた後、５％Ｈ２/Ｎ2ガスを０．１５ｃｍ３（Ｈ２：３．３×１０−７ｍｏｌ）の量で２５回パルスする。触媒学会参照触媒委員会金属分散度測定マニュアルに準拠した解析を行い、触媒体の水素吸着量から触媒１ｇあたりの水素吸着量を算出する。 In the present invention, the dispersibility of the transition metal particles supported on the carrier is determined by using a metal dispersity measuring device (for example, a metal dispersibility measuring device (BEL-METAL-1) manufactured by Nippon Bell Co., Ltd.). The amount of hydrogen adsorption per unit volume by the metal particles can be used as an index. Hydrogen adsorption is a metal dispersion measurement performed by a pulse method. The measurement conditions are described below. About 0.3 g of a catalyst body for producing carbon nanotubes is introduced into a measuring quartz tube and connected to a measuring system. Next, it is heated to 900 ° C. in an N 2 atmosphere for 30 minutes and then allowed to cool to 400 ° C. After stabilizing at 400 ° C. for 1 hour, 5% H 2 / N 2 gas is pulsed 25 times in an amount of 0.15 cm 3 (H 2 : 3.3 × 10 −7 mol). Analysis based on the Catalytic Society Reference Catalyst Committee Metal Dispersity Measurement Manual is performed, and the hydrogen adsorption amount per 1 g of catalyst is calculated from the hydrogen adsorption amount of the catalyst body.
担体に担持した遷移金属粒子の形状および平均粒径は透過型電子顕微鏡（ＴＥＭ）（例えば、日本電子社製ＪＥＭ−２１００）により評価することができる。例えば、倍率２５０，０００倍の観察写真より５０個の金属粒子の粒径の相加平均したものを平均粒径とする。なお、ＴＥＭ像が真円形でない場合、長径を測定するものとする。また、１視野中に５０個の金属粒子がない場合は、視野数を増やしても良い。 The shape and average particle diameter of the transition metal particles supported on the carrier can be evaluated by a transmission electron microscope (TEM) (for example, JEM-2100 manufactured by JEOL Ltd.). For example, an arithmetic average of the particle diameters of 50 metal particles from an observation photograph at a magnification of 250,000 times is taken as the average particle diameter. When the TEM image is not a perfect circle, the major axis is measured. If there are no 50 metal particles in one field of view, the number of fields of view may be increased.
本発明によって得られた触媒体は炭素含有化合物を接触させることによってカーボンナノチューブを製造することができる。その接触の温度は、５００〜１２００℃、好ましくは６００〜１０００℃である。通常、温度が低いと収率良くカーボンナノチューブを得ることが困難になり、温度が高いと使用する反応器の材質に制約が生じる。 The catalyst body obtained by the present invention can produce carbon nanotubes by contacting a carbon-containing compound. The temperature of the contact is 500-1200 degreeC, Preferably it is 600-1000 degreeC. Usually, it is difficult to obtain carbon nanotubes with a good yield when the temperature is low, and the material of the reactor to be used is limited when the temperature is high.
炭素含有化合物としては、気体、液体、固体いずれでも良いが、５００〜１２００℃の高温条件下でガス状となるものであることが、収率良くカーボンナノチューブを得られることから好ましい。炭素含有化合物の種類としては、炭素原子を含有していれば特に限定はないが、通常は一酸化炭素や炭化水素化合物であり、脂肪族であっても芳香族であってもよく、炭素-炭素結合も飽和結合であっても不飽和結合を含んでいても良い。これらは、単独で使用しても、混合して使用しても構わない。 The carbon-containing compound may be any of gas, liquid, and solid, but it is preferable that the carbon-containing compound is in a gaseous state under a high temperature condition of 500 to 1200 ° C. because carbon nanotubes can be obtained with high yield. The type of carbon-containing compound is not particularly limited as long as it contains a carbon atom, but is usually carbon monoxide or a hydrocarbon compound, which may be aliphatic or aromatic, The carbon bond may be a saturated bond or may contain an unsaturated bond. These may be used alone or in combination.
芳香族の炭化水素では、例えばベンゼン、トルエン、キシレン、クメン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、ナフタレン、フェナントレン、アントラセン又はこれらの混合物などを使用することができる。また、非芳香族の炭化水素では、例えばメタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、エチレン、プロピレンもしくはアセチレン、又はこれらの混合物等を使用することができる。炭化水素では、酸素を含むもの、例えばメタノール若しくはエタノール、プロパノール、ブタノールなどのアルコール類、アセトンなどのケトン類、及びホルムアルデヒドもしくはアセトアルデヒドなどのアルデヒド類、トリオキサン、ジオキサン、ジメチルエーテル、ジエチルエーテルなどのエーテル類、酢酸エチルなどのエステル類又はこれらの混合物であってもよい。中でも、得られるカーボンナノチューブの品質の点で、メタン、エタン、アセチレンを用いるのが好ましく、より好ましくはメタンを用いるのが好適である。 As the aromatic hydrocarbon, for example, benzene, toluene, xylene, cumene, ethylbenzene, diethylbenzene, trimethylbenzene, naphthalene, phenanthrene, anthracene, or a mixture thereof can be used. As non-aromatic hydrocarbons, for example, methane, ethane, propane, butane, pentane, hexane, heptane, ethylene, propylene or acetylene, or a mixture thereof can be used. Among hydrocarbons, those containing oxygen, for example, alcohols such as methanol or ethanol, propanol, butanol, ketones such as acetone, aldehydes such as formaldehyde or acetaldehyde, ethers such as trioxane, dioxane, dimethyl ether, diethyl ether, It may be an ester such as ethyl acetate or a mixture thereof. Among these, methane, ethane, and acetylene are preferably used in terms of the quality of the obtained carbon nanotube, and methane is more preferably used.
炭素含有化合物は、窒素、アルゴン、水素、ヘリウム等の不活性ガスとの混合物として用いても、単独で用いても構わないが、触媒体に炭素ガスが供給される反応場は、不活性ガス、または真空雰囲気下（減圧下）であることが、収率良くカーボンナノチューブが得られることから好ましい。 The carbon-containing compound may be used as a mixture with an inert gas such as nitrogen, argon, hydrogen, or helium, or may be used alone, but the reaction field where the carbon gas is supplied to the catalyst body is an inert gas. Or in a vacuum atmosphere (reduced pressure) is preferred because carbon nanotubes can be obtained with good yield.
触媒体と炭素含有化合物の接触のさせ方は特に限定されない。例えば、触媒体を加熱炉内に保持し、炭素含有化合物を加熱炉内に供給して加熱炉内で接触させる方法(固定床)や、触媒体を加熱炉内で流動させ、炭素含有化合物を加熱炉内に供給して加熱炉内で接触させる方法(流動床)などがある。好ましくは流動床である。
反応終了後に合成したままの状態で利用してもよいが、精製を行うことが好ましい。精製の方法としては、担体や触媒金属を除いて使用する方法や加熱酸化処理する方法あるいはこれらを組み合わせる方法がよい。
There is no particular limitation on how to contact the catalyst body and the carbon-containing compound. For example, the catalyst body is held in a heating furnace, the carbon-containing compound is supplied into the heating furnace and contacted in the heating furnace (fixed bed), or the catalyst body is flowed in the heating furnace, There is a method (fluidized bed) of supplying into the heating furnace and contacting in the heating furnace. A fluidized bed is preferred.
Although it may be used as synthesized after completion of the reaction, it is preferable to carry out purification. As a purification method, a method of using the carrier and the catalyst metal excluding them, a method of heat oxidation treatment, or a method of combining them is preferable.
担体や触媒金属を除いて使用する方法としては、担体や触媒金属は、酸などで取り除くことができる。例えば、担体としてマグネシア、触媒金属として鉄を使った場合には、塩酸などの無機酸でマグネシアおよび鉄を取り除くことができる。このような処理により、触媒金属の残存量を３ｗｔ％以下に低減させることができる。あるいは加熱酸化処理により、アモルファスカーボン等の炭素不純物を低減する。 As a method to be used without the support and the catalyst metal, the support and the catalyst metal can be removed with an acid or the like. For example, when magnesia is used as the carrier and iron is used as the catalyst metal, magnesia and iron can be removed with an inorganic acid such as hydrochloric acid. By such treatment, the remaining amount of catalyst metal can be reduced to 3 wt% or less. Alternatively, carbon impurities such as amorphous carbon are reduced by heat oxidation treatment.
加熱酸化処理は気相、液相およびこれらの組合せで行うことができる。気相における加熱酸化処理の方法としては、加熱温度を４００〜６００℃の範囲に調整した後に空気下で０．５〜５時間酸化処理を行うことで非晶質な炭素不純物を除去する方法が好ましい。このときの加熱温度は好ましくは４３０〜５５０℃程度であることがより好ましい。酸化処理時間は好ましくは１〜５時間である。さらに好ましくは２〜４時間である。 The heat oxidation treatment can be performed in a gas phase, a liquid phase, or a combination thereof. As a method of heat oxidation treatment in the gas phase, there is a method of removing amorphous carbon impurities by adjusting the heating temperature in the range of 400 to 600 ° C. and then performing oxidation treatment in the air for 0.5 to 5 hours. preferable. The heating temperature at this time is preferably about 430 to 550 ° C. The oxidation treatment time is preferably 1 to 5 hours. More preferably, it is 2 to 4 hours.
液相における加熱酸化処理の方法としては、硝酸、混酸、過酸化水素等の酸化性の液相で加熱処理を行う方法が挙げられ、なかでも硝酸が好ましい。 Examples of the method of heat oxidation treatment in the liquid phase include a method of heat treatment in an oxidizing liquid phase such as nitric acid, mixed acid, hydrogen peroxide, etc. Among them, nitric acid is preferable.
精製により得られたカーボンナノチューブ組成物は液体中に保持することが好ましい。そのため、精製後のカーボンナノチューブ、カーボンナノチューブ組成物を硝酸溶液等液相中で加熱酸化処理した場合はその酸化処理後、濾過等により固液分離した後、あるいはそのままで、乾燥させることなく、分散媒または分散剤またはその両方を混合してカーボンナノチューブ組成物を分散させて良い。これらを混合する順序は特に制限はなく、混合方法についてもカーボンナノチューブ組成物の分散液が得られるならば特に制限はない。 The carbon nanotube composition obtained by purification is preferably retained in a liquid. Therefore, when the purified carbon nanotubes and the carbon nanotube composition are heated and oxidized in a liquid phase such as nitric acid solution, after the oxidation treatment, they are separated by solid-liquid separation by filtration or the like, or they are dispersed without being dried. The carbon nanotube composition may be dispersed by mixing a medium or a dispersant or both. The order of mixing these is not particularly limited, and the mixing method is not particularly limited as long as a dispersion of the carbon nanotube composition can be obtained.
上記好ましい精製方法を用い、十分に精製したカーボンナノチューブ組成物は分散性に優れるため、前記分散液の製造方法に準じた方法で分散液とすることにより、０．３ｍｇ/ｍＬ以上カーボンナノチューブ組成物が分散した分散液が得られるので好ましい。 A carbon nanotube composition that has been sufficiently purified using the above-described preferred purification method is excellent in dispersibility. Is preferable because a dispersion in which is dispersed is obtained.
ここで、硝酸溶液等の液相中で加熱した後、乾燥させることなくとは、硝酸溶液等の液相中で加熱後、カーボンナノチューブ組成物がカーボン重量で９９ｗｔ％以下となるように液体を保持した状態が常に保たれていることをいう。例えば、硝酸溶液等の液相中での加熱終了後、ろ過、デカンテーション等で硝酸を除去する場合、ろ過、デカンテーション後、水、アルコール、有機溶媒等の液体で洗浄する場合についても、カーボンナノチューブ組成物がカーボン重量で９９ｗｔ％以下となるように液体を保持した状態が常に保たれているならば、本発明で規定する「乾燥させることなく」に当てはまると解釈する。その際のカーボン重量の下限は特に制限が無いが、少なくとも分散液を製造する時点（分散剤、分散媒と混合する時）では、製造しようとする分散液の濃度以上に調整しておく必要はある。 Here, after heating in a liquid phase such as a nitric acid solution, without drying, the liquid is heated so that the carbon nanotube composition has a carbon weight of 99 wt% or less after heating in a liquid phase such as a nitric acid solution. This means that the held state is always maintained. For example, when nitric acid is removed by filtration, decantation, etc. after heating in a liquid phase such as a nitric acid solution, or after washing with a liquid such as water, alcohol, organic solvent after filtration, decantation, etc. If the state in which the liquid is kept so that the nanotube composition is 99 wt% or less in terms of the carbon weight is always maintained, it is interpreted as “without drying” as defined in the present invention. The lower limit of the carbon weight in that case is not particularly limited, but at least at the time of producing the dispersion (when mixing with the dispersant and dispersion medium), it is necessary to adjust the concentration to be higher than the concentration of the dispersion to be produced. is there.
分散剤または分散媒と混合する際のカーボンナノチューブ組成物がカーボン重量で９９ｗｔ％以下となるように液体を保持した状態として好ましい態様は、扱い易さの点から、カーボン重量が０．０１〜８０ｗｔ％であり、さらに好ましくは０．１〜６５ｗｔ％、より好ましくは１．０〜５０ｗｔ％、最も好ましくは３〜４０ｗｔ％である。 In a preferred embodiment of the state in which the liquid is held so that the carbon nanotube composition when mixed with the dispersant or the dispersion medium is 99 wt% or less in terms of carbon weight, the carbon weight is 0.01 to 80 wt. %, More preferably 0.1 to 65 wt%, more preferably 1.0 to 50 wt%, and most preferably 3 to 40 wt%.
カーボンナノチューブの層数は透過型電子顕微鏡（ＴＥＭ）（例えば、日本電子社製ＪＥＭ−２１００）による倍率２５０，０００倍の観察写真より１００本のカーボンナノチューブの外径および層数を数え、それらの相加平均より、評価することが可能である。 The number of layers of carbon nanotubes is determined by counting the outer diameter and the number of layers of 100 carbon nanotubes from observation photographs at a magnification of 250,000 times with a transmission electron microscope (TEM) (for example, JEM-2100 manufactured by JEOL Ltd.). It is possible to evaluate from the arithmetic average.
通常カーボンナノチューブは層数が少ないほどグラファイト化度が高い、つまり導電性が高く、層数が増えるほどグラファイト化度が低下する傾向がある。２層カーボンナノチューブは層数が単層カーボンナノチューブよりも多いため、耐久性が高く、高いグラファイト化度も併せ持つため、耐久性が高く高導電性のカーボンナノチューブ集合体という点で２層カーボンナノチューブの割合は多いほど好ましい。 In general, the smaller the number of layers, the higher the degree of graphitization of carbon nanotubes, that is, the higher the conductivity, and the higher the number of layers, the lower the degree of graphitization. Since double-walled carbon nanotubes have more layers than single-walled carbon nanotubes, they are highly durable and have a high degree of graphitization. Therefore, they are durable and highly conductive aggregates of carbon nanotubes. The higher the ratio, the better.
本発明では上記方法で測定したときの２層カーボンナノチューブの割合は５０％以上、つまり１００本中５０本以上であることが好ましく、１００本中６０本以上が２層カーボンナノチューブであることがより好ましく、１００本中７０本以上が２層カーボンナノチューブであることが更に好ましい。本発明の触媒体によれば、上記のような２層カーボンナノチューブを容易に製造することができる。 In the present invention, the proportion of double-walled carbon nanotubes when measured by the above method is preferably 50% or more, that is, 50 or more of 100, and more than 60 of 100 are double-walled carbon nanotubes. Preferably, 70 or more of 100 are double-walled carbon nanotubes. According to the catalyst body of the present invention, the above-mentioned double-walled carbon nanotube can be easily produced.
本発明の方法で得られるカーボンナノチューブ組成物は１０℃／ｍｉｎで昇温した時の熱重量測定（Ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｙ）で、単位時間当たりの減少重量を表すＤＴＧ曲線から観測される発熱による燃焼ピーク温度が６５０℃〜８００℃の範囲であることが好ましい。本発明における発熱による燃焼ピーク温度とは、約１ｍｇの試料を示差熱分析装置（例えば、島津製作所製 ＴＧＡ-６０）に設置し、空気中、１０℃／分の昇温速度にて室温から９００℃まで昇温する。その時の熱重量測定で単位時間当たりの減少重量を表すＤＴＧ曲線から得られる。 The carbon nanotube composition obtained by the method of the present invention has a combustion peak temperature due to heat generation observed from a DTG curve representing a reduced weight per unit time by thermogravimetry when the temperature is raised at 10 ° C./min. It is preferable that it is the range of 650 degreeC-800 degreeC. The peak temperature of combustion due to heat generation in the present invention is about 1 mg of a sample placed in a differential thermal analyzer (for example, TGA-60 manufactured by Shimadzu Corporation), and is heated from room temperature to 900 ° C. at a heating rate of 10 ° C./min. The temperature is raised to ° C. It is obtained from a DTG curve representing the weight loss per unit time by thermogravimetry at that time.
一般に、アモルファスカーボンなどのカーボンナノチューブ以外の炭素不純物は４００℃以下で分解するため、アモルファスカーボンなどがカーボンナノチューブに付着した試料は燃焼ピーク温度が低くなる。また一本のカーボンナノチューブの長さが長いほど、又層数が多いほど燃焼ピーク温度は高くなると推定される。そのため、アモルファスカーボンの付着の少ない、長さの長いカーボンナノチューブの燃焼ピークは高くなり、高品質なカーボンナノチューブであるといえる。従って、燃焼ピーク温度を上記範囲にするためには、上記好ましい方法により製造されるような品質の高いカーボンナノチューブを用いて前記精製を充分に行えばよい。 Generally, carbon impurities other than carbon nanotubes, such as amorphous carbon, are decomposed at 400 ° C. or lower, so that a sample with amorphous carbon attached to the carbon nanotubes has a low combustion peak temperature. Further, it is estimated that the combustion peak temperature increases as the length of one carbon nanotube increases and the number of layers increases. For this reason, the combustion peak of carbon nanotubes with a long length and less adhesion of amorphous carbon is high, and it can be said that these are high-quality carbon nanotubes. Therefore, in order to set the combustion peak temperature within the above range, the purification may be sufficiently performed using high-quality carbon nanotubes produced by the preferred method.
該高純度、高品質なカーボンナノチューブは導電性が高いことから、タッチパネルや電子ペーパー等の透明導電フィルムへの展開が可能である。
Since the high-purity and high-quality carbon nanotubes have high conductivity, they can be applied to transparent conductive films such as touch panels and electronic paper.
以下、実施例により本発明を具体的に説明するが、下記の実施例は例示のために示すものであって、いかなる意味においても、本発明を限定的に解釈するものとして使用してはならない。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are given for illustrative purposes and should not be used in any way as a limited interpretation of the present invention. .
＜実施例１＞
（触媒体合成）
三口フラスコ中のトリエチレングリコール（アルドリッチ社製）９０ｍｌと両末端にカルボキシル基を有するポリエチレングリコール（アルドリッチ社製、数平均分子量６００）９．２４ｇ（１５ｍｍｏｌ）の混合溶液に塩化鉄（ＩＩＩ）・６水和物（和光純薬工業社製）を４．０６ｇ（１５ｍｍｏｌ）加え、空気雰囲気下、１００℃にてこれらを充分に溶解した。次いでこの溶液を空気雰囲気下、２６０℃で２４時間加熱還流を行った。反応終了後、反応混合物を室温まで徐冷し、反応混合物中にアセトンを加えることで両末端にカルボキシル基を有するポリエチレングリコールによって被覆された酸化鉄粒子を単離した。単離した酸化鉄粒子を減圧乾燥し、黒色の粉末を得た。また、得られた酸化鉄粒子は、水に再分散可能であった。
<Example 1>
(Catalyst synthesis)
To a mixed solution of 90 ml of triethylene glycol (manufactured by Aldrich) in a three-necked flask and 9.24 g (15 mmol) of polyethylene glycol having a carboxyl group at both ends (manufactured by Aldrich, number average molecular weight 600) was added iron (III) -6 4.06 g (15 mmol) of hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and these were sufficiently dissolved at 100 ° C. in an air atmosphere. Subsequently, this solution was heated and refluxed at 260 ° C. for 24 hours in an air atmosphere. After completion of the reaction, the reaction mixture was gradually cooled to room temperature, and acetone was added to the reaction mixture to isolate iron oxide particles coated with polyethylene glycol having carboxyl groups at both ends. The isolated iron oxide particles were dried under reduced pressure to obtain a black powder. Further, the obtained iron oxide particles were redispersible in water.
次いで上記で合成した酸化鉄粒子１．１４ｇをイオン交換水５００ｍｌに溶解した。この溶液に水酸化マグネシウム（岩谷化学工業社製ＭＨ−３０）１４４．７ｇを加え、マグネティックスターラーにより６０分間攪拌した。その後、懸濁液を吸引濾過により固形分を分離し、１２０℃の乾燥機中で加熱乾燥した。脱水された固形分は２０〜３２メッシュの粒径になるまで細粒化した。得られた固形分を電気炉中に導入し、大気下６００℃で３時間加熱した。担体の水酸化マグネシウムは該加熱処理により、脱水し酸化マグネシウムへと構造変化した。 Next, 1.14 g of the iron oxide particles synthesized above were dissolved in 500 ml of ion-exchanged water. To this solution, 144.7 g of magnesium hydroxide (MH-30 manufactured by Iwatani Chemical Industry Co., Ltd.) was added and stirred for 60 minutes with a magnetic stirrer. Thereafter, the solid content of the suspension was separated by suction filtration, and dried by heating in a dryer at 120 ° C. The dehydrated solid content was refined to a particle size of 20-32 mesh. The obtained solid content was introduced into an electric furnace and heated at 600 ° C. for 3 hours in the atmosphere. The carrier magnesium hydroxide was dehydrated by the heat treatment and changed in structure to magnesium oxide.
（ＴＥＭ測定）
日本電子社製の透過型電子顕微鏡（ＪＥＭ−２１００）を用いて合成後の分散剤被覆酸化鉄粒子を２５０，０００倍で観察した結果を図１に示す。酸化鉄粒子の粉末２ｍｇをイオン交換水３ｇに溶解したものを、コロジオン膜被覆銅グリッドに一滴落とし一晩常温乾燥したものを前述の方法で測定した。その結果、平均粒径は５．６ｎｍであった。また、担体に担持し、分散剤を除去した後の酸化鉄粒子を前述の方法で観察した結果を図２に示す。その結果、担体上に酸化鉄粒子が担持されていることが観察でき、担持前の粒径と比べて大きな凝集はみられなかった。
(TEM measurement)
The result of observing the synthesized dispersion-coated iron oxide particles at 250,000 times using a transmission electron microscope (JEM-2100) manufactured by JEOL Ltd. is shown in FIG. A solution obtained by dissolving 2 mg of iron oxide particle powder in 3 g of ion-exchanged water and dropping it onto a collodion film-coated copper grid and drying at room temperature overnight was measured by the method described above. As a result, the average particle size was 5.6 nm. Moreover, the result of having observed the iron oxide particle after carrying | supporting to a support | carrier and removing a dispersing agent by the above-mentioned method is shown in FIG. As a result, it was observed that iron oxide particles were supported on the carrier, and no large aggregation was observed compared to the particle size before the support.
（分散剤被覆金属粒子の熱分析）
約１ｍｇの試料を示差熱分析装置（島津製作所製 ＴＧＡ-６０）に設置し、空気中、１０℃／分の昇温速度にて室温から９００℃まで昇温した。そのときの重量変化を測定した。その結果燃焼ピークは２７８℃であり重量変化は５４．７％であった。この燃焼ピークは酸化鉄粒子を被覆していたポリエチレングリコールのものである。ＴＧＡの結果より、分散剤被覆金属粒子中の金属の割合は４５．３％である。
(Thermal analysis of dispersant-coated metal particles)
About 1 mg of a sample was placed in a differential thermal analyzer (TGA-60 manufactured by Shimadzu Corporation), and the temperature was increased from room temperature to 900 ° C. at a temperature increase rate of 10 ° C./min. The weight change at that time was measured. As a result, the combustion peak was 278 ° C. and the weight change was 54.7%. This combustion peak is that of polyethylene glycol that was coated with iron oxide particles. From the result of TGA, the ratio of the metal in the dispersion-coated metal particles is 45.3%.
（水素吸着測定）
日本ベル社製の水素吸着装置（ＢＥＬ−ＭＥＴＡＬ−１）を用いて、前述の方法で担体上におけるＦｅの水素吸着量を測定した。触媒１ｇあたりの水素吸着量は０．０９２ｃｍ３／ｇ（触媒）であった。
(Hydrogen adsorption measurement)
Using a hydrogen adsorption apparatus (BEL-METAL-1) manufactured by Nippon Bell Co., Ltd., the hydrogen adsorption amount of Fe on the support was measured by the method described above. The hydrogen adsorption amount per 1 g of the catalyst was 0.092 cm 3 / g (catalyst).
（カーボンナノチューブの合成）
図３に示した装置を用いてカーボンナノチューブの合成を行った。反応器１００は内径３２ｍｍ、長さは９００ｍｍの円筒形石英管である。中央部に石英焼結板１０１を具備し、石英管下方部には、不活性ガスおよび原料ガス供給ライン１０４である混合ガス導入管、上部には廃ガスライン１０５を具備する。さらに、反応器を任意温度に保持できるように反応器の円周を取り囲む加熱器１０６として電気炉を具備する。加熱器１０６には装置内の流動状態が確認できるよう点検口１０７が設けられている。
(Synthesis of carbon nanotubes)
Carbon nanotubes were synthesized using the apparatus shown in FIG. The
上記で調製した固体触媒体１２ｇをとり、密閉型触媒供給機１０２から触媒投入ライン１０３を通して、鉛直方向に設置した反応器の中央部の石英焼結板１０１上に導入することで触媒層１０８を形成した。触媒層を３０分間かけて８５０℃に加熱しながら、反応器底部から反応器上部方向へ向けてマスフローコントローラー（図示せず）を用いて窒素ガスを１９７０ｍＬ/ｍｉｎで３０分間供給し、触媒層を通過するように流通させた。その後、窒素ガスを供給しながら、さらにマスフローコントローラーを用いてメタンガスを９５．８ｍＬ／ｍｉｎで３０分間導入して触媒層を通過するように通気し、反応させた。メタンガスの導入を止め、窒素ガスを１９７０ｍＬ／ｍｉｎ通気させながら、石英反応管を室温まで冷却した。
The
上記のようにして得たカーボンナノチューブ含有組成物１１．７ｇを用いて４．８Ｎの塩酸水溶液２００ｍＬ中で１時間撹拌することで触媒金属である鉄とその担体であるＭｇＯを溶解した。得られた黒色懸濁液は濾過した後、濾取物は再度４．８Ｎの塩酸水溶液２００ｍＬに投入し脱ＭｇＯ処理をし、濾取した。この操作を３回繰り返した。 By using 11.7 g of the carbon nanotube-containing composition obtained as described above and stirring in 200 mL of a 4.8N hydrochloric acid aqueous solution for 1 hour, iron as a catalyst metal and MgO as a carrier thereof were dissolved. The resulting black suspension was filtered, and the filtered product was again put into 200 mL of a 4.8N hydrochloric acid aqueous solution, treated with MgO, and collected by filtration. This operation was repeated three times.
さらに、塩酸処理後のカーボンナノチューブ組成物０．２１５ｇを６０％の硝酸１００ｍＬ中で加熱還流し、酸化処理を行った。その結果、最終的なカーボンナノチューブの収量は１００ｇの触媒換算で２４３ｍｇであった。 Furthermore, 0.215 g of the carbon nanotube composition after the hydrochloric acid treatment was heated to reflux in 100 mL of 60% nitric acid to carry out an oxidation treatment. As a result, the final yield of carbon nanotubes was 243 mg in terms of 100 g of catalyst.
（硝酸処理後のカーボンナノチューブＴＥＭ観察）
日本電子社製の透過型電子顕微鏡（ＪＥＭ−２１００）を用いて精製後のカーボンナノチューブの形状を２５０，０００倍で観察し、１００本の層数および外径を解析した。結果を図４に示す。二層カーボンナノチューブは９５％含まれており、平均直径は１．７ｎｍであった。直径は直線性のよい部分で測定した値の算術平均とした。
(Carbon nanotube TEM observation after nitric acid treatment)
Using a transmission electron microscope (JEM-2100) manufactured by JEOL Ltd., the shape of the purified carbon nanotube was observed at 250,000 times, and the number of 100 layers and the outer diameter were analyzed. The results are shown in FIG. The double-walled carbon nanotubes contained 95% and the average diameter was 1.7 nm. The diameter was the arithmetic average of the values measured in the part with good linearity.
（硝酸処理後のカーボンナノチューブ熱分析）
濃硝酸による液相加熱酸化処理したカーボンナノチューブ組成物試料を約１ｍｇ示差熱分析装置（島津製作所製 ＤＴＧ−６０）に設置し、空気中、１０℃／分の昇温速度にて室温から９００℃まで昇温した。そのときの単位時間当たりの減少重量を表すＤＴＧ曲線から発熱による燃焼ピーク温度を読みとった。ＤＴＧ曲線から得られるピークは低温側と高温側に分かれるが、その高温側のピークの割合を高耐熱カーボンナノチューブと定義した場合、高耐熱カーボンナノチューブの割合は７７．９％であった。
(Thermal analysis of carbon nanotubes after nitric acid treatment)
About 1 mg of a carbon nanotube composition sample subjected to liquid phase heating oxidation treatment with concentrated nitric acid was placed in a differential thermal analyzer (DTG-60, manufactured by Shimadzu Corporation), and from room temperature to 900 ° C. at a temperature rising rate of 10 ° C./min. The temperature was raised to. The combustion peak temperature due to heat generation was read from the DTG curve representing the weight loss per unit time at that time. The peak obtained from the DTG curve is divided into a low temperature side and a high temperature side. When the ratio of the peak on the high temperature side was defined as a high heat resistant carbon nanotube, the ratio of the high heat resistant carbon nanotube was 77.9%.
収量と高耐熱カーボンナノチューブの割合から求めた高耐熱カーボンナノチューブの含有量は１００ｇの触媒換算で１８９ｍｇであった。 The content of the high heat-resistant carbon nanotubes determined from the yield and the ratio of the high heat-resistant carbon nanotubes was 189 mg in terms of 100 g of catalyst.
本手法により、直径が細く、高品質な２層カーボンナノチューブを選択的に得ることが可能であった。 By this method, it was possible to selectively obtain a high-quality double-walled carbon nanotube having a small diameter.
＜比較例＞
（触媒体合成）
クエン酸鉄アンモニウム（和光純薬工業社製）２．４６ｇをメタノール（関東化学社製）５００ｍｌに溶解した。この溶液に、水酸化マグネシウム（岩谷化学工業社製ＭＨ-30）を１４４．７ｇ加え、マグネティックスターラーで６０分間撹拌処理し、懸濁液を減圧下、４０℃で濃縮乾固した。得られた粉末を１２０℃で加熱乾燥してメタノールを除去し、水酸化マグネシウム粉末に金属塩が担持された固体触媒を得た。上記固体触媒は、２０〜３２メッシュの粒径になるまで細粒化した。得られた固形分を電気炉中に導入し、大気下６００℃で３時間加熱した。担体の水酸化マグネシウムは該加熱処理により、脱水し酸化マグネシウムへと構造変化した。
<Comparative example>
(Catalyst synthesis)
2.46 g of ammonium iron citrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 ml of methanol (manufactured by Kanto Chemical Co., Inc.). To this solution, 144.7 g of magnesium hydroxide (MH-30 manufactured by Iwatani Chemical Industry Co., Ltd.) was added and stirred with a magnetic stirrer for 60 minutes. The obtained powder was dried by heating at 120 ° C. to remove methanol, and a solid catalyst in which a metal salt was supported on magnesium hydroxide powder was obtained. The solid catalyst was refined to a particle size of 20-32 mesh. The obtained solid content was introduced into an electric furnace and heated at 600 ° C. for 3 hours in the atmosphere. The carrier magnesium hydroxide was dehydrated by the heat treatment and changed in structure to magnesium oxide.
（ＴＥＭ測定）
日本電子社製の透過型電子顕微鏡（ＪＥＭ−２１００）を用いて、担体へ担持後の鉄粒子の粒径を２５０，０００倍で観察した結果を図５に示す。その結果、いびつな形状をした鉄粒子の凝集体が観察された。その平均粒径２６．７ｎｍであった。
(TEM measurement)
FIG. 5 shows the results of observation of the particle size of the iron particles supported on the carrier at 250,000 times using a transmission electron microscope (JEM-2100) manufactured by JEOL. As a result, an aggregate of iron particles having an irregular shape was observed. The average particle size was 26.7 nm.
（水素吸着測定）
日本ベル社製の水素吸着装置（ＢＥＬ−ＭＥＴＡＬ−１）を用いて、担体上におけるＦｅの水素吸着量を測定した。触媒１ｇあたりの水素吸着量は０．０７０ｃｍ３／ｇ（触媒）であった。実施例１の場合と比較して水素吸着量が少なく、担持された金属粒子の平均粒径は大きいと判断される。
(Hydrogen adsorption measurement)
The hydrogen adsorption amount of Fe on the carrier was measured using a hydrogen adsorption device (BEL-METAL-1) manufactured by Nippon Bell. The hydrogen adsorption amount per 1 g of the catalyst was 0.070 cm 3 / g (catalyst). Compared to the case of Example 1, the amount of hydrogen adsorption is small, and the average particle size of the supported metal particles is judged to be large.
（カーボンナノチューブの合成）
実施例１と同様の操作を行った。精製後のカーボンナノチューブの回収率は濃硝酸による液相酸化処理後１００ｇの触媒換算で１７０ｍｇであった。
(Synthesis of carbon nanotubes)
The same operation as in Example 1 was performed. The recovery rate of the carbon nanotubes after purification was 170 mg in terms of 100 g of catalyst after liquid phase oxidation treatment with concentrated nitric acid.
（熱分析）
濃硝酸による液相加熱酸化処理したカーボンナノチューブ組成物試料を約１ｍｇ示差熱分析装置（島津製作所製 ＤＴＧ−６０）に設置し、空気中、１０℃／分の昇温速度にて室温から９００℃まで昇温した。そのときの単位時間当たりの減少重量を表すＤＴＧ曲線から求めた高耐熱カーボンナノチューブの割合は７６．６％であった。
収量と高耐熱カーボンナノチューブの割合から求めた高耐熱カーボンナノチューブの含有量は１００ｇの触媒換算で１３０ｍｇであった。
(Thermal analysis)
About 1 mg of a carbon nanotube composition sample subjected to liquid phase heating oxidation treatment with concentrated nitric acid was placed in a differential thermal analyzer (DTG-60, manufactured by Shimadzu Corporation), and from room temperature to 900 ° C. at a temperature rising rate of 10 ° C./min. The temperature was raised to. The proportion of the high heat-resistant carbon nanotubes determined from the DTG curve representing the weight loss per unit time at that time was 76.6%.
The content of the high heat-resistant carbon nanotubes determined from the yield and the ratio of the high heat-resistant carbon nanotubes was 130 mg in terms of 100 g of catalyst.
１００ 反応器
１０１ 石英焼結板
１０２ 密閉型触媒供給機
１０３ 触媒投入ライン
１０４ 原料ガス供給ライン
１０５ 廃ガスライン
１０６ 加熱器
１０７ 点検口
１０８ 触媒層
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| CN111514903A (en) * | 2019-12-25 | 2020-08-11 | 江西悦安新材料股份有限公司 | Method for preparing iron-based array carbon tube catalyst in large scale |
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