JP2016525061A - バルク密度が調節されたカーボンナノチューブ凝集体の製造方法 - Google Patents
バルク密度が調節されたカーボンナノチューブ凝集体の製造方法 Download PDFInfo
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- JP2016525061A JP2016525061A JP2016527962A JP2016527962A JP2016525061A JP 2016525061 A JP2016525061 A JP 2016525061A JP 2016527962 A JP2016527962 A JP 2016527962A JP 2016527962 A JP2016527962 A JP 2016527962A JP 2016525061 A JP2016525061 A JP 2016525061A
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- carbon nanotube
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Abstract
Description
本発明は、担持触媒、これから得られたカーボンナノチューブ凝集体及びこれらの製造方法に関する。
支持体とグラファイト化触媒金属前駆体水溶液とを混合し、ペーストを形成し、
前記ペーストを、下記の数式1により定義される水分除去率が5〜30重量%になるように乾燥した後、焼成して得られる担持触媒を提供する。
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。
前記担持触媒と、前記担持触媒上で成長されたカーボンナノチューブと、を含むカーボンナノチューブ凝集体を提供する。
前記カーボンナノチューブ凝集体を含む複合素材を提供する。
支持体とグラファイト化触媒金属前駆体水溶液とを混合し、ペーストを形成する段階と、
前記ペーストを、前記数式1により定義される水分除去率が5〜30重量%になるように乾燥した後、焼成する段階と、を含む担持触媒の製造方法を提供する。
支持体とグラファイト化触媒金属前駆体水溶液とを混合し、ペーストを形成する段階と、
前記ペーストを乾燥して水分を除去した後、焼成し、担持触媒を得る段階と、
加熱の下で炭素含有化合物と接触反応させ、カーボンナノチューブ凝集体を製造する段階と、を含むカーボンナノチューブ凝集体の製造方法において、
前記数式1により定義される前記ペーストの水分除去率を5〜30重量%に調節し、カーボンナノチューブのバルク密度を調節することを含むカーボンナノチューブ凝集体の製造方法を提供する。
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。
[数式2]
−2.9x+100≦y≦−2.9x+130
カーボンナノチューブ凝集体の収率(倍)=(反応後の総重量g−使用した担持触媒の重量g)/使用した担持触媒の重量g
扁平率=カーボンナノチューブの中心を貫通する最短直径/カーボンナノチューブの中心を貫通する最大直径
A.グラファイト化金属触媒の前駆体水溶液の製造
グラファイト化触媒としてFe金属触媒を準備した。Feの前駆体物質としてFe(NO3)2・6H2O 2,424gを水2,000gに投入した。製造された金属水溶液は、沈殿が見えない綺麗な溶液状態で観察された。
アルミニウム系支持体前駆体として水酸化アルミニウム(Aluminum-tri-hydroxide, Al(OH)3)を400℃で4時間第1焼成して得られたATH400 2,000gをフラスコBに準備した。XRD分析によれば、焼成後の支持体は、AlO(OH)を40重量%以上含むものと表された。
ATH400 2,000gをモル基準100に換算すれば、Feが30モルになるように、フラスコBに前記フラスコAの溶液4,424gを添加した。混合物の重量を測定した後、グラファイト化金属触媒の前駆体を十分にATH400に担持させるために、60℃の恒温槽で5分間撹拌して熟成させた。それを前記温度に維持しながら、80rpmで回転させ、真空乾燥させた後、乾燥後の重量を測定して水分除去率を測定した(約14.1%)。乾燥した触媒を600℃で4時間第2焼成させ、均質な担持触媒を製造した。
前記で製造されたカーボンナノチューブ合成用担持触媒を用いて、実験室規模の固定層反応装置でカーボンナノチューブ合成を行った。
具体的には、前記Cで製造されたカーボンナノチューブ合成用担持触媒を、直径55mmの内径を有する石英管の中央部に装着した後、窒素雰囲気で670℃まで昇温した後に維持させ、窒素、水素及びエチレンガスの体積混合比を同じ割合で分当たり180ml流しながら1時間合成して、所定量のカーボンナノチューブ凝集体を合成した。図2及び図3は、製造されたカーボンナノチューブ凝集体のSEM写真である。
水分除去率を変化させたことを除いては、実施例1と同様な方法により触媒を製造した後、これを用いてカーボンナノチューブ凝集体を合成した。
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。
[数式2]
−2.9x+100≦y≦−2.9x+130
Claims (17)
- 支持体とグラファイト化触媒金属前駆体水溶液とを混合し、ペーストを形成する段階と、
前記ペーストを乾燥して水分を除去した後、焼成し、担持触媒を得る段階と、
加熱の下で炭素含有化合物と接触反応させ、カーボンナノチューブ凝集体を製造する段階と、を含むカーボンナノチューブ凝集体の製造方法において、
下記の数式1により定義される前記ペーストの水分除去率を5〜30重量%に調節し、カーボンナノチューブのバルク密度を調節することを含む方法:
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。 - 前記水分除去率が低くなるほど、カーボンナノチューブ凝集体のバルク密度が増加する、請求項1に記載のカーボンナノチューブ凝集体の製造方法。
- 前記水分除去率 xと、カーボンナノチューブ凝集体のバルク密度yとが下記の数式2の関係を満たしている、請求項1または2に記載のカーボンナノチューブ凝集体の製造方法:
[数式2]
−2.9x+100≦y≦−2.9x+130 - 前記カーボンナノチューブが束状である、請求項1から3のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記カーボンナノチューブ凝集体のバルク密度が30kg/m3以上である、請求項1から4のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記炭素含有化合物が、一酸化炭素、メタン、エタン、エチレン、エタノール、アセチレン、プロパン、プロピレン、ブタン、ブタジエン、ペンタン、ペンテン、シクロペンタジエン、ヘキサン、シクロヘキサン、ベンゼン及びトルエンからなる群から選択された一つ以上である、請求項1から5のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記担持触媒と炭素含有化合物の反応が、前記炭素含有化合物の熱分解温度以上、かつ前記担持触媒の融点以下である、請求項1から6のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記支持体がアルミニウム系である、請求項1から7のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記支持体の前駆体が水酸化アルミニウム[Al(OH)3]である、請求項1から8のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記担持触媒が鉄(Fe)含有グラファイト化触媒である、請求項1から9のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記支持体は、支持体の前駆体を100℃〜500℃で焼成して得られた、請求項1から10のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記乾燥後のペーストの焼成温度が100℃〜700℃である、請求項1から11のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 前記鉄(Fe)含有グラファイト化触媒が、鉄(Fe)の一元系、またはコバルト(Co)、モリブデン(Mo)及びバナジウム(V)のうち一つ以上を含む多元系触媒である、請求項10に記載のカーボンナノチューブ凝集体の製造方法。
- 前記触媒金属の含量が、担持触媒100重量部を基準として5〜40重量部である、請求項1から13のいずれか1項に記載のカーボンナノチューブ凝集体の製造方法。
- 支持体とグラファイト化触媒金属前駆体水溶液とを混合し、ペーストを形成し、
前記ペーストを、下記の数式1により定義される水分除去率が5〜30重量%になるように乾燥した後、焼成し、担持触媒を製造する方法:
[数式1]
水分除去率={[(支持体の重量+触媒金属前駆体の重量)−乾燥後のペーストの重量]/(支持体の重量+触媒金属前駆体の重量)}×100
前記式中、触媒金属前駆体の重量は、触媒金属前駆体水溶液から溶媒として使われた水の重量を除いたものである。 - 請求項15に記載の方法により製造された担持触媒と、
前記担持触媒上で成長されたカーボンナノチューブと、を含むカーボンナノチューブ凝集体。 - 請求項16に記載のカーボンナノチューブ凝集体を含む複合素材。
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