JP2021526121A - カーボンナノチューブの製造方法 - Google Patents
カーボンナノチューブの製造方法 Download PDFInfo
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- JP2021526121A JP2021526121A JP2020567519A JP2020567519A JP2021526121A JP 2021526121 A JP2021526121 A JP 2021526121A JP 2020567519 A JP2020567519 A JP 2020567519A JP 2020567519 A JP2020567519 A JP 2020567519A JP 2021526121 A JP2021526121 A JP 2021526121A
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- carbon nanotubes
- drying
- producing carbon
- catalyst
- vacuum drying
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Abstract
Description
本出願は、2018年7月27日付韓国特許出願第10−2018−0088008号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
<担持触媒の製造>
Al(OH)3(商品名:BH39−622、製造社:日本軽金属)30gを400℃で4時間1次熱処理して支持体を製造した。主触媒前駆体としてCo(NO3)2・6H2O15.7g、助触媒前駆体としてNH4VO30.63g、クエン酸0.45g及び蒸留水20mlを投入して触媒前駆体溶液を製造した。前記触媒前駆体の溶液全量を前記支持体20mgに担持して活性担持体を製造した。前記活性担持体を80℃の恒温槽で15分間撹拌しながら熟成させた。
収得された担持触媒1gを流動層反応装置内に位置する内径が55mmである石英管の下部に装着した。流動層反応装置の内部を窒素雰囲気で660℃まで一定の速度で昇温させた後、維持し、窒素ガスとエチレンガスを3:1の体積比で2.1l/分で流しながら90時間合成し、カーボンナノチューブ21gを製造した。
主触媒前駆体としてCo(NO3)2・6H2O14.13g、助触媒前駆体としてNH4VO30.85g、(NH4)6Mo7O240.255g、クエン酸0.61g及び蒸留水20mlを投入し、触媒前駆体溶液を製造したこと以外の全ての条件は同様に行った。
1次真空乾燥した活性担持体を175℃、50mbarで1時間回転しながら2次真空乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
1次真空乾燥した活性担持体を300℃、10mbarで30分間回転しながら2次真空乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
1次真空乾燥した活性担持体を200℃、50mbarで30分間回転しながら2次真空乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
1次乾燥した活性担持体を170℃、10mbarで30分間回転しながら2次真空乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
1次乾燥した活性担持体に2次真空乾燥を行わず、200℃で2時間常圧乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
1次真空乾燥した活性担持体に2次真空乾燥を行わず、200℃で容器蓋を閉じて2時間常圧乾燥したことを除き、実施例1と同様の方法で担持触媒及びカーボンナノチューブを製造した。
実施例1、2及び比較例2で製造された担持触媒の物性を下記に記載の方法で測定し、その結果を下記図1及び表1に記載した。
V、電流:40mA)
−Cu Kα radiation(波長:1.54Å)
−LynxEye position sensitive detector(3.7゜slit)
実施例2で担持触媒の製造時、真空乾燥時間を多様化して真空乾燥時間によるカーボンナノチューブの比表面積の変化を図2に示した。
実施例及び比較例のカーボンナノチューブの物性を下記に記載の方法で測定し、その結果を下記表2に記載した。
実施例1と比較例1のカーボンナノチューブ2重量%、N−メチル−2−ピロリドン(NMP)97.6重量%、ポリビニルピロリドン(PVP)0.4重量%を高圧ホモジナイザー(商品名:Panda、製造社:GEA)に投入し、1,500barで30分間処理して導電材分散液を製造した。
本発明の一実施形態によるカーボンナノチューブの製造方法は、1)Al(OH)3を1次熱処理してAlO(OH)を含む支持体を製造する段階;2)主触媒前駆体及び助触媒前駆体を含む混合物を前記支持体に担持して活性担持体を製造する段階;3)真空乾燥が含まれた多段乾燥を介して、前記活性担持体を乾燥する段階;4)前記乾燥された活性担持体を2次熱処理して担持触媒を製造する段階;及び5)前記担持触媒の存在下に、カーボンナノチューブを製造する段階を含む。
先ず、Al(OH)3を1次熱処理してAlO(OH)を含む支持体を製造する。
次いで、主触媒前駆体及び助触媒前駆体を含む混合物を前記支持体に担持して活性担持体を製造する。
次いで、真空乾燥を含む多段乾燥を介して、前記活性担持体を乾燥する。
次いで、前記乾燥された活性担持体を2次熱処理して担持触媒を製造する。
次いで、前記担持触媒の存在下に、カーボンナノチューブを製造する段階を含む。
本発明の一実施形態による製造方法で製造されたカーボンナノチューブは、平均直径が5から20nmであるカーボンナノチューブ単位体を含む。
Claims (16)
- Al(OH)3を1次熱処理してAlO(OH)を含む支持体を製造する段階;
主触媒前駆体及び助触媒前駆体を含む混合物を前記支持体に担持して活性担持体を製造する段階;
真空乾燥を含む多段乾燥を介して、前記活性担持体を乾燥する段階;
前記乾燥された活性担持体を2次熱処理して担持触媒を製造する段階;及び
前記担持触媒の存在下に、カーボンナノチューブを製造する段階を含む、カーボンナノチューブの製造方法。 - 前記多段乾燥は、常圧乾燥及び真空乾燥を含むものである、請求項1に記載のカーボンナノチューブの製造方法。
- 前記常圧乾燥は、80から160℃で行われるものである、請求項2に記載のカーボンナノチューブの製造方法。
- 前記真空乾燥は、175から300℃で行われるものである、請求項1から3のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記真空乾燥は、1から200mbarで行われるものである、請求項1から4のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記真空乾燥は、10分間から3時間行われるものである、請求項1から5のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記多段乾燥は、第1温度で行われる1次真空乾燥と、前記第1温度より高い第2温度で行われる2次真空乾燥を含むものである、請求項1に記載のカーボンナノチューブの製造方法。
- 前記第1温度は、80から160℃である、請求項7に記載のカーボンナノチューブの製造方法。
- 前記第2温度は、175から300℃である、請求項7または8に記載のカーボンナノチューブの製造方法。
- 前記1次熱処理は、100から500℃で行われるものである、請求項1から9のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記2次熱処理は、600から800℃で行われるものである、請求項1から10のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記主触媒前駆体は、Co(NO3)2、Co(NO3)2・6H2O、Co2(CO)8、Co2(CO)6[HC=C(C(CH3)3)]、Co(CH3CO2)2、Fe(NO3)3、Fe(NO3)2・nH2O、Fe(CH3CO2)2、Ni(NO3)2、Ni(NO3)2・6H2O、Mn(NO3)2、Mn(NO3)2・6H2O、Mn(CH3CO2)2・n(H2O)及びMn(CO)5Brからなる群から選択される1種以上のものである、請求項1から11のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記助触媒前駆体は、NH4VO3、NaVO3、V2O5、V(C5H7O2)3、(NH4)6Mo7O24、及び(NH4)6Mo7O24・4H2Oからなる群から選択される1種以上のものである、請求項1から12のいずれか一項に記載のカーボンナノチューブの製造方法。
- 前記カーボンナノチューブは、バンドル型であるものである、請求項1から13のいずれか一項に記載のカーボンナノチューブの製造方法。
- 請求項1から請求項14のいずれか一項によって製造され、
平均直径が5から20nmであるカーボンナノチューブ単位体を含む、カーボンナノチューブ。 - 比表面積が200から350m2/gである、請求項15に記載のカーボンナノチューブ。
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