JP2010188337A - 薄型多層カーボンナノチューブ製造用触媒組成物とその調製方法 - Google Patents
薄型多層カーボンナノチューブ製造用触媒組成物とその調製方法 Download PDFInfo
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- JP2010188337A JP2010188337A JP2009272504A JP2009272504A JP2010188337A JP 2010188337 A JP2010188337 A JP 2010188337A JP 2009272504 A JP2009272504 A JP 2009272504A JP 2009272504 A JP2009272504 A JP 2009272504A JP 2010188337 A JP2010188337 A JP 2010188337A
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- catalyst composition
- catalyst
- carbon nanotubes
- carbon nanotube
- metal
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002048 multi walled nanotube Substances 0.000 title abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 96
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 85
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 239000011777 magnesium Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 17
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
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- 150000003624 transition metals Chemical class 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
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- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
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- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 2
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- 229910052802 copper Inorganic materials 0.000 abstract description 5
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 241000282326 Felis catus Species 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 150000002602 lanthanoids Chemical class 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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Classifications
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Abstract
【解決手段】より詳しくは、i)FeおよびAlからなる主触媒、ii)Mgからなる不活性担体、および、iii))Co、Ni、Cr、Mn、Mo、W、V、SnまたはCuから選ばれる少なくとも1種の任意の共触媒を含む多成分金属触媒に関する。さらに、本発明は、直径が5〜20nmであり、アスペクト比が100〜10,000である薄型多層カーボンナノチューブを高収率で得ることができる。
【選択図】なし
Description
このようなカーボンナノチューブは、一般的に、アーク放電法、レーザ蒸着法、プラズマCVD法、熱CVD法、気相成長法、または、電解法によって製造することができる。これらの中で、熱CVD法は、基板を用いることなく、炭化水素ガスと金属触媒とが直接反応することでカーボンナノチューブを成長させることができるので、好ましく用いられてきた。さらに、熱CVD法によれば大量の高純度カーボンナノチューブを経済的に製造することができる。
Hyperion Catalysis International Inc.によるアメリカ特許5165909(特許文献1)によれば、i)Al2O3にFe触媒を担持した後、空気中約500℃で触媒組成物を焼成し、ii)水素ガスを用いて、約900℃で触媒組成物を還元し、そして、iii)水素雰囲気下、約1000℃で、炭素源としてのベンゼンを反応させることで、炭素繊維を製造する方法が開示されている。しかしながら、この炭素繊維製造の触媒収率はそんなに良くなく、さらに、金属触媒を調製する過程では、か焼および還元の複雑な工程ならびに800℃以上の反応温度が必要となる。
Mgは、マグネシウム、その酸化物またはその誘導体からなる不活性担体を示し;
Mは、Co、Ni、Cr、Mn、Mo、W、V、SnまたはCuから選ばれる少なくとも1種の遷移金属、その酸化物またはその誘導体を示す。
前記共沈剤溶液としては、金属成分を含まない塩基性水溶液を使用することができる。さらに、共沈剤としては、炭酸水素アンモニウム(NH4HCO3)が好ましい。
さらに、本発明は、高分子複合材料中の導電性および強度向上フィラー、金属複合材料中の熱伝導性および強度向上フィラー、燃料電池の触媒担体、有機単位反応触媒の担体材料、メタンガスおよび水素ガスの貯蔵物質、リチウム二次電池の電極材料、リチウム二次電池の導電体、高容量電気二重層コンデンサ用電極材料、ディスプレイ用電界放出材料または膜材料として、カーボンナノチューブを使用する方法を提供する。
Mgは、マグネシウム、その酸化物またはその誘導体からなる不活性担体を示し;
Mは、Co、Ni、Cr、Mn、Mo、W、V、SnまたはCuから選ばれる少なくとも1種の遷移金属、その酸化物またはその誘導体を示す。
前記共沈剤溶液としては、金属成分を含まない塩基性水溶液を使用することができる。さらに、共沈剤としては、炭酸水素アンモニウム(NH4HCO3)が好ましい。
カーボンナノチューブの製造終了後、カーボンナノチューブ中の触媒成分を、物理的または化学的方法で取り除くことができる。このために、得られたカーボンナノチューブを、酸や塩基で処理したり、高温で熱処理することができる。
[実施例]
<実施例1>FeおよびAlのモル分率の変化に伴う触媒組成物の調製
遷移金属Mを含まない、Fe、AlおよびMgからなる触媒組成物を調製した。(Fe+Al)/Mgのモル分率を7/3に固定する。それゆえ、この触媒組成物には、遷移金属は存在しない。FeおよびAlのモル量の変化に伴う触媒組成物を調製した後、これらの触媒組成物を用いてカーボンナノチューブを製造した。それぞれの触媒組成物に対して触媒収率を測定した。
ここで、Mtotalは、カーボンナノチューブと触媒の重量の和を意味し、Mcatは、触媒の重量を意味する。
遷移金属Mを含まない、Fe、AlおよびMgからなる触媒組成物を調製した。(Fe+Al)/Mgのモル分率を7/3に固定する。それゆえ、この触媒組成物には、遷移金属は存在しない。FeおよびAlのモル量の変化に伴う触媒組成物を調製した後、これらの触媒組成物を用いてカーボンナノチューブを製造した。それぞれの触媒組成物に対して触媒収率を測定した。
Fe、Al、M(遷移金属)およびMgを含む触媒組成物をカーボンナノチューブ製造のために調製した。[Fe+Al]、MおよびMgのモル分率は6:1:3であり、FeとAlのモル分率は3.2:6.8である。さらに、触媒組成物として様々な種類の遷移金属(M)を用いた。カーボンナノチューブを製造した後で、それぞれの触媒組成物の触媒収率を測定した。
ここで、Mtotalは、カーボンナノチューブと触媒の重量の和を意味し、Mcatは、触媒の重量を意味する。
不活性担体として、Al(OH)3、アルミナまたはマグネシアを用いた。それゆえ、主触媒としてFeまたはFe+Alを有し、不活性担体としてアルミナまたはMgO粉末を有する触媒組成物を調製した。そして、これらの触媒組成物を用いて、カーボンナノチューブを製造した。
ここで、Mtotalは、カーボンナノチューブと触媒の重量の和を意味し、Mcatは、触媒の重量を意味する。
Claims (10)
- 下記式(1)で表されるカーボンナノチューブの製造用触媒組成物。
Mgは、マグネシウム、その酸化物またはその誘導体からなる不活性担体を示し;
Mは、Co、Ni、Cr、Mn、Mo、W、V、SnまたはCuから選ばれる少なくとも1種の遷移金属、その酸化物またはその誘導体を示す。
x、yおよびzは、それぞれ、[FeとAlの和]、MおよびMgのモル分率を示し、以下の式(2)を満たす。
- 前記[FeとAlの和]、MおよびMgのモル分率が、下記式(4)を満たし、FeおよびAlのモル分率が、下記式(5)を満たすことを特徴とする請求項1に記載のカーボンナノチューブ製造用触媒組成物。
- 下記工程(i)〜(v)を含んでなるカーボンナノチューブ製造用触媒組成物の調製プロセス。
(i)触媒組成物([Fea:Alb]x:My:Mgz)を得るための多成分金属塩をイオン交換水に溶解する工程
(ii)共沈剤溶液を添加することによって、多成分触媒組成物を共沈または配位沈殿する工程
(iii)得られた共沈した触媒組成物を濾過し、その後乾燥し、ついで粉砕する工程
(iv)400〜1200℃で熱酸化することで、粉砕した触媒組成物をか焼する工程
(v)熱酸化後のか焼した触媒組成物をさらに乾燥粉砕する工程 - 前記金属塩が、硝酸塩、硫酸塩、アルコキシド、炭酸塩または塩化物であることを特徴とする請求項3に記載のカーボンナノチューブ製造用触媒組成物の調製プロセス。
- 前記共沈剤溶液が、金属成分を含まない塩基性水溶液であることを特徴とする請求項3に記載のカーボンナノチューブ製造用触媒組成物の調製プロセス。
- 前記金属成分を含まない塩基性水溶液が、炭酸水素アンモニウム(NH4HCO3)であることを特徴とする請求項5に記載のカーボンナノチューブ製造用触媒組成物の調製プロセス。
- 下記工程(I)〜(III)を含んでなるカーボンナノチューブ製造プロセス。
(I)請求項1に記載のカーボンナノチューブ製造用触媒組成物を調製する工程
(II)500〜900℃で、水素と炭素数1〜4の飽和または不飽和炭化水素から選ばれる少なくとも1種の炭素源との混合ガスを反応容器に供給する工程
(III)熱CVD法によって、触媒組成物表面上に、供給した炭素源を蒸着させることで、カーボンナノチューブを成長させ、製造する工程 - 前記反応容器が、竪型固定床反応器、横型固定床反応器、ロータリーキルン反応器、移動床反応器または流動床反応器であることを特徴とする請求項7に記載のカーボンナノチューブ製造プロセス。
- 請求項7に記載のプロセスで製造した、直径が5〜20nmであり、アスペクト比が100〜10,000であるカーボンナノチューブ。
- 高分子複合材料中の導電性および強度向上フィラー、金属複合材料中の熱伝導性および強度向上フィラー、燃料電池の触媒担体、有機単位反応触媒の担体材料、メタンガスおよび水素ガスの貯蔵物質、リチウム二次電池の電極材料、リチウム二次電池の導電体、高容量電気二重層コンデンサ用電極材料、ディスプレイ用電界放出材料または膜材料として、請求項9に記載のカーボンナノチューブを使用する方法。
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KR100976174B1 (ko) | 2010-08-16 |
US20100207053A1 (en) | 2010-08-19 |
EP2223743A1 (en) | 2010-09-01 |
US8048821B2 (en) | 2011-11-01 |
CN101804355A (zh) | 2010-08-18 |
JP5250535B2 (ja) | 2013-07-31 |
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