CN1530321A - Catalyst for preparing carbon nanometer pipe with small pipe diameter - Google Patents
Catalyst for preparing carbon nanometer pipe with small pipe diameter Download PDFInfo
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- CN1530321A CN1530321A CNA031174485A CN03117448A CN1530321A CN 1530321 A CN1530321 A CN 1530321A CN A031174485 A CNA031174485 A CN A031174485A CN 03117448 A CN03117448 A CN 03117448A CN 1530321 A CN1530321 A CN 1530321A
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- carbon nanotube
- catalyzer
- preparation
- footpath
- tubule
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Abstract
A catalyst for preparing the small-diameter single-wall or multi-wall carbon nanotubes from C-contained micro-molecular gas at 700-1100 deg.C contains carrier (magnesium oxide or aluminium oxide), active component (metal Co), the first cocatalyst (molybdenum oxide), and the second cocatalyst (the oxide of alkali-earth element, rare-earth element, or other elements). Its advantages are high output rate and high purity of nanotube (more than 90%).
Description
Technical field
The invention discloses the catalyzer of a kind of preparation tubule footpath carbon nanotube (the carbon nanotube external diameter is less than 8 nanometers), belong to the synthetic field of inorganic materials, be particularly suitable for adopting catalystic pyrolysis to prepare the high purity Single Walled Carbon Nanotube.
Background technology
Carbon nanotube is a kind of novel high-tech content nano-carbon material that has emerged in large numbers since the nineties in 20th century.Wherein best embody the performance of carbon nanotube excellence especially with Single Walled Carbon Nanotube.The general in the world method for preparing Single Walled Carbon Nanotube mainly contains three kinds at present: laser ablation method, arc process and catalystic pyrolysis.Having catalystic pyrolysis only has the industrial applications prospect most, and its development research is of greatest concern.The existing catalyst body for preparing Single Walled Carbon Nanotube by catalystic pyrolysis is Co-Mo-Mg-O or Co-Mo-Al-O system, and carrier is magnesium oxide (MgO) or aluminum oxide (Al
2O
3), active element is cobalt (Co), molybdenum oxide is a promotor.This catalyzer activates back Co and exists with metallic forms under reaction atmosphere or under the nitrogen atmosphere, other element exists with oxide form.Adopt this Preparation of Catalyst Single Walled Carbon Nanotube, product purity is about 70% (weight percent), and every gram carbon deposition quantity of catalyst is below 0.5 gram.Change the made of carbon nanotubes condition and can not improve Single Walled Carbon Nanotube output and purity.
Tubule footpath multi-walled carbon nano-tubes (referring to that external diameter is less than 8 carbon nano tubes) degree of graphitization height, defective are few, strengthening, conduct electricity at material or leading has the important application prospect aspect the static, yet there are no the bibliographical information that catalystic pyrolysis prepares tubule footpath multi-walled carbon nano-tubes.
Tubule of the present invention footpath carbon nanotube comprises that Single Walled Carbon Nanotube and external diameter are less than two types of the multi-walled carbon nano-tubes of 8 nanometers.Described multi-walled carbon nano-tubes refers to the carbon nanotube of the number of plies more than two-layer and two-layer.
Summary of the invention
Purpose of the present invention provides a kind of high yield to prepare the catalyzer of tubule footpath carbon nanotube, and a kind of catalyzer for preparing the high purity Single Walled Carbon Nanotube particularly is provided, and increases substantially the quality of target product carbon nanotube, reduces cost.
The object of the present invention is achieved like this: a kind of catalyzer for preparing tubule footpath carbon nanotube, carrier is magnesium oxide (MgO) or aluminum oxide (Al
2O
3), active element is cobalt (Co), and promotor is molybdenum (Mo), it is characterized in that containing in the catalyzer among alkaline earth element, rare earth element or other element etc. one or more as second promotor, and this catalyzer has following chemical constitution formula: Co
aMo
bA
mFe
nB
xO
y, 0＜a≤0.2,0＜b≤0.2,0＜m≤0.2,0≤n≤a, 0.5≤x≤2,0.5≤y≤3, A is second promoter elements, B is Mg or Al.
The catalyzer of preparation tubule footpath carbon nanotube when the preparation Single Walled Carbon Nanotube temperature in 700 ℃ of-1050 ℃ of scopes.
By introduce another kind of element or several element (second promotor) in Co-Mo-Mg-O catalyst system or Co-Mo-Al-O catalyst system, the acid-basicity of allotment catalyst themselves is to reduce the possibility of growth agraphitic carbon on the catalyzer.Simultaneously because the adding of new element (second co-catalyst component), can effectively change the globule size of reactive metal element (as Co) behind the catalyst activation, make reactive metal unit crude granule become littler, active site is more.Reactive metal unit's crude granule and numerous active site just because of suitable size have determined catalyzer of the present invention that Single Walled Carbon Nanotube is had good selectivity and high Single Walled Carbon Nanotube productive rate.Because the macrobead reactive metal more helps the generation of multi-walled carbon nano-tubes or agraphitic carbon.
The present invention is by adding among alkaline earth element, rare earth element or other element etc. one or more as second promotor in existing C o-Mo-Mg-O or Co-Mo-Al-O catalyzer, the granular size and the distribution of active particle with the acid-basicity of allotment catalyzer and after changing catalyst activation.
Embodiment
Catalyzer of the present invention is a raw material with the soluble salt of respective element, prepares by the collosol and gel synthesis method.
By studies show that, alkaline earth element is the most effective catalyst acid alkalescence blender, and other element can reach same effect by two or more different elements composite.Ca, Sr in Co-Mo-Mg-O or Co-Mo-Al-O catalyzer in the interpolation alkaline earth element, Ba etc. can both increase substantially the productive rate of Single Walled Carbon Nanotube, and product purity also can increase substantially simultaneously.In Co-Mo-Mg-O or Co-Mo-Al-O catalyzer, add rare earth element and also can obtain reasonable effect.
After in Co-Mo-Mg-O or Co-Mo-Al-O catalyzer, having added alkaline earth element, can introduce other element again the acid-basicity of catalyzer is further allocated, to obtain best Single Walled Carbon Nanotube productive rate and selectivity.The element that is suitable as allotment again can be a metallic element, also can be non-metallic element.Wherein adopt elemental iron or nickel that the catalyzer that is obtained is allocated again and can obviously increase Single Walled Carbon Nanotube productive rate and selectivity.
Catalyzer of the present invention has following chemical constitution formula: Co
aMo
bA
mFe
nB
xO
y, 0＜a≤0.2,0＜b≤0.2,0＜m≤0.2,0≤n≤a, 0.5≤x≤2,0.5≤y≤3, A is second promoter elements, B is Mg or Al.
The mol ratio content a of reactive metal element cobalt is less than 0.08 in the preparation single-walled carbon nanotube catalyst.If the content of reactive metal will more help the generation of tubule footpath multi-walled carbon nano-tubes in the increase catalyzer.Prepare in the catalyzer of little many walls of caliber carbon mitron reactive metal mol ratio content a to be advisable at 0.05-0.2.
Adopt the productive rate of Preparation of Catalyst Single Walled Carbon Nanotube of the present invention can reach the above Single Walled Carbon Nanotube of every gram catalyzer product 1.0 grams, the thick product of Single Walled Carbon Nanotube can obtain the Single Walled Carbon Nanotube that purity surpasses 90% (weight percent) through simple acid treatment.Adopt Preparation of Catalyst tubule of the present invention footpath multi-walled carbon nano-tubes productive rate can reach every gram catalyzer and produce the above carbon nanotube of 5 grams, carbon nano pipe purity reaches more than 95% (weight percent).These results are that existing catalyzer is matchless.
Preparation of Catalyst carbon nanotube of the present invention is a unstripped gas with the gas mixture of gas mixture, acetylene and the hydrogen of pure methane, methane and hydrogen or carbon monoxide etc.
Embodiment
Below in conjunction with embodiment effect of the present invention is described.
Embodiment 1
Catalyzer consists of Co
0.1Sr
0.04Mo
0.05Mg
0.94O.Take by weighing the 0.100g catalyzer, place molybdenum boat, molybdenum boat places the middle part of tubular reactor (diameter 35mm).Earlier logical nitrogen excluding air begins after half an hour to heat up under nitrogen protection, switches to the gas mixture of hydrogen and methane after 750 ℃, H
2Flow 100ml/min, CH
4Flow 40ml/min.Temperature rise rate is 5 ℃ of per minutes.React after 50 minutes, switching hydrogen and methane blended gas is nitrogen, cool to room temperature.Weighing gets black product 0.218 gram, productive rate 118%.The purity of Single Walled Carbon Nanotube reaches 98% (weight percent) behind the employing nitric acid purifying, and output is 0.106g.Through the Raman spectroscopic analysis, the Single Walled Carbon Nanotube caliber that is obtained mainly concentrates on 1.1-1.5nm.The transmission electron microscope photo of the Single Walled Carbon Nanotube that is obtained is seen Figure of description 1, and the Raman spectrogram is seen Figure of description 2.
Embodiment 2
Catalyzer consists of Co
0.04Cu
0.02Mo
0.01Fe
0.01Mg
0.94O.Take by weighing the 0.100g catalyzer, place molybdenum boat, molybdenum boat places the middle part of tubular reactor (diameter 35mm).Earlier logical nitrogen excluding air begins after half an hour to heat up under nitrogen protection, switches to pure methane after 900 ℃, CH
4Flow 60ml/min.React 60 minutes postcooling to room temperature.Weighing gets black product 0.233 gram, productive rate 133%.The purity of Single Walled Carbon Nanotube reaches 95% (weight percent) behind the employing nitric acid purifying, and output is 0.113g.Through the Raman spectroscopic analysis, the Single Walled Carbon Nanotube caliber that is obtained mainly concentrates on 0.9-1.3nm.
Embodiment 3
Catalyzer consists of Co
0.1Ca
0.05Mo
0.01Mg
0.94O.Take by weighing the 0.100g catalyzer, place molybdenum boat, molybdenum boat places the middle part of tubular reactor (diameter 35mm).Earlier logical nitrogen excluding air begins after half an hour to heat up under nitrogen protection, switches to the gas mixture of hydrogen and methane after 800 ℃, H
2Flow 40ml/min, CH
4Flow 80ml/min.Temperature rise rate is 4 ℃ of per minutes.React after 50 minutes, switching hydrogen and methane blended gas is nitrogen, cool to room temperature.Weighing gets black product 0.603 gram, productive rate 503%.Adopt behind the nitric acid purifying institute's tubule that obtains directly the purity of multi-walled carbon nano-tubes reach 96% (weight percent), output is 0.483g.Through transmission electron microscope observing, the external diameter of carbon nanotube mainly concentrates on 3-8nm.
Claims (9)
1, a kind of catalyzer for preparing tubule footpath carbon nanotube, carrier is magnesium oxide (MgO) or aluminum oxide (Al
2O
3), active element is cobalt (Co), and promotor is molybdenum (Mo), it is characterized in that containing in the catalyzer among alkaline earth element, rare earth element or other element etc. one or more as second promotor, and this catalyzer has following chemical constitution formula: Co
aMo
bA
mFe
nB
xO
y, 0＜a≤0.2,0＜b≤0.2,0＜m≤0.2,0≤n≤a, 0.5≤x≤2,0.5≤y≤3, A is second promoter elements, B is Mg or Al.
2, the catalyzer of preparation tubule according to claim 1 footpath carbon nanotube, it is characterized in that: A is a kind of element or more than one elements compounding body among Cu, Zn, Al, Mg, Ba, Sr, Ca, Ce, Pr, La, Si, the S.
3, the catalyzer of preparation tubule according to claim 2 footpath carbon nanotube is characterized in that: A is a kind of in Cu, Ba or three kinds of elements of Sr, and B is element M g.
4, the catalyzer of preparation tubule according to claim 2 footpath carbon nanotube is characterized in that: at the chemical constitution formula Co of catalyzer
aMo
bA
mFe
nB
xO
yIn, a, b, m, n be at following scope: 0＜a≤0.1,0＜b≤0.1,0＜m≤0.1,0≤n≤a, 0.5≤x≤1.
5, the catalyzer of preparation tubule according to claim 1 footpath carbon nanotube when being used to prepare tubule footpath multi-walled carbon nano-tubes, is characterized in that: at the chemical constitution formula Co of catalyzer
aMo
bA
mFe
nB
xO
yIn, a, b, m, n be at following scope: 0.05＜a≤0.2,0＜b≤0.2,0＜m≤0.1,0≤n≤a, 0.5≤x≤1.
6, a kind of catalyzer for preparing tubule footpath carbon nanotube when the preparation Single Walled Carbon Nanotube temperature in 700 ℃ of-1050 ℃ of scopes.
7, the catalyzer of preparation tubule according to claim 6 footpath carbon nanotube is characterized in that: described Preparation of Catalyst Single Walled Carbon Nanotube is a unstripped gas with the gas mixture of gas mixture, acetylene and the hydrogen of pure methane, methane and hydrogen or carbon monoxide etc.
8, the catalyzer of preparation tubule according to claim 6 footpath carbon nanotube is characterized in that: described catalyzer can be removed its dissolving with diluted acid after the preparation Single Walled Carbon Nanotube.
9, the catalyzer of preparation tubule according to claim 6 footpath carbon nanotube is characterized in that: described tubule footpath carbon nanotube is the carbon nanotube of external diameter less than 8nm, comprises Single Walled Carbon Nanotube and the external diameter multi-walled carbon nano-tubes less than 8nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031174485A CN1530321A (en) | 2003-03-14 | 2003-03-14 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031174485A CN1530321A (en) | 2003-03-14 | 2003-03-14 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
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|---|---|
| CN1530321A true CN1530321A (en) | 2004-09-22 |
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ID=34284726
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|---|---|---|---|
| CNA031174485A Pending CN1530321A (en) | 2003-03-14 | 2003-03-14 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302846C (en) * | 2004-12-24 | 2007-03-07 | 宁波华实纳米材料有限公司 | Lanthanum doped monometallic catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof |
| CN1308071C (en) * | 2004-12-24 | 2007-04-04 | 宁波华实纳米材料有限公司 | Lanthanum doped catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof |
| CN1326613C (en) * | 2004-11-11 | 2007-07-18 | 宁波华实纳米材料有限公司 | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process |
| CN100434359C (en) * | 2005-01-05 | 2008-11-19 | 中国科学院大连化学物理研究所 | Method and device for continuously producing nanometer carbon material |
| CN102762296A (en) * | 2009-10-29 | 2012-10-31 | 英弗勒科技有限公司 | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof |
| CN103058164A (en) * | 2011-10-20 | 2013-04-24 | 苏州捷迪纳米科技有限公司 | Preparation method of single-walled carbon nanotube |
| US8496904B2 (en) | 2005-02-07 | 2013-07-30 | Hyperion Catalysis International, Inc. | Single-walled carbon nanotube catalysts and method for preparing same |
| CN105002475A (en) * | 2009-02-10 | 2015-10-28 | 日本瑞翁株式会社 | Base for producing oriented carbon nanotube aggregate, and method for producing oriented carbon nanotube aggregate |
| CN105451883A (en) * | 2013-07-19 | 2016-03-30 | 科思创德国股份公司 | Method for producing an efficient catalyst for generating multi-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube powder |
| CN111841561A (en) * | 2020-07-09 | 2020-10-30 | 江西铜业技术研究院有限公司 | High-efficiency catalyst for growing carbon nano tube and preparation and use methods thereof |
-
2003
- 2003-03-14 CN CNA031174485A patent/CN1530321A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326613C (en) * | 2004-11-11 | 2007-07-18 | 宁波华实纳米材料有限公司 | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process |
| CN1302846C (en) * | 2004-12-24 | 2007-03-07 | 宁波华实纳米材料有限公司 | Lanthanum doped monometallic catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof |
| CN1308071C (en) * | 2004-12-24 | 2007-04-04 | 宁波华实纳米材料有限公司 | Lanthanum doped catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof |
| CN100434359C (en) * | 2005-01-05 | 2008-11-19 | 中国科学院大连化学物理研究所 | Method and device for continuously producing nanometer carbon material |
| US8496904B2 (en) | 2005-02-07 | 2013-07-30 | Hyperion Catalysis International, Inc. | Single-walled carbon nanotube catalysts and method for preparing same |
| CN105002475A (en) * | 2009-02-10 | 2015-10-28 | 日本瑞翁株式会社 | Base for producing oriented carbon nanotube aggregate, and method for producing oriented carbon nanotube aggregate |
| CN102762296A (en) * | 2009-10-29 | 2012-10-31 | 英弗勒科技有限公司 | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof |
| CN102762296B (en) * | 2009-10-29 | 2015-03-25 | 英弗勒Xtl科技有限公司 | Catalyst for synthesis of hydrocarbons from CO and H2 and preparation method thereof |
| CN103058164A (en) * | 2011-10-20 | 2013-04-24 | 苏州捷迪纳米科技有限公司 | Preparation method of single-walled carbon nanotube |
| CN105451883A (en) * | 2013-07-19 | 2016-03-30 | 科思创德国股份公司 | Method for producing an efficient catalyst for generating multi-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube powder |
| CN111841561A (en) * | 2020-07-09 | 2020-10-30 | 江西铜业技术研究院有限公司 | High-efficiency catalyst for growing carbon nano tube and preparation and use methods thereof |
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